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WO2006129800A1 - Surface treating agent for pattern formation - Google Patents

Surface treating agent for pattern formation Download PDF

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Publication number
WO2006129800A1
WO2006129800A1 PCT/JP2006/311111 JP2006311111W WO2006129800A1 WO 2006129800 A1 WO2006129800 A1 WO 2006129800A1 JP 2006311111 W JP2006311111 W JP 2006311111W WO 2006129800 A1 WO2006129800 A1 WO 2006129800A1
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WO
WIPO (PCT)
Prior art keywords
group
monomer
surface treatment
fluorine
treatment agent
Prior art date
Application number
PCT/JP2006/311111
Other languages
French (fr)
Japanese (ja)
Inventor
Masamichi Morita
Takuji Ishikawa
Tsuneo Yamashita
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to JP2007519089A priority Critical patent/JP4924424B2/en
Publication of WO2006129800A1 publication Critical patent/WO2006129800A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

  • the present invention relates to a surface treatment agent for producing a pattern surface having lyophilic area and liquid repellent area force by a photolithography method.
  • Rf groups fluoroalkyl groups
  • JP-A-203-03300323 copolymers of Rf group-containing monomers and crosslinkable functional group-containing monomers
  • Rf group-containing monomer if a long-chain Rf group having 8 or more carbon atoms is used for the Rf group-containing monomer, there is a concern about the problem of accumulation in the environment and living body.
  • Rf group-containing compounds having long chain Rf groups with 8 to 12 carbon atoms which have been widely used as surface treatment agents to impart high water and oil repellency to substrates, have recently been Problems with accumulation in the living body have been pointed out.
  • telomers are synonymous with long-chain Rf groups. We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. And
  • an Rf group-containing compound having a short-chain Rf group having 1 to 6 carbon atoms is used as a water / oil repellent.
  • An object related to the first gist of the present invention is to provide a pattern forming surface treatment agent that has a sufficiently high water and oil repellency in a liquid repellent region even if it has a short-chain Rf group having 6 or less carbon atoms. Is to provide.
  • the purpose of the second aspect of the present invention is to form a small liquid repellent region on a substrate by a non-contact microdroplet discharge method, and the liquid repellent region must use a long-chain Rf group-containing compound.
  • Another object of the present invention is to provide a method for producing a patterned substrate having high liquid repellency.
  • the present invention provides a surface treatment agent for photolithography which also has a specific fluorine-based monomer and Z or a specific fluorine-based polymer power.
  • the present invention provides a surface treatment agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of the following fluorine-based monomer (A) and fluorine-based polymer (B). .
  • (A-2) a fluorine-containing cinresesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group
  • the fluoroalkyl group having 1 to 6 carbon atoms and the polymerizable group are SO (CH 3) (where n is 1 to 1
  • the fluorine monomer may be a mixture of the above two types (for example, a combination of monomer (A-1) and monomer (A-4))! /.
  • the present invention provides an electromagnetic wave curable composition
  • a pattern consisting of at least two different areas of different surface free energy is formed on the substrate by discharging it onto the substrate using a contact microdroplet discharge method and irradiating and curing the fine coating film with electromagnetic waves.
  • a method of manufacturing a pattern substrate to be formed is also provided.
  • the surface treatment agent of the present invention forms a patterned film exhibiting high water and oil repellency on a substrate.
  • ⁇ -substituted attalylate having a fluoroalkyl group having 1 to 6 carbon atoms (A-1), a polymerizable monomer having a perfluoropolyether group (3-3), a fluoroalkyl group having 1 to 6 carbon atoms And the polymerizable group are linked by SO (CH) (where n is 1 to 10, especially 3 to 6)
  • X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 ⁇ group (where X 1 and X 2 are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom ), Ciano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or straight chain having 1 to 20 carbon atoms Or branched alkyl group
  • Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group.
  • Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or at least selected from the group consisting of repeating units: —CFO—, —CFO and —CF 2 O—force.
  • a polymerizable group for example, a carbon-carbon double bond group
  • a fluoroalkyl group that is, instead of 0—Y—
  • Y 1 is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or cyclic.
  • An alkyl group, a is 0 or 1; ), -CH CH (OR U ) CH— group (where R U is a hydrogen atom)
  • n is O to 10
  • p is 0 or 1.
  • the monomers (A-1), (A-3), and (A-4) are represented by the formula:
  • examples of X are hydrogen and a methyl group in addition to the above atoms and groups.
  • the polymerizable monomer (A-3) and the polymerizable monomer (A-4) are monomers having a polymerizable group.
  • the polymerizable group may be a carbon-carbon group (for example, an ethenyl group) bonded by a double bond.
  • the polymerizable monomers (A-2) to (A-4) are atalates that are substituted at the ⁇ -position (that is, the ⁇ -position is not hydrogen or an alkyl group) [similar to the monomer (A-1)]. May be. Alternatively, it may be an acrylate having a hydrogen atom or a methyl group at the ⁇ -position.
  • the Rf group has 1 to 6, for example, 1 to 5, preferably 4.
  • the number of carbons having both liquid repellency and compatibility is 4. From the viewpoint of bioaccumulation, 4 is preferable to 6 carbon atoms.
  • F column of Rf group is one CF, -CF CF, -CF CF CF, one CF (CF), one CF CF CF C
  • Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or a cyclic fat.
  • Group or araliphatic group CH CH N (Ri) SO— group (where R 1 is an alkyl group having 1 to 4 carbon atoms), C
  • Aliphatic groups are alkylene groups (especially 1 to 4 carbon atoms, for example
  • aromatic group and the cycloaliphatic group may be either substituted or unsubstituted. -CH CH NCR ⁇ SO—group and
  • the atom bonded to Rf is the carbon atom in the methylene group.
  • a sulfur atom in a sulfone group but generally a sulfur atom in a sulfone group.
  • Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms or a small number selected from the group consisting of repeating units: —C F O, C F O and —CF O—
  • the fluorine-containing silsesquioxane monomer (A-2) containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group comprises (i) a fluorine-containing incompletely condensed silsesquioxane and (ii) a polymerizable functional group. It is obtained by reacting with a reactive silane having a group.
  • the fluorine-containing incompletely condensed silsesquioxane (i) is an incompletely condensed silsesquioxane having a fluoroalkyl group.
  • Silsesquioxane is also called POSS (Polyhedral Oligomeric Silsesquioxane).
  • silanol group of incompletely condensed silsesquioxane (i) is highly reactive and generally there are 1 to 3 silanol groups in the molecule.
  • the reactive silane (ii) having a polymerizable functional group has a polymerizable functional group and a reactive group.
  • examples of the polymerizable functional group include a (meth) acryl group, an alpha-substituted acryl group, an epoxy group, and a bur group.
  • examples of the reactive group are a trichlorosilyl group and a trialkoxysilyl group (the alkoxy group has 1 to 5 carbon atoms).
  • the reactive silane (ii) is, for example, represented by the general formula:
  • a 11 is a polymerizable functional group
  • a 21 is a direct bond or an alkyl group having 1 to 20 carbon atoms (for example, 1 to 10), and A 31 is a halogen atom (for example, chlorine atom and bromine atom) or an alkoxy group (the number of carbon atoms in the alkoxy group). Is 1-5.) ]
  • fluorine-containing silsesquioxane monomer (a) examples are as follows.
  • the fluoropolymer (B) is a copolymer
  • the fluoromonomer (B-1) unsaturated organic acids (B-2) and high softening point monomers (B-3) can be mentioned as copolymerization monomers to be copolymerized with the same fluorine-based monomer (A).
  • the fluorine-based polymer (B) is, for example,
  • (B2) a copolymer of a fluorine-based monomer (B-1) and an unsaturated organic acid (B-2), or
  • the unsaturated organic acid (B-2) is a monomer having at least one carbon-carbon double bond and at least one acid group [eg, carboxyl group (COOH group)].
  • unsaturated organic acids are unsaturated carboxylic acids, such as free unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
  • unsaturated organic acids (B-2) are (meth) acrylic acid, bulacetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, and kaycin acid.
  • the unsaturated organic acid (B-2) imparts to the fluoropolymer (B) crosslinkability with a crosslinking agent in the electromagnetic wave irradiation region and solubility with an alkali developer in the nonelectromagnetic wave irradiation region.
  • a saturated alkyl group having an atomic ratio of 0.58 or more having an atomic ratio of 0.58 or more.
  • R 2 isoborn, born, phensil (all of which are C,, carbon atoms
  • a hydroxyl group or an alkyl group may be attached to the crosslinked hydrocarbon ring.
  • Examples of high softening point monomers ( ⁇ -3) are methyl methacrylate, phenol methacrylate, hexamethyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) Atta relay And adamantyl (meth) acrylate.
  • An example of norbornyl (meth) atarylate is
  • Examples of adamantyl (meth) atalylate are: 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3 hydroxy-1 1-adamantyl (meth) acrylate, 1 —Adamantyl at-trifluoromethyl (meth) acrylate.
  • the glass transition point and melting point are the extrapolated glass transition end temperature (T) and melting peak temperature (T) defined in JIS K7121-1987 “Method for measuring plastic transition temperature”, respectively.
  • a high-soft point monomer (B-3) having a glass transition point or a melting point of 100 ° C or higher in the homopolymer state is used as the repeating unit of the fluoropolymer (B)
  • the substrate is heat-treated.
  • the liquid repellency of the fluorine-based monomer (B-1) is improved.
  • Macromonomer (A-5) as fluorinated monomer (B-1) and unsaturated organic acid monomer (B
  • COO (CH2) 3S02C4F9 is exemplified.
  • the degree of polymerization n of the fluorinated monomer in the macromonomer is preferably 5 to 20, particularly preferably 5 to 10.
  • the fluorine-based polymer (B), which is the binary or ternary copolymer, is particularly preferably a composition comprising a crosslinking agent (C), a photocrosslinking catalyst (D), and a diluent ⁇ . I like it.
  • the weight ratio of the fluorine-based monomer ( ⁇ -1) to the unsaturated organic acid ( ⁇ -2) is 60:40 to 98: 2, and the special weight ratio is 80:20 to 95: 5.
  • the amount of the high soft spot monomer ( ⁇ -3) may be 0 to 90% by weight, for example 1 to 80% by weight, in particular 10 to 70% by weight, based on the copolymer. .
  • Fluoropolymer ( ⁇ ) is, for example, Fluorine monomer (B- 1) 20 to 80 weight 0/0,
  • High softening point monomer (B-3) 10-70% by weight
  • the fluorine-based monomer (B-1) is 20 to 80% by weight, the liquid repellency is high and the compatibility with other components constituting the surface treatment agent for photolithography is good.
  • the unsaturated organic acid monomer (B-2) is 5 to 30% by weight, the crosslinking property with the crosslinking agent in the electromagnetic wave irradiation region is good, and the solubility with the alkali developer in the non-electromagnetic wave irradiation region is good.
  • liquid repellency is good.
  • the high softening point monomer (B-3) is 10 to 70% by weight, the effect of dimensional stability is good and the liquid repellency is good.
  • the monomer (B-2) When a monomer having a hydroxyl group such as hydroxypropyl (meth) ate is copolymerized (for example, in the range of 0.1 to 30% by weight, particularly in the range of 0.5 to 25% by weight), the monomer (B-2) This has the effect of enhancing the cross-linking property with the cross-linking agent in the electromagnetic wave irradiation region and the solubility with the alkali developer in the non-electromagnetic wave irradiation region.
  • a monomer having a hydroxyl group such as hydroxypropyl (meth) ate
  • Fluorine-based polymer is a copolymer of (B), optionally ⁇ - methacryloxypropyl trimethoxysilane silane group-containing monomer represented (e.g., 0.1 to 30 weight 0/0) co Polymerization You may do it.
  • ⁇ - methacryloxypropyl trimethoxysilane silane group-containing monomer represented (e.g., 0.1 to 30 weight 0/0) co Polymerization You may do it.
  • the present invention uses a fluorine monomer ( ⁇ ) or a fluorine polymer ( ⁇ ) to form a plurality of regional forces having different surface free energies, for example, by the following method.
  • No pattern substrate in other words, a patterned substrate composed of a plurality of patterned lyophobic and lyophilic regions (hereinafter simply referred to as “pattern substrate”).
  • Fluoropolymer ( ⁇ ) is dissolved in Diluent C.
  • this fluoropolymer solution is applied onto a substrate to form a uniform liquid-repellent film and irradiated with electromagnetic waves (for example, vacuum ultraviolet light having a wavelength of 172 nm) through a photomask, it is generated by electromagnetic energy and electromagnetic waves. Due to the acid action of ozone, only the irradiated area is photolyzed and becomes lyophilic, and a patterned substrate is obtained.
  • a photocatalytic technique may be used in combination to promote photolysis of the liquid repellent film.
  • Method (2) A composition containing a fluorine-based monomer (A), a crosslinking agent (C), and a photocrosslinking catalyst (D) (a diluent ⁇ may be added if necessary) is applied on a substrate.
  • a fluorine-based monomer A
  • C crosslinking agent
  • D photocrosslinking catalyst
  • a pattern substrate can be obtained by removing (developing) the film in the non-irradiated region using a diluent ⁇ that is insoluble in the irradiated region and dissolves only the non-irradiated region.
  • Method (3) A fluoropolymer ( ⁇ ⁇ ⁇ ⁇ ) having a crosslinkable functional group ( ⁇ ) and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Fluoropolymer ( ⁇ ) having a crosslinkable functional group ( ⁇ ), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • the photocrosslinking catalyst (D) is dissolved in the diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated areas.
  • Method (6) Fluorine polymer ( ⁇ ) and crosslinker (C) having acid group (F), crosslinkable functional group ( ⁇ ) and silicone chain (G), photocrosslinking catalyst (D) as diluent ⁇ Dissolve in
  • F acid group
  • ⁇ crosslinkable functional group
  • G silicone chain
  • D photocrosslinking catalyst
  • Method (7) Dissolve the fluorine-containing polymer ( ⁇ ) having an acidic group (F), the crosslinking agent (C), and the photocrosslinking catalyst (D) in the diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • Unlit A pattern substrate is obtained by developing with a solvent that dissolves only the projecting region.
  • Method (8) A fluoropolymer (B) having an acidic group (F) and a silicone chain (G), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • the pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Method (9) A fluorine-based polymer ( ⁇ ) having an acidic group (F) and a crosslinkable functional group ( ⁇ ) and a photocrosslinking catalyst (D) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured.
  • a pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
  • Method (10) A fluorine-containing polymer ( ⁇ ) having an acidic group (F), a crosslinkable functional group ( ⁇ ), and a silicone chain (G) and a photocrosslinking catalyst (D) are dissolved in the diluent ⁇ .
  • F acidic group
  • ⁇ crosslinkable functional group
  • G silicone chain
  • D photocrosslinking catalyst
  • Method (11) A fluorine-containing polymer ( ⁇ ) having an acid dissociable group ( ⁇ ) that is converted into an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid-repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
  • a fluorine-based polymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
  • Method (13) A fluorine-containing polymer ( ⁇ ) having an acid dissociable group ( ⁇ ) that is converted to an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ⁇ .
  • this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into an acid and becomes soluble in an alkaline aqueous solution.
  • a noturn substrate can be obtained.
  • Method (14) Dissolve an acid dissociable group (H) that is converted into an acidic group by the action of an acid, a fluorine-based polymer (B) having a silicone chain (G), and a photoacid generator (I) in a diluent ⁇ .
  • a fluorine-based polymer B
  • G silicone chain
  • I photoacid generator
  • heat treatment at about 50 to 250 ° C may be performed before (pre-beta) or after (post-beta) irradiation of electromagnetic waves.
  • PEB Post Exposure Bake
  • the cross-linking agent is a monofunctional or preferably a compound having two or more functional groups, and may be of a type force that cures by a radical polymerization reaction or a type that cures by a cationic polymerization reaction.
  • an unsaturated double bond group, an taliloyl group, a vinyl group is a functional group
  • an epoxy group, a vinyl ether group, or an oxetane group is a functional group.
  • (A) to (l) are types that cure by a radical polymerization reaction
  • (g) to (i) are types that cure by a cationic polymerization reaction.
  • (a) to (e) are those obtained by adding a (meth) attalyloyl group to rosin, and are often expressed as oligomers, base resins, prepolymers, and the like.
  • Urethane (meth) atalylate has a urethane bond and a (meth) atalyloyl group in the molecule.
  • Tris (2-hydroxyethyl) isocyanurate diatalylate, tris (2 —Hi Examples include poly [(meth) atalylooxyalkyl] isocyanurate, which is typified by droxychetyl) isocyanurate triatalylate.
  • Epoxy (meth) atalylate is obtained by adding an epoxy group with a (meth) atalyloyl group, and bisphenol A, bisphenol F, phenol novolak, and an alicyclic compound were used as starting materials. Things are common.
  • Polyester (meth) acrylate is a product obtained by adding (meth) acrylate to a polybasic acid and an ester resin having a polybasic acidity.
  • Polyhydric alcohols include ethylene glycol, 1,4 butanediol, 1,6 hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, etc.
  • Basic acid is phthalic acid
  • Adipic acid maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alk-succinic acid, and the like.
  • Polyether (meth) acrylate is a diol polyether resin with a (meth) atrelate added to it.
  • Polyethylene glycol di (meth) acrylate and polypropylene diol diol (meth) Examples include attalylate, polyethylene glycol, polypropylene glycol di (meth) acrylate, and the like.
  • Silicone (meth) acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 modified at one end or both ends with a (meth) atallyloyl group. Is done.
  • (D (meth) acrylate monomer is a monofunctional or polyfunctional alkyl (meth) atrelate, a low viscosity polyether (meth) acrylate having a viscosity of 500 mPa s (25 ° C) or less, methyl ( Meta) Atylate, Ethyl (Meth) Atylate, n-Propyl (Meth) Atalylate, Isopropyl (Meth) Atalylate, n-Butyl (Meth) Atylate, Isobutyl (Meth) Atalylate, sec— Butyl (Meth) Atalylate, t-butyl (meth) atarylate, n-pentyl (meth) atrelate, 3-methylbutyl (meth) atarylate, n-hexyl (meth) atalylate, 2-ethylyl n-hexyl (meth) Atalylate, n-oct
  • Epoxy monomers are glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolak, cresolol novolak; alcohols such as butanediol, polyethylene glycol, and polypropylene glycol.
  • Ethers epoxy monomers such as glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid, and oligomers or alicyclic epoxides thereof.
  • bisphenol A glycidyl ether monomer or oligomer can be preferably used.
  • Epico ⁇ 828 (molecular weight 380), Epico ⁇ 834 (molecular weight 470), Epico ⁇ 1001 (molecular weight 900), Epico ⁇ 1002 (molecular weight 1,060), Epico Illustrative are 1055 (molecular weight 1,350) and Epico 100 100 (molecular weight 2,900).
  • the butyl ether monomer includes 2 hydroxyethyl vinyl ether, 4 hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, cis 1,1,3 trimethyl 5 vinyloxycyclohexane, trans 1, 1, 3 Trimethyl mono 5 -Buroxycyclohexane, 1—Isopropyl-4 methyl-2-Buroxy chlorohexane, 2 Buroxy 7—Oxabicyclo [3.2.1] octane-6one, 2 Methyl 2— Buloxiadamantane, 2-Ethyl 2—Buloxiadamantane, 1, 3 Bis (Buroxy) adamantane, 1—Buroxiadamantanol, 3—Buroxydamantanol, 1, 3 , 5 Tris (Buroxy) adamantane, 3, 5 Bis (Buroxy), 1 Adamantanol, 5 Buruoxy 1, 3 Ada Manta Diol, 1, 3,
  • oxetane-based monomers are 1,4 bis ⁇ [(3-ethyl-3-oxeta-l) methoxy] ethyl ⁇ benzene (Aronoxetane OXT-121) manufactured by Toagosei Co., Ltd., 3-ethyl 3-hydroxymethyloxetane ( Examples include Tolonsei Alonoxetane OXT-101).
  • an acid crosslinking agent may be used as the crosslinking agent.
  • the acid crosslinking agent includes a plurality of (for example, 2 to 10) reactive groups (for example, carboxylic acid, hydroxyl group, amino group, isocyanate group, N-methylol group, alkyl ether group N—) that crosslink with an acidic group in one molecule.
  • amino succinic acid examples include compounds obtained by hydroxymethylating a part or all of amino groups such as melamine compounds, guanamine compounds and urea compounds, or hydroxyl groups of the hydroxymethylated compounds.
  • various amino coffins of imino type examples include compounds obtained by hydroxymethylating a part or all of amino groups such as melamine compounds, guanamine compounds and urea compounds, or hydroxyl groups of the hydroxymethylated compounds.
  • Epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol 'novolac type epoxy resin, talesol' novolac type epoxy resin, trisphenol methane type epoxy resin, bromine Glycidyl etherols such as epoxidized epoxy resin, 3, 4 epoxycyclohexenolemethinole 3, 4-epoxycyclohexane strength ruboxylate, bis (2, 3 epoxycyclopentyl) ether, etc.
  • Glycidyl esters such as diglycidinolehexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate, glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylvalaminophenol, triglycidyl isocyanurate, etc.
  • glycidyl esters such as diglycidinolehexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate, glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylvalaminophenol, triglycidyl isocyanurate, etc.
  • glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylval
  • the oxazoline compounds include 2-bi-ro 2-oxazoline, 2-bi-ro 4-methyl lu 2--oxazoline, 2-vinyl 5--methyl-2-oxazoline, 2-isopropenyl lu 2-oxazoline, 2-iso-probe 4 methyl 2-oxazoline And a copolymer of polymerizable monomers such as
  • the curing speed is improved.
  • the amount of the multi-sensitive thiol may be, for example, 0.1 to 20 parts by weight, for example 1 to 10 parts by weight with respect to 100 parts by weight of the crosslinking agent.
  • the cross-linking agent When used in combination with a fluorinated monomer, the cross-linking agent is 1 to LOO, 000 parts by weight, particularly 10 to L00, 000 parts by weight with respect to 100 parts by weight of the fluorinated monomer.
  • the fluorine-based polymer When used in combination with a fluorine-based polymer, it is 1 to L00 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the fluorine-based polymer.
  • the photocrosslinking catalyst examples include a radical photopolymerization initiator and a photoacid generator.
  • Radical photopolymerization initiators are compounds that generate radicals by light, such as OC-diketones such as benzyl and diacetyl, acyloines such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • Thiaxanthones such as thixanthone, 2, 4 jetylthioxanthone, thixanthone 4-sulfonic acid, benzophenone, 4, 4, monobis (dimethylamino) benzophenone, 4, Benzophenones such as 4, 1-bis (jetylamino) benzophenone, acetophenone, 2- (4 toluenesulfo-ruxoxy) 2 pheulacetophenone, p dimethylaminoacetophenone, 2, 2, -dimethoxy 2-phenol-lucacetophenone, p-methoxya Cetofenones such as cetophenone, 2 methyl [4 (methylthio) phenol] 2 morpholino 1 propanone, 2 benzil 2-dimethylamino 1- (4-morpholinophenol) 1-butane 1-one, To quinones such as anthraquinone and 1,4 naphthoquinone, 2 ethyl dimethylaminobenzoate
  • a photoacid generator is a material that generates acid by reacting with light.
  • PAG is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating light of a specific wavelength to PAG with such a structure, PAG is excited and the acid precursor part begins. Generates acid.
  • PAG is, for example, diazonium salt, phospho-um salt, sulfo-um salt, iodonium salt, CF SO p—CH PhSO p—NO PhSO
  • Examples thereof include sulfonyl chloride or sulfonic acid ester.
  • the organic halogen compound is a compound forming a halogen hydrohydroacid, and such compounds are disclosed in US Pat. No. 3,515,551, US Pat. No. 3,536,489, US Pat. , 779, 778 and West German Patent Publication No. 2,243,621, etc. (the disclosures of which are incorporated herein).
  • the amount of the photocrosslinking catalyst is 0.1 to 20 parts by weight, particularly 1 to 100 parts by weight of the fluorine monomer and the crosslinking agent, or the fluorine polymer, or the fluorine polymer and the crosslinking agent in total. ⁇ 10 parts by weight.
  • the fluoropolymer (B) When used in combination with a photocrosslinking catalyst, the fluoropolymer (B) comprises a crosslinkable functional group (E), an acidic group (F), and an acid dissociable functional group (H) that is converted into an acidic group by the action of an acid. It preferably has at least one group selected from the group consisting of The fluoropolymer (B) may further have a silicone chain (G).
  • the crosslinkable functional group imparted to the fluorine-based polymer is an unsaturated double bond group such as an allyloyl group or a buyl group as a type that cures by radical polymerization reaction, and an epoxy type that cures by a cationic polymerization reaction.
  • Group, oxetane group and the like are exemplified. It may also be a reactive group that crosslinks with an acidic group, for example, a carboxylic acid, a hydroxyl group, an amino group, an isocyanate group, an N-methylol group, an alkyl etherified N-methylol group, etc.
  • the method of imparting a crosslinkable functional group is: (1) A method in which a monomer having a crosslinkable functional group is synthesized in advance and copolymerized with a fluorinated monomer.
  • the amount of the crosslinkable functional group in the fluoropolymer is generally from 0.1 to 20 mol%, particularly from 1 to LOm, based on the total number of the repeat units in the polymer. ol%.
  • acidic groups are carboxyl groups, hydroxyl groups (particularly phenolic hydroxyl groups), and sulfonic acid groups.
  • a method for adding an acidic group to a fluorine-based polymer includes:
  • examples of the monomer having an acidic group include the following.
  • examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
  • examples of the monomer having a hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • one or more hydrogen atoms of these benzene rings alkyl groups such as methyl, ethyl and n -butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms and one or more hydrogen atoms of alkyl groups Haloalkyl group substituted with a halogen atom, nitro group, cyano group, and compounds substituted with amide group.
  • Examples of monomers having a sulfonic acid group include butyl sulfonic acid, styrene sulfonic acid, (meth) aryl sulfonic acid, 2-hydroxy-3- (meth) aryloxypropane sulfonic acid, (Meth) acrylic acid—2-sulfoethyl, (meth) acrylic acid—2-sulfopropyl, 2-hydroxy-3— (meth) talyloxypropane sulfonic acid, 2 -— (meth) acrylamide—2-methylpropane
  • Examples include sulfonic acids and their salts. These may be used alone or in combination of two or more.
  • a composition distribution occurs in the copolymer due to the difference in reactivity between the fluorine-based monomer and the monomer having an acidic group, which may adversely affect the patterning.
  • a structure in which the structure of the bull group of the fluorinated monomer is the same as that of the monomer having an acidic group For example, when a-C1 acrylate containing an Rf group is used as a fluorine-based monomer, it is preferable to use a-C1 acrylic acid as a monomer having an acidic group.
  • the amount of acidic groups in the fluoropolymer is generally 0.1 to 20 mol%, particularly 1 to LOmol%, based on the total number of repeating units in the polymer.
  • the silicone chain (G) is dimethylpolysiloxane having a molecular weight of 1,000 to 10,000.
  • the method of adding a silicone chain to the fluoropolymer is as follows:
  • the silicone (meth) phthalate described in the crosslinking agent (C) may be used.
  • the amount of silicone chain in the fluoropolymer is generally 0.1 to 50 mol%, especially 1 to LOmol%, based on the total number of repeating units in the polymer.
  • Acid-dissociable functional groups that can be converted to acidic groups by the action of acid are t-butoxycarbol (t-BOC), isopropoxycarbol, tetrahydrobiral, trimethylsilyl, t-butoxycarboromethyl Group or protected with these acid-dissociable functional groups Examples include phenolic hydroxyl groups.
  • a method for imparting an acid-dissociable functional group to a fluoropolymer is as follows.
  • the amount of acid-dissociable functional groups in the fluoropolymer is generally 0.1 to 50 mol%, particularly 1 to 10 mol%, based on the total number of repeating units in the polymer. .
  • a water-soluble organic solvent an organic solvent (especially an oil-soluble organic solvent), water
  • the diluent is the same as that used for producing the fluoropolymer.
  • the diluent is inert and dissolves in the fluorinated monomer (A) or the fluorinated polymer (B).
  • Examples of diluents include water-soluble organic solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ethenore acetate, dipropylene glycol.
  • the diluent is used in a range of 50 to 2000 parts by weight, for example, 50 to L000 parts by weight, with respect to 100 parts by weight of the total of the fluorine-based monomer (A) or fluorine-based polymer (B).
  • a fluorine-type polymer can be manufactured as follows. A method is adopted in which a monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization catalyst is added and the mixture is stirred in the range of 20 to 120 ° C. for 1 to 20 hours.
  • the solvent an organic solvent, a water-soluble organic solvent, water or the like can be used, and it is the same as the diluent ⁇ .
  • the solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of monomers.
  • a chain transfer agent such as mercaptans and alkyl halides may be added.
  • Mercaptans include ⁇ -butyl mercaptan, ⁇ -dodecyl mercaptan, t-butyl mercaptan, thioglycolic acid ethyl, 2-glycolyl thioglycolate, 2-mercaptoethanol, isooctyl mercapto acid, thioglycolic acid, 3-
  • the halogenated alkyls such as mercaptopropionic acid, methoxybutyl thioglycolate, and silicone mercaptan (KF-2001, manufactured by Shin-Etsu Chemical) include black mouth form, carbon tetrachloride, and carbon tetrabromide. These may be used alone or in combination of two or more.
  • the weight average molecular weight of the fluoropolymer may be, for example, 1,000 to 500,000, particularly 2,000 to 100,000, and the special IJ may be 3,000 to 20,000.
  • the weight average molecular weight of the fluorinated positive mer is determined by GPC (gel permeation chromatography) (standard polystyrene conversion).
  • GPC gel permeation chromatography
  • a monomer having a fluoroalkyl group having 8 to 12 carbon atoms as required for example, perfluorooctylethyl acrylate
  • a polymer having this monomer as a repeating unit may be blended.
  • Non-fluorine polymer may be used in combination with the surface treatment agent for photolithography of the present invention.
  • Non-fluorinated polymers are, for example, alkali-soluble resins, such as Japanese Patent No. 2505033, Japanese Patent Application Laid-Open No. 3-170554, Japanese Patent Application Laid-Open No. 6-118646, Novolak type phenol resin, Japanese Patent Application Laid-Open No. No.
  • black pigments include carbon black, graphite, titanium black, iron oxide, bismuth sulfide, and perylene black.
  • an acid scavenger may be added to the photolithography surface treatment agent of the present invention to control the diffusion of the acid generated from the acid generator in the film.
  • organic amines, basic ammonium salts, basic sulfo salt, etc. are used, so long as they do not sublimate or deteriorate the resist performance.
  • organic amines are preferred because of their excellent image performance.
  • JP-A-63-149640 JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683 JP-A-5-289340, JP-A-5-232706, JP-A-5-257282, JP-A-6-24 2605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110.
  • the acid scavenger is preferably 1,5 diazabicyclo [4. 3. 0] — 5 nonene, 1, 8-diazabicyclo [5. 4. 0] — 7 undecene, 1, 4 diazabici [2. 2.
  • octane 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4, 4, diaminodiphenyl ether, Pyridinium p-toluenesulfonate, 2, 4, 6 trimethylpyridium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine, etc. Can be mentioned. Among these, 1,5 diazabicyclo [4. 3.
  • octane 4 dimethylamino Organic amines such as pyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine, and tributylamine are preferred.
  • additives are used in the surface treatment agent for photolithography of the present invention as necessary.
  • fluorine-based, silicone-based, hydrocarbon-based surfactants for improving film smoothness for improving film smoothness
  • silane coupling agents for improving film adhesion for improving film adhesion
  • titanate coupling agents etc.
  • Heat polymerization inhibitors for improving film adhesion
  • UV absorbers for improving film adhesion
  • antioxidants for suppressing dark reactions
  • antifoaming agents are used in the surface treatment agent for photolithography of the present invention as necessary.
  • the base material used for the substrate of the present invention is silicon, synthetic resin, glass, metal, ceramics, etc. It is.
  • the synthetic resin may be either a thermoplastic resin or a thermosetting resin, for example, polyolefins such as polyethylene, polypropylene, ethylene prepylene copolymer, ethylene butyl acetate copolymer (EVA), Cyclic polyolefin, modified polyolefin, polychlorinated butyl, polychlorinated polyvinylidene, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly (4 methylbenten 1), ionomer, acrylic resin, polyethylene methacrylate, Acrylic styrene copolymer (AS resin), butadiene styrene copolymer, Polio copolymer (EVOH), Polyethylene terephthalate (PET), Polypropylene terephthalate (PBT), Polycyclohexane terephthalate (PCT), etc.
  • polyolefins such as polyethylene, polypropylene, ethylene prepylene cop
  • TEL polyetherketone
  • PEEK Reether ether ketone
  • polyetherimide polyacetal
  • polyphenylene oxide modified polyphenylene oxide
  • polyarylate aromatic polyester (liquid crystal polymer)
  • fluoroelastomers styrenes, polyolefins, polyvinyl chlorides, polyurethanes, fluororubbers, chlorinated polyethylenes, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, Melamine resin, unsaturated polyester, silicone resin, polyurethane, etc., or their main copolymers, blends, polymer alloys, etc. are mentioned, and one or more of these are combined. (For example, as a laminate of two or more layers). If a synthetic resin substrate is used, the substrate can be provided with features such as light weight, transparency, low cost, and bending.
  • Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda ash glass, potassium lime glass, lead (alkali) glass, norium glass, borosilicate glass, and the like.
  • Ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), sulfites ( Examples thereof include carbide (eg, cadmium sulfate), carbide (eg, carbide), and a mixture thereof may be used.
  • pretreatment such as plasma treatment or UV ozone treatment is performed. It is okay.
  • lyophilic functional groups for example, OH groups, COOH groups, NH groups
  • the shape of the pattern surface may be a circle, a rectangle, a triangle, a straight line, a curve, etc., as long as an appropriate one is selected according to the purpose of the element to be finally manufactured.
  • the patterns can be touching or distant.
  • the line width and line spacing may be 0.5 to: LOO m, for example, 120 m.
  • the line widths may be equally spaced or the widths may vary.
  • the shape of the line may be a straight line or a curve.
  • the surface treatment agent (fluorine-containing compound) is uniformly treated on the surface of these substrates in a liquid phase or a gas phase.
  • a known coating method can be adopted as long as the film thickness can be controlled.
  • roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted.
  • the substrate is heated at 150 ° C for 1 second to 10 minutes (eg, 110 ° C for 1 minute) to dry the solvent from the fluorine-containing compound film. Yes.
  • Pattern substrate production method (1 (11) to (14) provides a uniform liquid-repellent surface with a water contact angle of 60 ° or more, particularly 80 ° or more, without irradiation with light.
  • a liquid repellent surface having a water contact angle of 60 ° or more, particularly 80 ° or more is formed in the irradiated region.
  • the electromagnetic wave irradiated to the film in the present invention is light having a wavelength of 10 to 400 nm, such as ultraviolet (UV, 200 to 400 nm), vacuum ultraviolet (VUV, 150 to 200 nm), extreme ultraviolet (EUV, 10 to 120 nm), etc.
  • UV ultraviolet
  • VUV vacuum ultraviolet
  • EUV extreme ultraviolet
  • a commercially available xenon excimer lamp that can emit VUV with a wavelength of 172 nm can be used.
  • UV is used, a mercury xenon lamp, mercury-silver lamp, xenon lamp, or xenon excimer lamp can be used as the light source.
  • a 248 nm Kr F excimer laser, a 193 nm ArF excimer laser, and a 157 nm F2 excimer laser may be used.
  • the exposure dose may be from 1 to 10,000 mj / cm 2 , in particular from 1 to L000 mj / cm 2 .
  • X-rays with a wavelength of 0.1 to 10 nm, electron beams with a wavelength of 0.001 to 0.01 nm, and electromagnetic waves of a laser beam with a wavelength of 10 to 3 OO nm may be used!
  • the film may be irradiated with light through a photomask, or a DMD (digital micromirror device) developed by Texas Instruments, Inc.
  • DMD digital micromirror device
  • a simple semiconductor may be used to irradiate light in a pattern without a mask.
  • DMD lays out 480,000 to 1,130,000 micron-sized ultra-fine mirrors, reflects the lamp light to the mirror, and irradiates the film with light in a pattern.
  • Electron beam exposure is 10 to 10,000 ⁇ for raster drawing In shot drawing, it may be 100 to 100,0001 C / dot, particularly l, 000 to 10,000 fC / dot.
  • the solvent-soluble region may be removed, that is, so-called “development” may be performed using the contrast of solubility in the solvent after irradiation with the electromagnetic wave.
  • the solvent (developer) used for development the one used for the production of a fluoropolymer or an alkaline aqueous solution is used.
  • Alkaline aqueous solutions include inorganic alkaline aqueous solutions such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine.
  • Secondary amines such as jetylamine and di-n-pylamine; tertiary amines such as triethylamine, methyljetylamine and N-methylpyrrolidone; dimethylethanolamine and triethanolamine Any alcohol amines; quaternary ammonium salts such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, etc .; using an organic alkaline aqueous solution consisting of alkalis of cyclic amines such as pyrrole and piperidine . These can be used alone or in combination of two or more! Also, a surfactant may be added.
  • the developing method may be performed in the range of 10 seconds to 10 minutes by an immersion method, a liquid filling method, or the like.
  • the following method for producing a patterned substrate can be used.
  • an electromagnetic wave curable composition comprising a fluoromonomer-containing fluoromonomer (A), a crosslinking agent (B), and a photocrosslinking catalyst (C) is applied onto a substrate by a non-contact microdroplet discharge method.
  • a film having a microstructure is formed by discharging, and the film is cured by irradiation with electromagnetic waves.
  • Examples of the non-contact minute droplet discharge method include an ink jet method and a microdispenser method.
  • a piezo method can be used.
  • the piezo method is also used in inkjet printers because of its excellent droplet controllability and high degree of freedom in ink selection.
  • the piezo method has MLP (Multi Layer Piezo) type and MLChip (Multi Layer Ceramic Hyper Integrated Piezo segments).
  • the thermal method ink jet generates heat and generates bubbles to push out ink liquid.
  • the volume per droplet discharged by the ink jet method is 0.1 pL to ln L.
  • the physical properties at 25 ° C. of the electromagnetic wave curable composition (ink) suitable for the ink jet method are as follows. Viscosity: 1-50 mPa's, surface tension: 19-30 mN / m, boiling point: 100-250 ° C.
  • microdispenser method a tubing method or an air compression method can be used.
  • the volume per droplet discharged by the microdispenser method is generally [In 1 to 1 ⁇ m].
  • electromagnetic waves may be irradiated in an atmosphere of an inert gas such as nitrogen or argon.
  • a liquid-repellent film is formed on the surface of the substrate, and the surface free energy
  • a pattern substrate composed of a plurality of (at least two) different region forces in other words, a pattern substrate composed of at least one lyophobic region that has been turned into one and at least one lyophilic region force (hereinafter simply referred to as “pattern”).
  • pattern a pattern substrate composed of at least one lyophobic region that has been turned into one and at least one lyophilic region force
  • substrate Abbreviated as “substrate”.
  • the thickness of the liquid repellent film may generally be from lnm to 1000 ⁇ m, such as from 10 nm to 200 ⁇ m, in particular from 50 nm to 100 / ⁇ ⁇ .
  • the liquid repellent region exhibits liquid repellency of, for example, a water contact angle of 70 ° or more, particularly 80 ° or more.
  • Examples of the shape of the pattern of the liquid repellent region include straight lines, curves, circles, squares, triangles, and the like that can be selected according to the purpose of the element to be finally manufactured. Mutual patterns may be in contact or separated.
  • the width of the line may be 10 to: LOOO / zm, for example, 100 to 500 / ⁇ ⁇ .
  • the ratio of the line and the space is arbitrary, for example, 1/10 to 10/1.
  • the shape of the line can be straight or curved.
  • the functional compound solution or dispersion is applied to the substrate on which the pattern is formed.
  • the functional compound solution can be applied by spin coating, dip coating, casting, roll coating, printing, transfer, ink jet [P. Calvert, Chem. Mater., 13, 3299 (2001)], the bar code method, the one-way method.
  • a layer of the functional compound is formed on the patterned fluorine-containing compound film.
  • the layer of the functional compound can be formed by applying a solution obtained by dissolving a functional compound in a solvent on the pattern surface and removing the solvent.
  • a functional compound solution When a functional compound solution is applied to multiple areas with different surface free energies, the functional compound solution avoids areas with a water contact angle of 60 ° or more, especially 80 ° or more, and has a water contact angle of 50 ° or less, especially 3 Adheres only to areas below 0 °.
  • a layer of functional compound is formed on the lyophilic region patterned on the substrate.
  • Examples of the functional compound include a semiconductor compound, a conductive compound, a dye or pigment for forming a display pixel, a photochromic compound, a thermochromic compound, a lens material, a life science drug, and the like.
  • Organic compounds are preferred as semiconductor compounds, for example, pentacene derivatives, polythiophene derivatives, phthalocyanine derivatives, polyfluorene derivatives, poly (p-fluoro-lenbi-re). And layered herosky toy compounds.
  • the conductive compound has a conductivity of 10 2 S / cm or more at room temperature.
  • a conductivity 10 2 S / cm or more at room temperature.
  • polyacetylene derivatives, polythiophene derivatives, polypyrrole, poly p-phenylene vinylene, polyarine and the like can be mentioned. Conductivity may be improved by doping these compounds.
  • nanoparticles in which nanoparticles such as gold, silver and copper are dispersed in a liquid can be mentioned.
  • the photochromic compound is preferably an organic compound, for example, an azobenzene derivative, a spiropyran derivative, a fulgide derivative, a diarylethene derivative, or the like.
  • a thermochemical compound is a general term for compounds in which the color of a substance changes reversibly with changes in temperature.For example, salicylidene dilins, polythiophene derivatives, tetrahalogeno complexes, ethylene diamine derivative complexes, dinitrodiammine copper complexes. 1,4-diazasic octane (daco) complex, hexamethylenetetramine (hmta) complex, saltyl aldehyde (sa len) complex and the like.
  • the thickness of the functional compound layer may be 0.1 nm to 100 ⁇ m, for example, 1 nm to 1 ⁇ m.
  • Examples of the solvent that dissolves the functional compound are an organic solvent (particularly an oil-soluble organic solvent), a water-soluble organic solvent, and water.
  • an organic solvent especially an oil-soluble organic solvent
  • a water-soluble organic solvent especially an oil-soluble organic solvent
  • water especially an oil-soluble organic solvent
  • the solvent that dissolves the functional compound is preferably an organic solvent having a surface tension of 40 mNZm or less, for example, 30 mN / m or less.
  • the surface tension is 40 mNZm or less, the solution can easily spread along the pattern shape.
  • Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (for example, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvents are not allowed to be fluorinated. But either is fine.
  • Specific examples of the organic solvent include perfluorodecalin, hydrated fluoroether, HCFC225, chloroformated form, 1,1,2,2-tetrachloroethane, tetrachloroethylene, cyclobenzene, butyl acetate, hexane, Examples include isopentane, toluene, xylene, and tetrahydrofuran.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl caffeosolve, cellosolve Examples thereof include acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl acetate, isopropyl alcohol, methanol, and ethanol.
  • the surface tension may be reduced by adding a surfactant or the above water-soluble organic solvent.
  • the concentration of the functional compound in the solution of the functional compound may be 0.1 to 20% by weight, for example, 1 to 10% by weight.
  • the solvent can be removed by evaporation or the like.
  • the solvent can be removed by heating the substrate (for example, 60 to 200 ° C.).
  • the solvent removal may be performed under reduced pressure (for example, 0.01-: LOOPa).
  • the substrate of the present invention can be used in a wide range of devices such as electronic, optical, medical and chemical analyses.
  • electronic devices can be used in integrated circuits such as transistors, memories, light emitting diodes (EL), lasers, and solar cells. With these device capabilities, flexible displays, wireless tags, and wearable computers are manufactured.
  • Optical devices include display pixels, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, and medical devices include DNA arrays. It can be used for biochips such as protein arrays.
  • As a chemical analysis device it can be used for micro chemical chips such as micro chemical plants and micro chemical analysis systems.
  • the surface treatment agent for photolithography of the present invention is extremely useful for the liquid repellency of a black matrix, which is necessary when producing a color filter for display by the inkjet method.
  • the inkjet method is expected as a technology for manufacturing color filters at a low cost, but the inkjet technology alone has a landing accuracy that accurately prints red, green, and blue ink in the black matrix (pixel area). Is lacking. For this reason, it is necessary to repel the upper part of the black matrix and draw back ink droplets that have been accidentally removed into the pixels. Also
  • red, green, and blue inks are injected in amounts exceeding the height of the black matrix in order to increase the pixel film thickness, the liquid repellent layer on the top of the black matrix is essential.
  • the former liquid repellency is indicated by the drop angle of the ink solution, and the latter liquid repellency is indicated by the static contact angle.
  • Fluorine gas such as CHF was adsorbed on the black matrix (JP 2000 353594).
  • the fluoropolymers disclosed in these documents have not been able to achieve both liquid repellency and compatibility with other materials forming the photosensitive composition.
  • the surface treatment agent for photolithography of the present invention has both extremely high liquid repellency and compatibility.
  • the black matrix is made liquid repellent by using the surface treatment agent for photolithography of the present invention. Two methods for doing this will be described.
  • the first method uses a black pigment dispersed in a lyophilic transparent substrate by a photolithography method using a surface treatment agent for photolithography of the present invention in which a black pigment is dispersed. It is a method of forming.
  • a surface treatment agent for photolithography at this time for example,
  • Fluoropolymer (B) having crosslinkable functional group (E) and acidic group (F) having crosslinkable functional group (E) and acidic group (F)
  • Photocrosslinking catalyst (D) 1—5% by weight 20% carbon black dispersion 10-20% by weight
  • the second method is to apply a photolithographic surface treatment agent of the present invention uniformly on a photosensitive resin black layer uniformly formed on a lyophilic transparent substrate.
  • One method is to form a lyophobic black matrix on a lyophilic transparent substrate.
  • surface treatment agents for photolithography at this time include, for example, a fluorine-based polymer (B) having an acidic group (F) 5 to 10% by weight
  • Photocrosslinking catalyst (D) 1—5% by weight
  • a red, black, or yellow pigment dispersion for color filter is applied by an ink jet method, and the solvent is removed to remove the color filter. Can be manufactured at an extremely low cost.
  • the static contact angle was obtained by dropping 2 L of microsyringe-powered water or n-hexadecane on a horizontally placed substrate and taking a still image 1 second after dropping with a video microscope. .
  • the sliding angle was determined by the following method. Drop 20 ⁇ L for water and 5 ⁇ L for n-hexadecane and propylene glycol monomethyl etherate (PGMEA) from a microsyringe onto a horizontally placed substrate, and add the substrate at a rate of 2 ° per second. It was tilted and recorded as a moving picture with a video microscope until the droplet started to fall. The video was replayed and the angle at which the droplet began to fall was defined as the falling angle.
  • PMEA propylene glycol monomethyl etherate
  • Fluorine monomer CH C (F) COOCH CH C F (abbreviation ⁇ -F) 100g, HCFC225 40 in a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirrer
  • the weight average molecular weights were 16,000, 9,000, and 15,000, respectively.
  • the substrate silicon wafer was cleaned with acetone, and then the surface was made superhydrophilic by irradiation with vacuum ultraviolet light.
  • a 1 wt% solution prepared by diluting the fluoropolymers of Production Examples 1 to 3 and Comparative Production Example 1 with HC FC225 was spin-coated on this substrate at 2000 rpm for 1 minute to obtain a film thickness (solvent Excluded film thickness)
  • An lOOnm film was prepared.
  • the static contact angle and rolling angle of this film were measured. The results are shown in Table 1.
  • the glass transition point shown is measured for Balta polymer.
  • the static contact angle is almost the same between the example and the comparative example, but the falling angle is much smaller in the example than in the comparative example, and the liquid tends to roll.
  • a photomask of line / space 10 ⁇ m / 10 ⁇ m was adhered to these films and irradiated with vacuum ultraviolet light for 10 minutes to make the irradiated region lyophilic, and the lyophobic region and lyophilic solution.
  • Example 4 bisphenol A-dihirochetyl ether diatalylate (crosslinking agent) 45% by weight, a-F (fluorine monomer) 25% by weight, both ends modified with methacryloyl groups and having a molecular weight of 5,000 Dimethylpolysiloxane (cross-linking agent) 25% by weight, 2-hydroxy-2-methyl-1 phenol propane (photopolymerization initiator) 5% by weight are mixed and dissolved, and this solution is deposited on the substrate using a doctor blade. The film was applied so that the film thickness (excluding the solvent) was 100 m. In Example 5 and Comparative Example 2, —F was replaced with ⁇ Cl and a—H, respectively.
  • Comparative Production Example 2 was obtained by replacing the fluorinated monomer of Production Example 4 with ⁇ -H.
  • the weight average molecular weight was 32,000.
  • Fluoropolymer 10% by weight in Production Example 4 or Comparative Production Example 2 acid generator WPAG-1 99 (Wako Pure Chemicals) 1% by weight, acid crosslinking agent Cymel 303 (Nippon Cytec Industries) 5% by weight, propylene glycol monomethyl ether a solution of 84 weight 0/0 and was spin-coated to form a film having a thickness (excluding the solvent! was ⁇ thickness) 5 mu m on a substrate same substrate as in example 1.
  • the irradiated region is cross-linked and becomes insoluble in the solvent.
  • 2.3 8 wt 0/0 tetramethylammonium - was developed by immersion for 1 minute in Umuhidorokishido aqueous solution, washed with water, to produce a patterned substrate made of liquid-repellent region and the lyophilic region.
  • Comparative Production Example 3 was obtained by replacing the fluorinated monomer of Production Example 5 with ⁇ -H.
  • the weight average molecular weight was 33,000.
  • fluoroatalylate CH C (Cl) COOCH CH C F (abbreviation ⁇ Cl) 50 g, methacrylolic acid 20 g
  • AdEMA 2-ethyl 2-adamantyl metatalylate
  • lauryl mercaptan 5 g
  • propylene glycol monomethyl ether acetate 300 g
  • 2,2′azobisisobutyl-tolyl lg 3 g
  • Residual monomer in reaction solution is analyzed by gas chromatography As a result, it was confirmed that the polymerization rate was 95% or more.
  • the obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer.
  • the weight average molecular weight was 11,000 (polystyrene conversion).
  • the glass transition point measured by DSC was 135 ° C. DSC temperature range and heating rate are 1 st RUN:-50-200 ° C (10 ° C / min), 2nd RUN:-50-200 ° C (10 ° C / min), and glass transition point Is the extrapolated glass transition end temperature of 2nd RUN.
  • COOCH CH C F (abbreviation a-H) replaced with production examples 7, 8, comparative production example 3 and
  • the weight average molecular weights were 9, 000, 12,000, and 10,000, respectively.
  • the glass transition points were 115 °, 87 °, and 71 °, respectively.
  • the film was developed by immersing it in a 15% aqueous solution of alkaline developer P3 disperse M (Henkel Japan) for 1 minute, washed with water, dried, and heated at 200 ° C for 1 hour. A patterned substrate consisting of regions was produced. When the pattern was observed with a field-effect scanning electron microscope (FE—SEM), in Examples 8 to 10, the line width was 10 m. A clear line pattern was formed. On the other hand, in Comparative Example 5, disorder was observed in the line shape.
  • FE—SEM field-effect scanning electron microscope
  • a colorant for a liquid crystal display color filter was applied to these pattern substrates by an inkjet method.
  • the ink jet device used Litrex 70 manufactured by Litrex
  • a uniformly hydrophilic substrate it was observed with an optical microscope that a thin film with a diameter of about 200 m was formed after solvent drying.
  • a noturn substrate was used, in Examples 8 to 10, a color thin film that was clearly split along the lyophilic region having a line width of 10 ⁇ m was formed.
  • Comparative Example 5 there were portions where a thin film was formed not only in the lyophilic region but also in the lyophobic region, and the color thin film was not completely split.
  • Production examples 9 to 20 and comparative production example 4 were obtained by replacing the fluoroatalylate and the high soft spot monomer of Production Example 6 with those shown in Table 2.
  • the relationship between compound names and abbreviations is as follows.
  • CH CHCOOCH CH C F (abbreviation C8 a— H), 2-methyl-2-adaman
  • AdMMA Tylmetatalylate
  • MMA Methylmetatalylate
  • iBMA Isovol Metatalylate
  • PhMA Phenol Metatalylate
  • NBMA Norbornyl Methyl Metatalylate
  • CHMA Cyclohe Xylmethalate
  • Examples 11 to 22 and Comparative Example 6 were obtained by replacing the fluoropolymer of Production Example 8 (Production Example 6) with Production Examples 7 to 20 and Comparative Production Example 4.
  • Noturn was observed with FE-SEM, in Examples 11 to 22, a clear line pattern having a line width of 10 m was formed.
  • Comparative Example 6 disorder was observed in the line shape.
  • a color filter colorant was applied to these patterned substrates by an inkjet method.
  • Examples 11 to 22 a force-strength film that was clearly split along the lyophilic region having a line width of 10 / z m was formed.
  • Comparative Example 6 there was a portion where a thin film was formed not only in the lyophilic region but also in the lyophobic region.
  • a solution of 82% by weight of rumonomethyl ether acetate was spin-coated on a superhydrophilic glass substrate in the same manner as in Example 1, and a film thickness (film thickness excluding the solvent) of 2 ⁇ m was formed on the substrate.
  • a patterned substrate composed of a liquid repellent region and a lyophilic region was prepared in the same manner as in Example 8 below. When Noturn was observed with FE-SEM, a clear line pattern with a line width of 10 m was formed.
  • the graft copolymer replaced with COO (CH2) 3S02C4.F9 was used as Production Example 21.
  • the weight average molecular weight was 13,000 and the glass transition point was 125 ° C.
  • Example 24 A case where the fluoropolymer (random copolymer) of Example 16 is replaced with the graft copolymer of Production Example 21 is referred to as Example 24.
  • Example 24 When the pattern was observed with FE-SEM, a clear line pattern with a line width of 10 ⁇ m was formed.
  • a color thin film clearly divided along the lyophilic region having a line width of 10 m was formed.
  • the falling angle for n-hexadecane was 10
  • the sliding angle with respect to PGMEA was 14 °, and the performance was further improved as compared with Example 16 using a random copolymer.
  • the contact angle should be measured as it is. I can't. Therefore, in order to measure the contact angle, a large area liquid repellent region was prepared by the following method.
  • the electromagnetic wave curable composition of the present invention is uniformly applied to a 3 cm ⁇ 3 cm substrate by a spin coating method (2000 rpm, 30 seconds), and the coating film is cured by irradiating with an ultraviolet ray having an integrated illuminance lOOOmjZcm 2 in a nitrogen atmosphere. It was.
  • the contact angle was measured with a fully automatic contact angle meter after dropping 2 L of water or n-hexadecane from a microsyringe onto a horizontally placed substrate.
  • HX—2A Hexanediol ditalylate
  • Table 1 shows the contact angles of this electromagnetic wave curable composition. Even water and n-hexadecane showed high liquid repellency even in the case of liquid droplets.
  • the silicon wafer was cleaned with acetone and then irradiated with vacuum ultraviolet light to make the surface superhydrophilic.
  • the film of the electromagnetic wave curable composition was cured by irradiating the substrate with ultraviolet rays having an integrated illuminance of lOOOOmjZcm 2 in a nitrogen atmosphere.
  • Example 26 pentaerythritol tetratalate (abbreviated as PEN-4A) was used.
  • TMP-3A trimethylolpropane tritalylate
  • PEN-4A pentaerythritol tetratalate
  • Example 28 [R C6) Abbreviated as talate] was used as Example 28 when Irgacure 907 was 1% by weight. In this system, when 2% by weight or more of Irgacure 907 was added, the electromagnetic wave curable composition was not dissolved uniformly. This electromagnetic wave curable composition showed high liquid repellency, and the F8 thin film had good splitting properties with respect to the pattern substrate.
  • Example 25 Q (Laylyl atylate was used instead of C1 atylate, and HX—2A, TMP—3A, and PEN—4A were used as multifunctional acrylates. 10 and 11.
  • This electromagnetic wave curable composition had almost no liquid repellency to n-xadecane, and the F8 thin film had poor splitting ability to the pattern substrate.

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Abstract

Disclosed is a surface treating agent for photolithography containing at least one of a fluorine monomer (A) described below and a fluorine polymer (B) containing the fluorine monomer. The fluorine monomer (A) is at least one fluorine monomer selected from (A-1) an a-substituted acrylate containing a fluoroalkyl group having 1-6 carbon atoms; (A-2) a fluorine-containing silsesquioxane monomer containing a fluoroalkyl group having 1-6 carbon atoms and a polymerizable group; (A-3) a polymerizable monomer containing a perfluoropolyether group; (A-4) a monomer wherein a fluoroalkyl group having 1-6 carbon atoms and a polymerizable group are linked by -SO2(CH2)n- (wherein n is 1-10); and (A-5) a macromonomer containing at least one of the monomers (A-1)-(A-4) as a repeating unit and having a (meth)acryloyl group at a polymer end. This surface treating agent provides a liquid repellent region with sufficiently high water repellency and oil repellency even thought it has a short-chain Rf group (short-chain fluoroalkyl group) having 6 or less carbon atoms.

Description

明 細 書  Specification
パターン形成用表面処理剤  Surface treatment agent for pattern formation
技術分野  Technical field
[0001] 本発明は、親液領域および撥液領域力もなるパターン表面をフォトリソグラフィ一法 により作製するための表面処理剤に関する。  The present invention relates to a surface treatment agent for producing a pattern surface having lyophilic area and liquid repellent area force by a photolithography method.
背景技術  Background art
[0002] フルォロアルキル基（以下、 Rf基と省略）含有モノマー [J. Poly. Sci. Part A, 37, 77( 1999)]、または、 Rf基含有モノマー 架橋性官能基含有モノマーの共重合体 (特開 20 03— 300323)を、架橋性モノマーおよび光重合開始剤とブレンドし、光重合する技術 が開示されて ヽる。これらの技術は濡れ性の異なる撥液性と親液性の領域カゝら構成 されるパターン表面をフォトリソグラフィ一法で作製するための表面処理剤として適用 可能である。従来技術では、撥液性に有利な炭素数 8以上の長鎖 Rf基を有する Rf基 含有モノマーが用いられてきた。  [0002] Monomers containing fluoroalkyl groups (hereinafter abbreviated as Rf groups) [J. Poly. Sci. Part A, 37, 77 (1999)], or copolymers of Rf group-containing monomers and crosslinkable functional group-containing monomers ( JP-A-203-03300323) is disclosed a technique of blending with a crosslinkable monomer and a photopolymerization initiator and performing photopolymerization. These techniques can be applied as a surface treatment agent for producing a pattern surface composed of liquid repellent and lyophilic regions having different wettability by a photolithography method. In the prior art, an Rf group-containing monomer having a long-chain Rf group having 8 or more carbon atoms, which is advantageous for liquid repellency, has been used.
[0003] しかし、炭素数 8以上の長鎖 Rf基を有する Rf基含有モノマー、ある 、は、 Rf基含有モ ノマーの共重合体が表面処理剤を構成する架橋性モノマー、光重合開始剤、溶媒 などに相溶しにくい問題があった。  [0003] However, an Rf group-containing monomer having a long-chain Rf group having 8 or more carbon atoms, a crosslinkable monomer in which a copolymer of Rf group-containing monomers constitutes a surface treatment agent, a photopolymerization initiator, There was a problem that it was difficult to dissolve in solvents.
[0004] 一方、 Rf基含有モノマーに炭素数 8以上の長鎖 Rf基を用いると環境、生体への蓄積 性の問題が懸念される。従来、基材に高い撥水撥油性を付与するために表面処理 剤として汎用されてきた炭素数 8〜12の長鎖 Rf基を有する Rf基含有ィ匕合物は、最近 になって環境、生体への蓄積性の問題が指摘されている。最近の研究結果 [EPAレ ポ ~~ト〃 Draft Risk Assessment of the Potential Human Health Effects Associated Wit h Exposure to Perfluorooctanoic Acid and Its Salts (PFOA)" (http://www.epa.g0v/0 pptintr/pfoa/pfoarisk.pdi)]などから、長鎖 Rf基含有化合物の一種である PFOA (peril uorooctanoic acid)に対する人体への蓄積性の懸念が明ら力となってきており、 2003 年 4月 14日に EPA (米国環境保護庁)が PFOAに対する科学的調査を強化すると発表 した。 [0004] On the other hand, if a long-chain Rf group having 8 or more carbon atoms is used for the Rf group-containing monomer, there is a concern about the problem of accumulation in the environment and living body. Conventionally, Rf group-containing compounds having long chain Rf groups with 8 to 12 carbon atoms, which have been widely used as surface treatment agents to impart high water and oil repellency to substrates, have recently been Problems with accumulation in the living body have been pointed out. Recent Research Results [EPA Report -Drft Risk Assessment of the Potential Human Health Effects Associated Wit h Exposure to Perfluorooctanoic Acid and Its Salts (PFOA) "(http: //www.epa.g0v/0 pptintr / pfoa /pfoarisk.pdi)], and the like, the concern about the accumulation of PFOA (peril uorooctanoic acid), a long-chain Rf group-containing compound, in the human body has become apparent. The EPA (United States Environmental Protection Agency) announced that it would strengthen scientific research on PFOA.
[0005] 一方、 Federal Register(FR Vol.68, No.73/April 16, 2003 [FRL— 2303— 8] , http:/ /www. epa.gov/opptintr/pfoa/pfoafr.pdf)や EPA Environmental News FOR RELEA SE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gOv/opptintr/pfoa/pfoaprs.p df)や EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opptintr/pfoa /pfoafacts.pdf)は、テロマーが分解または代謝により PFOAを生成する可能性がある と公表している（テロマーとは長鎖 Rf基と同義である）。また、テロマーが、撥水撥油性 、防汚性を付与された泡消火剤、ケア製品、洗浄製品、カーペット、テキスタイル、紙 、皮革などの多くの製品に使用されて 、ることをも公表して 、る。 [0005] On the other hand, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL— 2303— 8], http: / /www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEA SE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gOv/opptintr/ pfoa / pfoaprs.p df) and EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) can cause telomers to produce PFOA through degradation or metabolism. (Telomers are synonymous with long-chain Rf groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. And
[0006] このような環境問題のために、長鎖 Rf基含有ィ匕合物の代替物質として、炭素数 1〜6 の短鎖 Rf基を有する Rf基含有ィ匕合物を撥水撥油剤として利用する必要性が生じてき た。しかし、従来の骨格をそのまま短鎖 Rf基に置換しても撥液領域の撥水撥油性が 不十分であった。 [0006] Because of such environmental problems, as an alternative to a long-chain Rf group-containing compound, an Rf group-containing compound having a short-chain Rf group having 1 to 6 carbon atoms is used as a water / oil repellent. The need to use as However, even if the conventional skeleton is replaced with a short-chain Rf group as it is, the water and oil repellency of the liquid repellent region is insufficient.
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明の第 1の要旨に関する目的は、炭素数 6以下の短鎖 Rf基を有していても、撥 液領域に充分に高い撥水撥油性を与えるパターン形成用表面処理剤を提供するこ とである。 [0007] An object related to the first gist of the present invention is to provide a pattern forming surface treatment agent that has a sufficiently high water and oil repellency in a liquid repellent region even if it has a short-chain Rf group having 6 or less carbon atoms. Is to provide.
本発明の第 2の要旨に関する目的は、非接触な微量液滴吐出法により、基材に微 小な撥液領域を形成させ、さらにその撥液領域は長鎖 Rf基含有化合物を用いなくと も高い撥液性を有するパターン基板の製造方法を提供することである。  The purpose of the second aspect of the present invention is to form a small liquid repellent region on a substrate by a non-contact microdroplet discharge method, and the liquid repellent region must use a long-chain Rf group-containing compound. Another object of the present invention is to provide a method for producing a patterned substrate having high liquid repellency.
課題を解決するための手段  Means for solving the problem
[0008] 第 1の要旨によれば、本発明は、特定のフッ素系モノマーおよび Zまたは特定のフ ッ素系ポリマー力もなるフォトリソグラフィー用表面処理剤を提供する。 [0008] According to the first aspect, the present invention provides a surface treatment agent for photolithography which also has a specific fluorine-based monomer and Z or a specific fluorine-based polymer power.
フッ素系モノマーとしては、例えば、  As the fluorine-based monomer, for example,
'炭素数 1〜6の Rf基を有する α位置換アタリレートモノマー（ α位の置換基は例えば F, C1である。 )、  'Α-substituted attalylate monomer having an Rf group having 1 to 6 carbon atoms (substituents at the α-position are, for example, F and C1),
'炭素数 1〜6の Rf基を有する重合性シルセスキォキサンモノマー、  'A polymerizable silsesquioxane monomer having an Rf group having 1 to 6 carbon atoms,
'パーフルォロポリエーテル基を有する重合性モノマー、 '炭素数 1〜6のフルォロアルキル基と重合性基が SO (CH )一（nは 1〜10、特に 3 'A polymerizable monomer having a perfluoropolyether group, 'When the fluoroalkyl group having 1 to 6 carbon atoms and the polymerizable group are SO (CH) 1 (n is 1 to 10, especially 3
2 2 n  2 2 n
〜6)により連結された重合性モノマー  ~ 6) polymerizable monomers linked
'これらモノマーの少なくとも 1種を繰り返し単位とするポリマーの末端に (メタ）アタリ口 ィル基を有するマクロモノマー  'A macromonomer having a (meth) aryl group at the end of a polymer having at least one of these monomers as a repeating unit
を適用する。  Apply.
[0009] 本発明は、以下のフッ素系モノマー (A)およびフッ素系ポリマー（B)からなる群から 選択された少なくとも 1種の含フッ素化合物を含有してなるフォトリソグラフィー用表面 処理剤を提供する。  [0009] The present invention provides a surface treatment agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of the following fluorine-based monomer (A) and fluorine-based polymer (B). .
參フッ素系モノマー（A)  參 Fluorine monomer (A)
(A— 1)炭素数 1〜6のフルォロアルキル基を有する α位置換アタリレートモノマー ( α位の置換基:フッ素原子、塩素原子、臭素原子、ヨウ素原子、 CFXY基 (但し、 X 1および X2は、水素原子、フッ素原子または塩素原子である。）、シァノ基、炭素数 1〜 20の直鎖状または分岐状のフルォロアルキル基、置換または非置換のベンジル基、 置換または非置換のフ ニル基、ある!、は炭素数 1〜20の直鎖状または分岐状アル キル基）、 (A-1) α-substituted acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms (substituent at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, CFXY group (however, X 1 and X 2 Is a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group , Yes! Is a straight or branched alkyl group having 1 to 20 carbon atoms),
(A— 2)炭素数 1〜6のフルォロアルキル基および重合性基を含有する含フッ素シ ノレセスキォキサンモノマー、  (A-2) a fluorine-containing cinresesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group,
(A- 3)パーフルォロポリエーテル基を有する重合性モノマー、  (A-3) a polymerizable monomer having a perfluoropolyether group,
(A 4)炭素数 1〜6のフルォロアルキル基と重合性基が SO (CH )一（nは 1〜1  (A 4) The fluoroalkyl group having 1 to 6 carbon atoms and the polymerizable group are SO (CH 3) (where n is 1 to 1
2 2 n  2 2 n
0、特に 3〜6)により連結された重合性モノマー  Polymerizable monomers linked by 0, in particular 3-6)
(A- 5)モノマー（A— 1)〜（A—4)の少なくとも 1種を繰り返し単位とするポリマ 一の末端に (メタ)アタリロイル基を有するマクロモノマー  (A-5) Macromonomer having a (meth) atallyloyl group at the end of a polymer having at least one monomer (A-1) to (A-4) as a repeating unit
力 なる群力 選択された少なくとも 1種のモノマー  Force group power at least one monomer selected
フッ素系モノマーは、上記の 2種の混合物（例えば、モノマー（A— 1)とモノマー（A -4)の組合せ）であってもよ！/、。  The fluorine monomer may be a mixture of the above two types (for example, a combination of monomer (A-1) and monomer (A-4))! /.
[0010] 參フッ素系ポリマー（B) [0010] 參 Fluoropolymer (B)
フッ素系モノマー (A)と同様である繰り返し単位 (B- 1)から誘導された繰り返し単 位を有するフッ素系ポリマーであり、単独重合体であっても共重合体であっても良 、 。共重合体の場合はランダム、交互、ブロック、グラフトのいずれでも良い。 It is a fluorine-based polymer having a repeating unit derived from the repeating unit (B-1) which is the same as the fluorine-based monomer (A), and may be a homopolymer or a copolymer. . In the case of a copolymer, any of random, alternating, block, and graft may be used.
[0011] 第 2の要旨によれば、本発明は、フルォロアルキル基を含有するフッ素系モノマー（ A)、架橋剤 (B)、光架橋触媒 (C)を含んでなる電磁波硬化組成物を、非接触な微 量液滴吐出法で基材に吐出し、その微細な塗膜に電磁波を照射して硬化させること により、表面自由エネルギーが異なる少なくとも 2つの領域力 構成されるパターンを 基材上に形成するパターン基板の製造方法をも提供する。  [0011] According to the second aspect, the present invention provides an electromagnetic wave curable composition comprising a fluorine-containing monomer (A) containing a fluoroalkyl group, a crosslinking agent (B), and a photocrosslinking catalyst (C). A pattern consisting of at least two different areas of different surface free energy is formed on the substrate by discharging it onto the substrate using a contact microdroplet discharge method and irradiating and curing the fine coating film with electromagnetic waves. A method of manufacturing a pattern substrate to be formed is also provided.
発明の効果  The invention's effect
[0012] 本発明の表面処理剤は、基板上に、パターン化された高い撥水撥油性を発現する 膜を形成する。  [0012] The surface treatment agent of the present invention forms a patterned film exhibiting high water and oil repellency on a substrate.
発明を実施するための形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0013] 炭素数 1〜6のフルォロアルキル基を有する α位置換アタリレート（A— 1)、パーフ ルォロポリエーテル基を有する重合性モノマー（Α— 3)、炭素数 1〜6のフルォロアル キル基と重合性基が SO (CH )一（nは 1〜10、特に 3〜6)により連結された重合性 [0013] α-substituted attalylate having a fluoroalkyl group having 1 to 6 carbon atoms (A-1), a polymerizable monomer having a perfluoropolyether group (3-3), a fluoroalkyl group having 1 to 6 carbon atoms And the polymerizable group are linked by SO (CH) (where n is 1 to 10, especially 3 to 6)
2 2 n  2 2 n
モノマー（A— 4)は、  Monomer (A-4)
(A)式：  Formula (A):
[化 1]  [Chemical 1]
0 X  0 X
Rf— Y ~ 0— C— C=CH2 (I) Rf— Y ~ 0— C— C = CH 2 (I)
[式中、 Xは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、 CFX1^基 (但し、 X1お よび X2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、 シァノ基、炭素数 1〜21の直鎖状または分岐状のフルォロアルキル基、置換または 非置換のベンジル基、置換または非置換のフエ二ル基、あるいは炭素数 1〜20の直 鎖状または分岐状アルキル基 [Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 ^ group (where X 1 and X 2 are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom ), Ciano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or straight chain having 1 to 20 carbon atoms Or branched alkyl group
Yは、直接結合、酸素原子を有していてもよい炭素数 1〜10の脂肪族基、酸素原子 を有していてもよい炭素数 6〜10の芳香族基、環状脂肪族基または芳香脂肪族基、 -CH CH N(Ri)SO—基（但し、 R1は炭素数 1〜4のアルキル基である。）、 CHY is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, -CH CH N (Ri) SO- group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms), CH
2 2 2 22 2 2 2
CHCOY^CH—基 (但し、 Y1は水素原子またはァセチル基である。）、または、 (C CHCOY ^ CH— group (where Y 1 is a hydrogen atom or acetyl group), or (C
2  2
H ) SO一基（nは 1〜10)である。 Rfは炭素数 1〜6の直鎖状または分岐状のフルォロアルキル基、または、繰り返し単 位：— C F O—、— C F O および— CF O—力 なる群から選択された少なくともH) One SO group (n is 1 to 10). Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or at least selected from the group consisting of repeating units: —CFO—, —CFO and —CF 2 O—force.
3 6 2 4 2 3 6 2 4 2
一種の繰り返し単位の合計数が 1〜 200のフルォロエーテル基である。 ] で示されるフッ素含有基を有する含フッ素単量体であってよい。  It is a fluoroether group having a total number of one type of repeating unit of 1 to 200. ] The fluorine-containing monomer which has a fluorine-containing group shown by these may be sufficient.
[0014] 上記式にお 、て、重合性基 (例えば、炭素炭素二重結合基）とフルォロアルキル基 との間に（すなわち、 0—Y—に代えて）、 [0014] In the above formula, a polymerizable group (for example, a carbon-carbon double bond group) and a fluoroalkyl group (that is, instead of 0—Y—),
O— Y1— O— Y 1 —
(ここで、 Y1は、直接結合、酸素原子を有していてもよい炭素数 1〜10の脂肪族基、 酸素原子を有していてもよい炭素数 6〜10の芳香族基または環状脂肪族基または 芳香脂肪族基、 -CH CH N(Ri)SO— (CH CH )一基 (但し、 R1は炭素数 1〜4の (Where Y 1 is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or cyclic. An aliphatic group or an araliphatic group, -CH 2 CH N (Ri) SO— (CH 2 CH 3) 1 group (provided that R 1 has 1 to 4 carbon atoms)
2 2 2 2 2 a  2 2 2 2 2 a
アルキル基、 aは 0または 1である。）、 -CH CH(ORU)CH—基 (但し、 RUは水素原 An alkyl group, a is 0 or 1; ), -CH CH (OR U ) CH— group (where R U is a hydrogen atom)
2 2  twenty two
子またはァセチル基である。）または、 (CH ) S〇—基 (nは 〜 10)である。）、あるい  Child or acetyl group. ) Or (CH 3) S 0 — group (n is ˜10). )
2 n 2  2 n 2
は  Is
Y2 (CH ) -Z-]— (CH ) Y 2 (CH) -Z-] — (CH)
2 m p 2 n  2 m p 2 n
(ここで、 Y2は、 Ο または一 ΝΗ であり； Ζは、 S または一 SO—であり； mは (Where Y 2 is Ο or 1 ；; Ζ is S or 1 SO—; m is
2  2
1〜10、 nは O〜10、 pは 0または 1である。 )  1 to 10, n is O to 10, and p is 0 or 1. )
を有していてもよい。  You may have.
[0015] したがって、モノマー（A—l)、（A— 3)、（A— 4)は、式： Accordingly, the monomers (A-1), (A-3), and (A-4) are represented by the formula:
CH =CX-C(=0)-B-Rf  CH = CX-C (= 0) -B-Rf
2  2
[式中、 Bは、 O— Y1—または— Y2— [― (CH ) -Z-] -(CH ) -[Where B is O— Y 1 — or — Y 2 — [— (CH) -Z-]-(CH)-
2 m p 2 n 2 m p 2 n
(ここで、
Figure imgf000006_0001
Ζ、 m、 η、および ρは上記と同意義である。 ) (here,
Figure imgf000006_0001
Ζ, m, η, and ρ are as defined above. )
Xおよび Rfは上記と同意義である。 ]  X and Rf are as defined above. ]
で示される化合物であってょ 、。  It is a compound represented by
[0016] パーフルォロポリエーテル基を有する重合性モノマー（A— 3)、および炭素数 1〜6 のフルォロアルキル基と重合性基が— SO (CH ) - (nは 1〜10、特に 3〜6)により連 [0016] A polymerizable monomer having a perfluoropolyether group (A—3), and a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group —SO (CH 3) − (n is 1 to 10, especially 3 ~ 6)
2 2 n  2 2 n
結された重合性モノマー (A— 4)においては、 Xの例は、上記原子および基に加えて 、水素およびメチル基である。  In the bonded polymerizable monomer (A-4), examples of X are hydrogen and a methyl group in addition to the above atoms and groups.
[0017] 重合性モノマー (A— 3)および重合性モノマー (A—4)は、重合性基を有するモノ マーである。重合性基は、二重結合で結合された炭素 炭素基 (例えば、ェテニル 基)であってよい。重合性モノマー (A— 2)〜(A— 4)は、 [モノマー (A— 1)と同様に ] α位が置換されている（すなわち、 α位が水素またはアルキル基でない）アタリレー トであってもよい。あるいは、 α位に水素原子またはメチル基を有するアタリレートで あってもよい。 [0017] The polymerizable monomer (A-3) and the polymerizable monomer (A-4) are monomers having a polymerizable group. Ma. The polymerizable group may be a carbon-carbon group (for example, an ethenyl group) bonded by a double bond. The polymerizable monomers (A-2) to (A-4) are atalates that are substituted at the α-position (that is, the α-position is not hydrogen or an alkyl group) [similar to the monomer (A-1)]. May be. Alternatively, it may be an acrylate having a hydrogen atom or a methyl group at the α-position.
[0018] 上記式 (I)において、 Rf基の炭素数は、 1〜6、例えば 1〜5、好ましくは 4である。一 般に Rf基が長くなるほど撥液性が優れ、短くなるほど相溶性が優れる傾向があり、撥 液性と相溶性が両立する炭素数は 4である。生体蓄積性の観点でも炭素数 6よりも 4 の方が好ましい。  [0018] In the above formula (I), the Rf group has 1 to 6, for example, 1 to 5, preferably 4. In general, the longer the Rf group, the better the liquid repellency, and the shorter the Rf group, the better the compatibility. The number of carbons having both liquid repellency and compatibility is 4. From the viewpoint of bioaccumulation, 4 is preferable to 6 carbon atoms.
Rf基の f列は、一 CF、 -CF CF、 -CF CF CF、 一 CF(CF ) 、 一 CF CF CF C  F column of Rf group is one CF, -CF CF, -CF CF CF, one CF (CF), one CF CF CF C
3 2 3 2 2 3 3 2 2 2 2 3 2 3 2 2 3 3 2 2 2 2
F、 -CF CF(CF ) 、 一 C(CF ) 、 一 (CF ) CF、 一 (CF ) CF(CF )、 一 CF C(CF )F, -CF CF (CF), one C (CF), one (CF) CF, one (CF) CF (CF), one CF C (CF)
3 2 3 2 3 3 2 4 3 2 2 3 2 2 3 33 2 3 2 3 3 2 4 3 2 2 3 2 2 3 3
、— CF(CF )CF CF CF、― (CF ) CF、— (CF ) CF(CF )等である。 , —CF (CF) CF CF CF, — (CF) CF, — (CF) CF (CF), and the like.
3 2 2 3 2 5 3 2 3 3 2  3 2 2 3 2 5 3 2 3 3 2
[0019] Yは、直接結合、酸素原子を有していてもよい炭素数 1〜10の脂肪族基、酸素原 子を有していてもよい炭素数 6〜10の芳香族基、環状脂肪族基または芳香脂肪族 基、 CH CH N(Ri)SO—基 (但し、 R1は炭素数 1〜4のアルキル基である。）、 C [0019] Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or a cyclic fat. Group or araliphatic group, CH CH N (Ri) SO— group (where R 1 is an alkyl group having 1 to 4 carbon atoms), C
2 2 2  2 2 2
H CHCOY^CH—基 (但し、 Y1は水素原子またはァセチル基である。）、または、—（H CHCOY ^ CH— group (where Y 1 is a hydrogen atom or a acetyl group) or — (
2 2 twenty two
CH ) SO一基 (nは 1〜10)である。脂肪族基はアルキレン基 (特に炭素数 1〜4、例え CH 2) SO 1 group (n is 1 to 10). Aliphatic groups are alkylene groups (especially 1 to 4 carbon atoms, for example
2 n 2 2 n 2
ば、 1または 2)であることが好ましい。芳香族基および環状脂肪族基は、置換されて いてもあるいは置換されていなくてもどちらでもよい。 -CH CH NCR^SO—基およ  For example, 1 or 2) is preferable. The aromatic group and the cycloaliphatic group may be either substituted or unsubstituted. -CH CH NCR ^ SO—group and
2 2 2 び (CH ) SO一基において Rfに結合する原子は、メチレン基における炭素原子ま  In the 2 2 2 and (CH 2) 2 SO 1 groups, the atom bonded to Rf is the carbon atom in the methylene group.
2 n 2  2 n 2
たはスルホン基における硫黄原子のどちらであってもよいが、一般に、スルホン基に おける硫黄原子であってょ 、。  Or a sulfur atom in a sulfone group, but generally a sulfur atom in a sulfone group.
[0020] 上記含フッ素単量体の例は、次のとおりである。  [0020] Examples of the fluorine-containing monomer are as follows.
[0021] [化 2]
Figure imgf000008_0001
[0021] [Chemical 2]
Figure imgf000008_0001
[化 3]
Figure imgf000008_0002
[Chemical 3]
Figure imgf000008_0002
O CIO CI
II I II I
Rf-CH2CH2—— O— C-C=CH2 [0022] [化 4] Rf-CH 2 CH 2 —— O— CC = CH 2 [0022] [Chemical 4]
O Br II I  O Br II I
Rf-CH2CH2— O— C— C二 CH2 Rf-CH 2 CH 2 — O— C— C 2 CH 2
O IO I
II I II I
Rf-CH2CH2—— O— C— C=CH2 [0023] [化 5] Rf-CH 2 CH 2 —— O— C— C = CH 2 [0023] [Chemical 5]
O CF3 II I O CF 3 II I
Rf-CH2CH2—— O— C— C=CH2 Rf-CH 2 CH 2 —— O— C— C = CH 2
O CNO CN
II I II I
Rf-CH2CH2—— O— C— C=CH2 Rf-CH 2 CH 2 —— O— C— C = CH 2
O Rf II I O Rf II I
Rf-CH2CH2—— O— C— C=CH2 Rf-CH 2 CH 2 —— O— C— C = CH 2
[化 6] ϋ CH - C6H [Chemical 6] ϋ CH-C 6 H
I I I  I I I
Rf-CH2CH2— O— C— C CH2 Rf-CH 2 CH 2 — O— C— C CH 2
o CeH5 o CeH 5
Rf— CH2CH2— O— C- -C=CH2 Rf— CH 2 CH 2 — O— C- -C = CH 2
[化 7]
Figure imgf000009_0001
[Chemical 7]
Figure imgf000009_0001
3  Three
I  I
Rf-S02NGH2CH2—— O- -G— C=GH2 Rf-S0 2 NGH 2 CH 2 —— O- -G— C = GH 2
C2H5 O F C 2 H 5 OF
Rf-S02NCH2CH2—— O- -C— C=CH2 Rf-S0 2 NCH 2 CH 2 —— O- —C— C = CH 2
G4H9 O CI G 4 H 9 O CI
I I  I I
Rf-S02NCH2CH2—— O- -C— C=CH2 Rf-S0 2 NCH 2 CH 2 —— O- —C— C = CH 2
GH3 0 CF3 GH 3 0 CF 3
I  I
Rf-S02NGH2CH2—— O- -G— C=GH2 Rf-S0 2 NGH 2 CH 2 —— O- -G— C = GH 2
OH 〇 F  OH ○ F
Rf— CH2CHCH2 〇- -G— G=GH2 Rf— CH 2 CHCH 2 ○--G— G = GH 2
OH 〇 Gl  OH 〇 Gl
I  I
Rf— CH2CHCH2 〇_ -G— G==CH2 Rf— CH 2 CHCH 2 ○ _ -G— G == CH 2
OCOCHg O F  OCOCHg OF
1 I  1 I
Rf-CH2CHCH2 O- - C C二 CH2 Rf-CH 2 CHCH 2 O--CC 2 CH 2
OCOCHg 〇 CI  OCOCHg ○ CI
I I  I I
Rf-CH2CHCH2 O- - C C二 CH2 Rf-CH 2 CHCH 2 O--CC 2 CH 2
Rf— SO (CH ) - OCO - CH=CH  Rf— SO (CH)-OCO-CH = CH
CH =c (- -F)- -c(=o)- -o- (CH ) - - S— ]  CH = c (--F)--c (= o)--o- (CH)--S—]
2 2  twenty two
CH -F)- C(=〇) - -o- (CH ) - CH -F)-C (= 〇)--o- (CH)-
2 -s-i 2 -s-i
2 2 2 2 2 2 2 2
CH C (- -F)- C(=0)- - 0— (CH ) -CH C (--F)-C (= 0)--0— (CH)-
2 -so 2 -so
2 2 2  2 2 2
CH -F)- C(=0)- - 0— (CH ) - CH -F)-C (= 0)--0— (CH)-
2 -so 2 -so
2 2 2 2 2 2 2 2 2 2
CH =C (- F)- C(=0)- -NH — (CH ) Rf CH = C (-F)-C (= 0)--NH — (CH) Rf
2 2 CH =C(-Cl)-C(=0)-0 (CH ) -S-Rf twenty two CH = C (-Cl) -C (= 0) -0 (CH) -S-Rf
2 2 2  2 2 2
CH =C(-Cl)-C(=0)-0 -(CH ) -S-(CH ) -Rf  CH = C (-Cl) -C (= 0) -0-(CH) -S- (CH) -Rf
2 2 2 2 2  2 2 2 2 2
CH =C(-Cl)-C(=0)-0 -(CH ) SO -Rf  CH = C (-Cl) -C (= 0) -0-(CH) SO -Rf
2 2 2 2  2 2 2 2
CH =C(-Cl)-C(=0)-0 -(CH ) SO -(CH ) -Rf  CH = C (-Cl) -C (= 0) -0-(CH) SO-(CH) -Rf
2  2
CH =C( - CI) - C(=0) - NH - (CH ) Rf  CH = C (-CI)-C (= 0)-NH-(CH) Rf
2 2 2  2 2 2
CH =C( - CI) - C(=0) - O - (CH ) -S-Rf  CH = C (-CI)-C (= 0)-O-(CH) -S-Rf
2 2 3  2 2 3
CH =C( - CI) - C(=0) - O - (CH ) SO— Rf  CH = C (-CI)-C (= 0)-O-(CH) SO- Rf
2 2 3 2  2 2 3 2
CH =C(— CH )-C(=0)-0-(CH ) -Rf  CH = C (— CH) -C (= 0) -0- (CH) -Rf
2 3 2 2  2 3 2 2
CH =C(H)-C(=0)-0-(CH ) -Rf  CH = C (H) -C (= 0) -0- (CH) -Rf
2 2 2  2 2 2
[0026] [式中、 Rfは炭素数 1〜6の直鎖状または分岐状のフルォロアルキル基、または、繰 り返し単位：— C F O 、 C F O および— CF O—力 なる群から選択された少  [In the formula, Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms or a small number selected from the group consisting of repeating units: —C F O, C F O and —CF O—
3 6 2 4 2  3 6 2 4 2
なくとも一種の繰り返し単位の合計数が 1〜200のパーフルォロポリエーテル基であ る。]  It is a perfluoropolyether group having a total number of at least one kind of repeating unit of 1 to 200. ]
[0027] 炭素数 1〜6のフルォロアルキル基および重合性基を含有する含フッ素シルセスキ ォキサンモノマー (A— 2)は、（i)含フッ素不完全縮合シルセスキォキサンと (ii)重合 性官能基をもつ反応性シランとを反応することによって得られるものである。  [0027] The fluorine-containing silsesquioxane monomer (A-2) containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group comprises (i) a fluorine-containing incompletely condensed silsesquioxane and (ii) a polymerizable functional group. It is obtained by reacting with a reactive silane having a group.
含フッ素不完全縮合シルセスキォキサン (i)は、フルォロアルキル基を有する不完 全縮合シルセスキォキサンである。  The fluorine-containing incompletely condensed silsesquioxane (i) is an incompletely condensed silsesquioxane having a fluoroalkyl group.
[0028] シルセスキォキサンは POSS(Polyhedral Oligomeric Silsesquioxane)とも呼ばれる。 [0028] Silsesquioxane is also called POSS (Polyhedral Oligomeric Silsesquioxane).
不完全縮合シルセスキォキサン (i)のシラノール基は反応性が高ぐ一般に、分子 中に 1〜3個存在する。  The silanol group of incompletely condensed silsesquioxane (i) is highly reactive and generally there are 1 to 3 silanol groups in the molecule.
[0029] 不完全縮合シルセスキォキサン (0の具体例は、例えば次のもの (構造式 I)などであ る。  [0029] Incompletely condensed silsesquioxane (specific examples of 0 include, for example, the following (Structural Formula I)).
[化 8] [Chemical 8]
Figure imgf000011_0001
Figure imgf000011_0001
(構造式 I)  (Structure I)
[0030] 重合性官能基をもつ反応性シラン (ii)は、重合性官能基および反応性基を有する 。反応性シラン (ii)において、重合性官能基の例は、（メタ)アクリル基、アルファ置換 アクリル基、エポキシ基、ビュル基などである。反応性シラン (ii)において、反応性基 の例は、トリクロロシリル基およびトリアルコキシシリル基 (アルコキシ基の炭素数は 1 〜5である。）である。  [0030] The reactive silane (ii) having a polymerizable functional group has a polymerizable functional group and a reactive group. In the reactive silane (ii), examples of the polymerizable functional group include a (meth) acryl group, an alpha-substituted acryl group, an epoxy group, and a bur group. In the reactive silane (ii), examples of the reactive group are a trichlorosilyl group and a trialkoxysilyl group (the alkoxy group has 1 to 5 carbon atoms).
[0031] 反応性シラン (ii)は、例えば、一般式：  [0031] The reactive silane (ii) is, for example, represented by the general formula:
A11— A21— Si(A31) A 11 — A 21 — Si (A 31 )
3  Three
中、 A11は、重合性官能基であり、 A 11 is a polymerizable functional group,
A21は、直接結合または炭素数 1〜20 (例えば、 1〜10)のアルキル基であり、 A31は、ハロゲン原子 (例えば、塩素原子および臭素原子)またはアルコキシ基 (アル コキシ基の炭素数は 1〜5である。）である。 ] A 21 is a direct bond or an alkyl group having 1 to 20 carbon atoms (for example, 1 to 10), and A 31 is a halogen atom (for example, chlorine atom and bromine atom) or an alkoxy group (the number of carbon atoms in the alkoxy group). Is 1-5.) ]
で示される化合物である。  It is a compound shown by these.
[0032] 含フッ素シルセスキォキサン単量体（a)の例は、次のとおりである。 [0032] Examples of the fluorine-containing silsesquioxane monomer (a) are as follows.
[化 9]  [Chemical 9]
Figure imgf000011_0002
Figure imgf000011_0002
[0033] フッ素系ポリマー（B)が共重合体である場合には、フッ素系モノマー（B— 1) (すな わち、フッ素系モノマー (A)と同様のもの）と共重合させる共重合モノマーとして、不 飽和有機酸 (B— 2)および高軟化点モノマー (B— 3)が挙げられる。 [0033] When the fluoropolymer (B) is a copolymer, the fluoromonomer (B-1) In other words, unsaturated organic acids (B-2) and high softening point monomers (B-3) can be mentioned as copolymerization monomers to be copolymerized with the same fluorine-based monomer (A).
フッ素系ポリマー（B)は、例えば、  The fluorine-based polymer (B) is, for example,
(B1)フッ素系モノマー（B— 1)の単独重合体、  (B1) Fluoromonomer (B-1) homopolymer,
(B2)フッ素系モノマー（B— 1)と不飽和有機酸 (B— 2)の共重合体、または  (B2) a copolymer of a fluorine-based monomer (B-1) and an unsaturated organic acid (B-2), or
(B3)フッ素系モノマー（B— 1)と不飽和有機酸 (B— 2)と高軟化点モノマー（B— 3) の共重合体  (B3) Copolymer of fluorinated monomer (B-1), unsaturated organic acid (B-2) and high softening point monomer (B-3)
であってよい。  It may be.
[0034] 不飽和有機酸 (B— 2)は、少なくとも 1つの炭素 炭素二重結合、および少なくとも 1つの酸基 [例えば、カルボキシル基（COOH基）]を有するモノマーである。不飽和 有機酸の特に好ましい例は、不飽和カルボン酸、例えば、遊離の不飽和カルボン酸 および不飽和カルボン酸無水物である。不飽和有機酸 (B— 2)の例は、（メタ)アクリル 酸、ビュル酢酸、クロトン酸、ィタコン酸、無水ィタコン酸、マレイン酸、無水マレイン酸 、フマル酸、およびケィ皮酸である。不飽和有機酸 (B— 2)は、電磁波照射領域にお ける架橋剤との架橋性、および、電磁波非照射領域におけるアルカリ現像液との溶 解性をフッ素系ポリマー（B)に付与する。  [0034] The unsaturated organic acid (B-2) is a monomer having at least one carbon-carbon double bond and at least one acid group [eg, carboxyl group (COOH group)]. Particularly preferred examples of unsaturated organic acids are unsaturated carboxylic acids, such as free unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Examples of unsaturated organic acids (B-2) are (meth) acrylic acid, bulacetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, and kaycin acid. The unsaturated organic acid (B-2) imparts to the fluoropolymer (B) crosslinkability with a crosslinking agent in the electromagnetic wave irradiation region and solubility with an alkali developer in the nonelectromagnetic wave irradiation region.
[0035] 高軟化点モノマー（B— 3)は、  [0035] The high softening point monomer (B-3)
'ホモポリマーの状態でガラス転移点または融点が 100°C以上、特に 120°C以上の モノマー、  'Monomer with glass transition point or melting point of 100 ° C or higher, especially 120 ° C or higher in homopolymer state,
または、  Or
•CH =C(R1)COOR2 [Ι^:Ηまたは CH、 R2:炭素数 4〜20で水素原子に対する炭• CH = C (R 1 ) COOR 2 [Ι ^: Η or CH, R 2 : carbon with 4 to 20 carbon atoms for hydrogen atoms
2 3 twenty three
素原子の比率が 0.58以上の飽和アルキル基]である。  A saturated alkyl group having an atomic ratio of 0.58 or more.
R2の例は、イソボル-ル、ボル-ル、フェンシル (以上はいずれも C Η ,炭素原子 Examples of R 2 are isoborn, born, phensil (all of which are C,, carbon atoms
10 17  10 17
/水素原子 =0.58)、ァダマンチル (C Η ,炭素原子/水素原子 =0.66)、ノルボル- / Hydrogen atom = 0.58), adamantyl (C 炭素, carbon atom / hydrogen atom = 0.66), norvol
10 15 10 15
ル (C Η ,炭素原子/水素原子 =0.58)などの架橋炭化水素環が挙げられる。これら Bridged hydrocarbon rings such as ru (C Η, carbon atom / hydrogen atom = 0.58). these
7 12 7 12
の架橋炭化水素環に水酸基やアルキル基が付 、て 、ても良 、。  A hydroxyl group or an alkyl group may be attached to the crosslinked hydrocarbon ring.
[0036] 高軟化点モノマー（Β— 3)の例は、メチルメタタリレート、フエ-ルメタタリレート、シク 口へキシルメタタリレート、イソボル-ル (メタ)アタリレート、ノルボル-ル (メタ)アタリレー ト、およびァダマンチル (メタ)アタリレートである。ノルボルニル (メタ)アタリレートの例は[0036] Examples of high softening point monomers (Β-3) are methyl methacrylate, phenol methacrylate, hexamethyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) Atta relay And adamantyl (meth) acrylate. An example of norbornyl (meth) atarylate is
、 3—メチルーノルボル-ルメチル (メタ)アタリレート、ノルボル-ルメチル (メタ)アタリレ ート、ノルボル-ル (メタ)アタリレート、 1,3,3 トリメチルーノルボル-ル (メタ)アタリレ ート、ミルタ-ルメチル (メタ)アタリレート、イソピノカンファ -ル (メタ)アタリレート、 2— { [ 5— ( , 1 ' , 1，一トリフルォロ一 2，一トリフルォロメチル一 2，一ヒドロキシ）プロピル] ノルボル-ル }(メタ)アタリレートである。ァダマンチル (メタ)アタリレートの例は、 2—メ チル— 2—ァダマンチル (メタ)アタリレート、 2—ェチル— 2—ァダマンチル (メタ)アタリ レート、 3 ヒドロキシ一 1—ァダマンチル (メタ)アタリレート、 1—ァダマンチル一 at—ト リフルォロメチル (メタ)アタリレートである。 , 3-methyl-norbornyl methyl (meth) acrylate, norbornyl methyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3 trimethyl-norbornyl (meth) acrylate, milter -Rumethyl (meth) atarylate, isopinocamphor-l (meth) attalylate, 2— {[5— (, 1 ', 1, 1 trifluoro-1, 2, trifluoromethyl, 1, 2, hydroxy) propyl] Norbol} (meth) atarylate. Examples of adamantyl (meth) atalylate are: 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3 hydroxy-1 1-adamantyl (meth) acrylate, 1 —Adamantyl at-trifluoromethyl (meth) acrylate.
[0037] ガラス転移点、融点は、それぞれ JIS K7121— 1987「プラスチックの転移温度測 定方法」で規定される補外ガラス転移終了温度 (T )、融解ピーク温度 (T )とする。  [0037] The glass transition point and melting point are the extrapolated glass transition end temperature (T) and melting peak temperature (T) defined in JIS K7121-1987 "Method for measuring plastic transition temperature", respectively.
eg pm  eg pm
フッ素系ポリマー（B)の繰り返し単位に、ホモポリマーの状態でガラス転移点あるい は融点が 100°C以上の高軟ィ匕点モノマー（B— 3)を用いると、基板にを熱処理したと きの寸法安定性が優れる効果に加え、フッ素系モノマー（B— 1)の撥液性を向上す る効果ちある。  If a high-soft point monomer (B-3) having a glass transition point or a melting point of 100 ° C or higher in the homopolymer state is used as the repeating unit of the fluoropolymer (B), the substrate is heat-treated. In addition to the excellent dimensional stability, the liquid repellency of the fluorine-based monomer (B-1) is improved.
[0038] マクロモノマー（A— 5)をフッ素系モノマー（B— 1)として不飽和有機酸モノマー（B  [0038] Macromonomer (A-5) as fluorinated monomer (B-1) and unsaturated organic acid monomer (B
2)および高軟ィ匕点モノマー（B— 3)と共重合すると、フッ素系モノマー（B— 1)、不 飽和有機酸 (B— 2)、高軟化点モノマー (B— 3)それぞれの効果が高まる。  When copolymerized with 2) and high soft spot monomer (B-3), the effects of fluorine monomer (B-1), unsaturated organic acid (B-2), and high softening point monomer (B-3) Will increase.
マクロモノマーの f列として、 As f column of macromonomer,
CH3 CH3
CH2=C i  CH2 = C i
I I COOCH2CHCH2OCOCH2S -(CH2-C)n-H  I I COOCH2CHCH2OCOCH2S-(CH2-C) n-H
OH COOCH2CH2C4F9  OH COOCH2CH2C4F9
CH3 CH3
CH2=C  CH2 = C
COOCH2CHCH2OCOCH2S一 (CH2-CH)n - H COOCH2CHCH2OCOCH2S One (CH2-CH) n-H
I I OH COO(CH2)3S02C4F9  I I OH COO (CH2) 3S02C4F9
CH3 CH3
]  ]
CH2=C ci  CH2 = C ci
COOCH2CH2NHCOOCH2CH2S― (CH2-C)n - H  COOCH2CH2NHCOOCH2CH2S― (CH2-C) n-H
COOCH2CH2C4F9  COOCH2CH2C4F9
CH3 CH3
I I
CH2=C CH2 = C
I I
COOCH2CH2NHCOOCH2CH2S -(CH2-CH)n - H COOCH2CH2NHCOOCH2CH2S-(CH2-CH) n-H
COO(CH2)3S02C4F9 が例示される。マクロモノマー中のフッ素系モノマーの重合度 nは好ましくは 5〜20、 特に好ましくは 5〜 10である。  COO (CH2) 3S02C4F9 is exemplified. The degree of polymerization n of the fluorinated monomer in the macromonomer is preferably 5 to 20, particularly preferably 5 to 10.
[0039] 上記の二元または三元の共重合体であるフッ素系ポリマー（B)は、架橋剤 (C)、光 架橋触媒 (D)、および希釈剤 ωから成る組成物とすることが格段に好ま ヽ。 [0039] The fluorine-based polymer (B), which is the binary or ternary copolymer, is particularly preferably a composition comprising a crosslinking agent (C), a photocrosslinking catalyst (D), and a diluent ω. I like it.
[0040] 共重合体において、フッ素系モノマー（Β— 1)と不飽和有機酸（Β— 2)の重量比は 、 60 :40〜98 : 2、特【こ80 : 20〜95 : 5でぁってょ ヽ。  [0040] In the copolymer, the weight ratio of the fluorine-based monomer (Β-1) to the unsaturated organic acid (Β-2) is 60:40 to 98: 2, and the special weight ratio is 80:20 to 95: 5. Oh, ヽ
共重合体において、高軟ィ匕点モノマー（Β— 3)の量は、共重合体に対して、 0〜90 重量％、例えば 1〜80重量％、特に 10〜70重量％であってよい。  In the copolymer, the amount of the high soft spot monomer (Β-3) may be 0 to 90% by weight, for example 1 to 80% by weight, in particular 10 to 70% by weight, based on the copolymer. .
フッ素系ポリマー（Β)は、例えば、 フッ素系モノマー（B— 1) 20〜80重量0 /0、 Fluoropolymer (Β) is, for example, Fluorine monomer (B- 1) 20 to 80 weight 0/0,
不飽和有機酸 (B— 2) 5〜30重量％、および  5-30% by weight of unsaturated organic acid (B— 2), and
高軟化点モノマー（B— 3) 10〜70重量％  High softening point monomer (B-3) 10-70% by weight
からなつていてよい。  You can start.
[0041] フッ素系モノマー（B— 1)が 20〜80重量％であると、撥液性が高ぐかつフォトリソ グラフィー用表面処理剤を構成するその他の成分との相溶性が良好である。不飽和 有機酸モノマー (B— 2)が 5〜30重量％であると、電磁波照射領域における架橋剤 との架橋性が良好であり、および、電磁波非照射領域におけるアルカリ現像液との溶 解性が良好であり、撥液性が良好である。高軟化点モノマー（B— 3)が 10〜70重量 %であると、寸法安定性の効果が良好であり、撥液性が良好である。  [0041] When the fluorine-based monomer (B-1) is 20 to 80% by weight, the liquid repellency is high and the compatibility with other components constituting the surface treatment agent for photolithography is good. When the unsaturated organic acid monomer (B-2) is 5 to 30% by weight, the crosslinking property with the crosslinking agent in the electromagnetic wave irradiation region is good, and the solubility with the alkali developer in the non-electromagnetic wave irradiation region is good. And liquid repellency is good. When the high softening point monomer (B-3) is 10 to 70% by weight, the effect of dimensional stability is good and the liquid repellency is good.
[0042] 不飽和有機酸モノマー（B— 2)に加えて、 2—ヒドロキシェチル (メタ）アタリレート、 2  [0042] In addition to the unsaturated organic acid monomer (B-2), 2-hydroxyethyl (meth) acrylate, 2
ーヒドロキシプロピル (メタ）アタリレートのような水酸基を有するモノマーを（例えば 0. 1〜30重量％、特に、 0. 5〜25重量％の範囲で）共重合すると、モノマー（B— 2)の 電磁波照射領域における架橋剤との架橋性、および、電磁波非照射領域における アルカリ現像液との溶解性が増強される効果がある。  When a monomer having a hydroxyl group such as hydroxypropyl (meth) ate is copolymerized (for example, in the range of 0.1 to 30% by weight, particularly in the range of 0.5 to 25% by weight), the monomer (B-2) This has the effect of enhancing the cross-linking property with the cross-linking agent in the electromagnetic wave irradiation region and the solubility with the alkali developer in the non-electromagnetic wave irradiation region.
フッ素系ポリマー（B)の共重合体には、必要に応じて γ—メタクリロキシプロピルトリ メトキシシランに代表されるシラン基含有モノマー（例えば、 0. 1〜30重量0 /0)を共重 合しても良い。シラン基含有モノマーを共重合することにより、例えば、基板との密着 性が改善される。 Fluorine-based polymer is a copolymer of (B), optionally γ- methacryloxypropyl trimethoxysilane silane group-containing monomer represented (e.g., 0.1 to 30 weight 0/0) co Polymerization You may do it. By copolymerizing the silane group-containing monomer, for example, adhesion to the substrate is improved.
[0043] 參パターン某板の作製方法  [0043] Method for producing cocoon pattern stencil
第 1の要旨によれば、本発明においては、フッ素系モノマー (Α)またはフッ素系ポリ マー（Β)を用いて、例えば、次の方法により、表面自由エネルギーが異なる複数の領 域力ら構成されるノターン基板、言い換えると、パターン化された複数の撥液領域と 親液領域から成るパターン基板 (以下、単に「パターン基板」と省略する）を作製する  According to the first aspect, the present invention uses a fluorine monomer (Α) or a fluorine polymer (Β) to form a plurality of regional forces having different surface free energies, for example, by the following method. No pattern substrate, in other words, a patterned substrate composed of a plurality of patterned lyophobic and lyophilic regions (hereinafter simply referred to as “pattern substrate”).
[0044] 方法（1)： フッ素系ポリマー（Β)を希釈剤 C に溶解する。このフッ素系ポリマー溶 液を基板上に塗布して均一な撥液膜を形成し、フォトマスクを介して電磁波（例えば 、波長 172nmの真空紫外光)を照射すると、電磁波エネルギーと電磁波により発生す るオゾンの酸ィ匕作用により、照射領域のみが光分解して親液性となり、パターン基板 が得られる。光触媒技術を併用して、撥液膜の光分解を促進しても良い。 [0044] Method (1): Fluoropolymer (系) is dissolved in Diluent C. When this fluoropolymer solution is applied onto a substrate to form a uniform liquid-repellent film and irradiated with electromagnetic waves (for example, vacuum ultraviolet light having a wavelength of 172 nm) through a photomask, it is generated by electromagnetic energy and electromagnetic waves. Due to the acid action of ozone, only the irradiated area is photolyzed and becomes lyophilic, and a patterned substrate is obtained. A photocatalytic technique may be used in combination to promote photolysis of the liquid repellent film.
方法 (2)： フッ素系モノマー (A)、架橋剤 (C)、光架橋触媒 (D)を含有する組成物 (必要に応じて希釈剤 ωを加えても良 ヽ)を基板上に塗布して膜を形成し、フォトマ スクを介して電磁波を照射すると、照射領域のみが硬化して撥液膜となる。照射領域 には不溶で非照射領域のみを溶解する希釈剤 ωを用いて、非照射領域の膜を除 去する（現像)することにより、パターン基板が得られる。  Method (2): A composition containing a fluorine-based monomer (A), a crosslinking agent (C), and a photocrosslinking catalyst (D) (a diluent ω may be added if necessary) is applied on a substrate. When a film is formed and an electromagnetic wave is irradiated through a photomask, only the irradiated region is cured to form a liquid repellent film. A pattern substrate can be obtained by removing (developing) the film in the non-irradiated region using a diluent ω that is insoluble in the irradiated region and dissolves only the non-irradiated region.
[0045] 方法 (3)： 架橋性官能基 (Ε)を有するフッ素系ポリマー (Β)と光架橋触媒 (D)を希 釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上に塗布して撥液膜を形成し 、フォトマスクを介して電磁波を照射すると、照射領域のみが硬化する。非照射領域 のみを溶解する溶媒で現像することにより、パターン基板が得られる。  [0045] Method (3): A fluoropolymer (ポ リ マ ー) having a crosslinkable functional group (Ε) and a photocrosslinking catalyst (D) are dissolved in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. A pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
方法 (4)： 架橋性官能基 (Ε)を有するフッ素系ポリマー (Β)と架橋剤 (C)、光架橋 触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上に塗布して撥 液膜を形成し、フォトマスクを介して電磁波を照射すると、照射領域のみが硬化する。 非照射領域のみを溶解する溶媒で現像することにより、パターン基板が得られる。  Method (4): Fluoropolymer (Β) having a crosslinkable functional group (Ε), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. A pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
[0046] 方法 (5)： 酸性基 (F)と架橋性官能基 (Ε)を有するフッ素系ポリマー (Β)と架橋剤 Method (5): Fluoropolymer (Β) having acidic group (F) and crosslinkable functional group (Ε) and crosslinking agent
(C)、光架橋触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上 に塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射すると、照射領域の みが硬化する。非照射領域のみを溶解する溶媒で現像することにより、パターン基板 が得られる。  (C) The photocrosslinking catalyst (D) is dissolved in the diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. A pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated areas.
方法 (6)： 酸性基 (F)と架橋性官能基 (Ε)とシリコーン鎖 (G)を有するフッ素系ポ リマー (Β)と架橋剤 (C)、光架橋触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリ マー溶液を基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射す ると、照射領域のみが硬化する。非照射領域のみを溶解する溶媒で現像することに より、パターン基板が得られる。  Method (6): Fluorine polymer (Β) and crosslinker (C) having acid group (F), crosslinkable functional group (Ε) and silicone chain (G), photocrosslinking catalyst (D) as diluent ω Dissolve in When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. A pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated areas.
[0047] 方法 (7)： 酸性基 (F)を有するフッ素系ポリマー (Β)と架橋剤 (C)、光架橋触媒（ D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上に塗布して撥液膜 を形成し、フォトマスクを介して電磁波を照射すると、照射領域のみが硬化する。非照 射領域のみを溶解する溶媒で現像することにより、パターン基板が得られる。 [0047] Method (7): Dissolve the fluorine-containing polymer (Β) having an acidic group (F), the crosslinking agent (C), and the photocrosslinking catalyst (D) in the diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. Unlit A pattern substrate is obtained by developing with a solvent that dissolves only the projecting region.
方法 (8)： 酸性基 (F)とシリコーン鎖 (G)を有するフッ素系ポリマー (B)と架橋剤（ C)、光架橋触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上に 塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射すると、照射領域のみ が硬化する。非照射領域のみを溶解する溶媒で現像することにより、パターン基板が 得られる。  Method (8): A fluoropolymer (B) having an acidic group (F) and a silicone chain (G), a crosslinking agent (C), and a photocrosslinking catalyst (D) are dissolved in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. The pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region.
[0048] 方法 (9)： 酸性基 (F)と架橋性官能基 (Ε)を有するフッ素系ポリマー (Β)と光架橋 触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を基板上に塗布して撥 液膜を形成し、フォトマスクを介して電磁波を照射すると、照射領域のみが硬化する。 非照射領域のみを溶解する溶媒で現像することにより、パターン基板が得られる。 方法（10)： 酸性基 (F)と架橋性官能基 (Ε)とシリコーン鎖 (G)を有するフッ素系 ポリマー（Β)と光架橋触媒 (D)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を 基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射すると、照射 領域のみが硬化する。非照射領域のみを溶解する溶媒で現像することにより、パター ン基板が得られる。  [0048] Method (9): A fluorine-based polymer (Β) having an acidic group (F) and a crosslinkable functional group (Ε) and a photocrosslinking catalyst (D) are dissolved in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. A pattern substrate is obtained by developing with a solvent that dissolves only the non-irradiated region. Method (10): A fluorine-containing polymer (Β) having an acidic group (F), a crosslinkable functional group (Ε), and a silicone chain (G) and a photocrosslinking catalyst (D) are dissolved in the diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated area is cured. By developing with a solvent that dissolves only the non-irradiated areas, a patterned substrate can be obtained.
[0049] 方法（11)： 酸の作用によって酸性基に変換する酸解離基 (Η)を有するフッ素系 ポリマー（Β)、光酸発生剤 (I)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を 基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射すると、照射 領域のみが酸に解離して親液性となり、パターン基板が得られる。  [0049] Method (11): A fluorine-containing polymer (Β) having an acid dissociable group (Η) that is converted into an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid-repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
方法（12)： 酸の作用によって酸性基に変換する酸解離基 (Η)とシリコーン鎖 (G) を有するフッ素系ポリマー (Β)、光酸発生剤 (I)を希釈剤 ωに溶解する。このフッ素 系ポリマー溶液を基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を 照射すると、照射領域のみが酸に解離して親液性となり、パターン基板が得られる。  Method (12): Dissolve an acid dissociable group (Η) that is converted into an acid group by the action of an acid, a fluorine-containing polymer (Β) having a silicone chain (G), and a photoacid generator (I) in a diluent ω. When this fluorine-based polymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into acid and becomes lyophilic, and a patterned substrate is obtained.
[0050] 方法（13)： 酸の作用によって酸性基に変換する酸解離基 (Η)を有するフッ素系 ポリマー（Β)、光酸発生剤 (I)を希釈剤 ωに溶解する。このフッ素系ポリマー溶液を 基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を照射すると、照射 領域のみが酸に解離し、アルカリ水溶液に可溶となる。アルカリ水溶液で現像するこ とにより、ノターン基板が得られる。 方法（14)： 酸の作用によって酸性基に変換する酸解離基 (H)とシリコーン鎖 (G) を有するフッ素系ポリマー (B)、光酸発生剤 (I)を希釈剤 ωに溶解する。このフッ素 系ポリマー溶液を基板上に塗布して撥液膜を形成し、フォトマスクを介して電磁波を 照射すると、照射領域のみが酸に解離し、アルカリ水溶液に可溶となる。アルカリ水 溶液で現像することにより、パターン基板が得られる。 [0050] Method (13): A fluorine-containing polymer (Β) having an acid dissociable group (Η) that is converted to an acidic group by the action of an acid, and a photoacid generator (I) are dissolved in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into an acid and becomes soluble in an alkaline aqueous solution. By developing with an alkaline aqueous solution, a noturn substrate can be obtained. Method (14): Dissolve an acid dissociable group (H) that is converted into an acidic group by the action of an acid, a fluorine-based polymer (B) having a silicone chain (G), and a photoacid generator (I) in a diluent ω. When this fluoropolymer solution is applied onto a substrate to form a liquid repellent film and irradiated with electromagnetic waves through a photomask, only the irradiated region is dissociated into an acid and becomes soluble in an aqueous alkali solution. A pattern substrate is obtained by developing with an alkaline water solution.
[0051] (1)〜（14)の 、ずれの方法にぉ 、ても電磁波を照射する前 (プリベータ)や後（ボス トベータ）に 50〜250°C程度の熱処理を行っても良い。光酸発生剤を用いるときは同 じ温度範囲で PEB (Post Exposure Bake)処理を行っても良い。  [0051] According to the displacement method of (1) to (14), heat treatment at about 50 to 250 ° C may be performed before (pre-beta) or after (post-beta) irradiation of electromagnetic waves. When using a photoacid generator, PEB (Post Exposure Bake) treatment may be performed in the same temperature range.
[0052] 鲁架橋剤 (C)  [0052] Vaginal crosslinking agent (C)
架橋剤は単官能、または、好ましくは二個以上の官能基を有する化合物であり、ラ ジカル重合反応により硬化するタイプ力、あるいは、カチオン重合反応により硬化す るタイプであって良!、。前者は不飽和二重結合基であるアタリロイル基ゃビニル基が 官能基であり、後者はエポキシ基、ビニルエーテル基、ォキセタン基が官能基となり、 The cross-linking agent is a monofunctional or preferably a compound having two or more functional groups, and may be of a type force that cures by a radical polymerization reaction or a type that cures by a cationic polymerization reaction. In the former, an unsaturated double bond group, an taliloyl group, a vinyl group is a functional group, and in the latter, an epoxy group, a vinyl ether group, or an oxetane group is a functional group.
(a) ウレタン (メタ)アタリレート (a) Urethane (meth) acrylate
(b) エポキシ (メタ)アタリレート  (b) Epoxy (meth) acrylate
(c) ポリエステル (メタ）アタリレート  (c) Polyester (meth) acrylate
(d) ポリエーテル (メタ)アタリレート  (d) Polyether (meth) acrylate
(e) シリコーン (メタ)アタリレート  (e) Silicone (meth) acrylate
(D (メタ)アタリレートモノマー  (D (meth) acrylate monomer
(g) エポキシ系モノマー ( g ) Epoxy monomer
(h) ビニノレエーテノレ系モノマー  (h) Vinylenoetenore monomer
(0 ォキセタン系モノマー  (0 Oxetane monomer
に分類される。（a)〜(l)がラジカル重合反応で硬化するタイプであり、（g)〜(i)はカチォ ン重合反応により硬化するタイプである。  are categorized. (A) to (l) are types that cure by a radical polymerization reaction, and (g) to (i) are types that cure by a cationic polymerization reaction.
[0053] (a)〜(e)は榭脂に (メタ)アタリロイル基を付加したものであり、オリゴマー、ベースレジ ン、プレボリマーなどと表現されることが多い。 [0053] (a) to (e) are those obtained by adding a (meth) attalyloyl group to rosin, and are often expressed as oligomers, base resins, prepolymers, and the like.
[0054] (a) ウレタン (メタ)アタリレートは分子中にウレタン結合と (メタ)アタリロイル基を有す るものであり、トリス（2—ヒドロキシェチル)イソシァヌレートジアタリレート、トリス（2—ヒ ドロキシェチル)イソシァヌレートトリアタリレートに代表されるポリ〔(メタ)アタリロイルォ キシアルキル〕イソシァヌレートなどが例示される。 [0054] (a) Urethane (meth) atalylate has a urethane bond and a (meth) atalyloyl group in the molecule. Tris (2-hydroxyethyl) isocyanurate diatalylate, tris (2 —Hi Examples include poly [(meth) atalylooxyalkyl] isocyanurate, which is typified by droxychetyl) isocyanurate triatalylate.
[0055] (b) エポキシ (メタ）アタリレートはエポキシ基に (メタ)アタリロイル基を付カ卩したもので あり、出発原料としてビスフエノール A、ビスフエノール F、フエノールノボラック、脂環 化合物を用いたものが一般的である。  [0055] (b) Epoxy (meth) atalylate is obtained by adding an epoxy group with a (meth) atalyloyl group, and bisphenol A, bisphenol F, phenol novolak, and an alicyclic compound were used as starting materials. Things are common.
[0056] (c) ポリエステル (メタ）アタリレートは多価アルコールと多塩基酸力 なるエステル 榭脂に (メタ)アタリレートを付加したものである。多価アルコールは、エチレングリコー ル、 1,4 ブタンジオール、 1,6 へキサンジオール、ジエチレングリコール、トリメチロ ールプロパン、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコ ール、ペンタエリスリトール、ジペンタエリスリトールなどであり、多塩基酸は、フタル酸 [0056] (c) Polyester (meth) acrylate is a product obtained by adding (meth) acrylate to a polybasic acid and an ester resin having a polybasic acidity. Polyhydric alcohols include ethylene glycol, 1,4 butanediol, 1,6 hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, etc. Basic acid is phthalic acid
、アジピン酸、マレイン酸、トリメリット酸、ィタコン酸、コハク酸、テレフタル酸、ァルケ -ルコハク酸などである。 Adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alk-succinic acid, and the like.
[0057] (d) ポリエーテル (メタ)アタリレートはジオールのポリエーテル榭脂に (メタ)アタリレー トを付カ卩したものであり、ポリエチレングリコールジ (メタ)アタリレート、ポリプロピレンダリ コールジ (メタ)アタリレート、ポリエチレングリコール ポリプロピレングリコールジ (メタ） アタリレートなどが例示される。  [0057] (d) Polyether (meth) acrylate is a diol polyether resin with a (meth) atrelate added to it. Polyethylene glycol di (meth) acrylate and polypropylene diol diol (meth) Examples include attalylate, polyethylene glycol, polypropylene glycol di (meth) acrylate, and the like.
[0058] (e) シリコーン (メタ)アタリレートは、分子量 1,000〜10,000のジメチルポリシロキサン の片末端、あるいは、両末端を (メタ)アタリロイル基で変性したものであり、例えば、 以下のものが例示される。 (0058) (e) Silicone (meth) acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 modified at one end or both ends with a (meth) atallyloyl group. Is done.
[0059] CHs [0059] CHs
I I
CH2=C CHs CHs CHs CH2 = C CHs CHs CHs
I I I I COO-{CH2)3-Si-O^Si-0^ Si-CHs IIII COO- {CH 2 ) 3-Si-O ^ Si-0 ^ Si-CHs
CHs CH3 CH3  CHs CH3 CH3
CH3  CH3
I I
CH2=C CHs CHs CHs CH2 = C CHs CHs CHs
I I I I COO-(CH2)3-Si-0 -^ShO ^ Si-C2Hs IIII COO- (CH 2 ) 3-Si-0-^ ShO ^ Si-C2Hs
CH3 CHs CHs  CH3 CHs CHs
CH3 CH3 CH3 CH3
I I CH2=C CHs CHs CHs C=Chb  I I CH2 = C CHs CHs CHs C = Chb
I I I I I I I I I I
COO-(CH2)3-Si-0 -(Si-O ^ Si-(CH2)3-OCO COO- (CH 2 ) 3-Si-0-(Si-O ^ Si- (CH 2 ) 3 -OCO
CHs CHs CHs  CHs CHs CHs
[0060] (D (メタ)アタリレートモノマーは、単官能あるいは多官能のアルキル (メタ)アタリレー トゃ、 500mPa s (25°C)以下の低粘度ポリエーテル (メタ)アタリレートであり、メチル (メタ )アタリレート、ェチル (メタ）アタリレート、 n—プロピル (メタ）アタリレート、イソプロピル (メタ）アタリレート、 n—ブチル (メタ）アタリレート、イソブチル (メタ）アタリレート、 sec— ブチル (メタ）アタリレート、 t—ブチル (メタ）アタリレート、 n—ペンチル (メタ）アタリレー ト、 3—メチルブチル (メタ）アタリレート、 n—へキシル (メタ）アタリレート、 2—ェチルー n—へキシル (メタ）アタリレート、 n—ォクチル (メタ）アタリレート、シクロへキシル (メタ） アタリレート、イソボル-ル (メタ）アタリレート、ベンジル (メタ)アタリレート、 2—ヒドロキ シェチル (メタ）アタリレート、 2—ヒドロキシプロピル (メタ）アタリレート、 3—ヒドロキシ プロピル (メタ）アタリレート、 4—ヒドロキシブチル (メタ）アタリレート、 5—ヒドロキシぺ ンチル (メタ）アタリレート、 6—ヒドロキシへキシル (メタ）アタリレート、 4—ヒドロキシシク 口へキシル (メタ）アタリレート、ネオペンチルグリコールモノ（メタ）アタリレート、 3—クロ 口— 2—ヒドロキシプロピル (メタ）アタリレート、 (1, 1—ジメチルー 3—ォキソブチル）（ メタ）アクリルレート、 2—ァセトァセトキシェチル (メタ）アタリレート、 2—メトキシェチル (メタ）アタリレート、 2—エトキシェチル (メタ）アタリレート、ネオペンチルグリコールモ ノ (メタ）アタリレート、 3—クロ口一 2—ヒドロキシプロピル (メタ）アタリレート、グリセリン モノ（メタ）アタリレート、エチレングリコールジアタリレート、プロピレングリコールジァク リレート、 1,6 へキサンジオールジアタリレート、 1,9ーノナンジオールジアタリレート 、 1,10—デカンジオールジアタリレート、トリメチロールプロパントリアタリレート、ペン タエリスリトールテトラアタリレートなどが例示される。 (0060) (D (meth) acrylate monomer is a monofunctional or polyfunctional alkyl (meth) atrelate, a low viscosity polyether (meth) acrylate having a viscosity of 500 mPa s (25 ° C) or less, methyl ( Meta) Atylate, Ethyl (Meth) Atylate, n-Propyl (Meth) Atalylate, Isopropyl (Meth) Atalylate, n-Butyl (Meth) Atylate, Isobutyl (Meth) Atalylate, sec— Butyl (Meth) Atalylate, t-butyl (meth) atarylate, n-pentyl (meth) atrelate, 3-methylbutyl (meth) atarylate, n-hexyl (meth) atalylate, 2-ethylyl n-hexyl (meth) Atalylate, n-octyl (meth) atarylate, cyclohexyl (meth) attalylate, isobornyl (meth) acrylate, benzyl (meth) aterelate 2-hydroxychetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy propyl (meth) acrylate, 4-hydroxy butyl (meth) acrylate, 5-hydroxy pentyl (meth) Atalylate, 6-Hydroxyhexyl (meth) atarylate, 4-Hydroxysic Oral hexyl (meth) attalylate, Neopentylglycol mono (meth) attalylate, 3—Black mouth—2-Hydroxypropyl (meth) atari (1, 1-dimethyl-3-oxobutyl) (meth) acrylate, 2-acetocetoxychetyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy ethyl (meth) acrylate, neo Pentylglycol mono (meth) acrylate, 3—black mouth 2—hydroxy group Lopyr (meth) acrylate, glycerin Mono (meth) acrylate, ethylene glycol ditalylate, propylene glycol diacrylate, 1,6 hexanediol ditalylate, 1,9-nonanediol ditalylate, 1,10-decanediol ditalylate, Examples include trimethylolpropane tritalylate, pentaerythritol tetraatalylate and the like.
[0061] (g) エポキシ系モノマーは、ビスフエノール A、ビスフエノール F、レゾルシノール、フ エノールノボラック、クレゾ一ルノボラックなどのフエノール類のグリシジルエーテル；ブ タンジオール、ポリエチレングリコール、ポリプロピレングリコールなどのアルコール類 のグリシジルエーテル；フタル酸、イソフタル酸、テトラヒドロフタル酸などのカルボン 酸のグリシジルエステル等のエポキシモノマーやこれらのオリゴマーもしくは脂環型ェ ポキシドを挙げることができる。中でも、ビスフエノール Aグリシジルエーテルモノマー もしくはオリゴマーを好ましく使用できる。具体的には、油化シェル社製造のェピコ一 卜 828 (分子量 380)、ェピコ一卜 834 (分子量 470)、ェピコ一卜 1001 (分子量 900)、 ェピコ一卜 1002 (分子量 1, 060)、ェピコ一卜 1055 (分子量 1, 350)、ェピコ一卜 100 7 (分子量 2, 900)などが例示される。  [0061] (g) Epoxy monomers are glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolak, cresolol novolak; alcohols such as butanediol, polyethylene glycol, and polypropylene glycol. Ethers: epoxy monomers such as glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid, and oligomers or alicyclic epoxides thereof. Among them, bisphenol A glycidyl ether monomer or oligomer can be preferably used. Specifically, Epico の 828 (molecular weight 380), Epico 卜 834 (molecular weight 470), Epico 卜 1001 (molecular weight 900), Epico 卜 1002 (molecular weight 1,060), Epico Illustrative are 1055 (molecular weight 1,350) and Epico 100 100 (molecular weight 2,900).
[0062] (h) ビュルエーテル系モノマーは、 2 ヒドロキシェチルビ-ルエーテル、 4 ヒドロ キシブチルビニルエーテル、シクロへキサンジオールモノビニルエーテル、シス 1, 1, 3 トリメチル 5 ビニルォキシシクロへキサン、トランス一 1, 1, 3 トリメチル一 5 -ビュルォキシシクロへキサン、 1—イソプロピル - 4 メチル - 2-ビュルォキシシ クロへキサン、 2 ビュルォキシ 7—ォキサビシクロ [3. 2. 1]オクタンー6 オン、 2 メチル 2—ビュルォキシァダマンタン、 2—ェチル 2—ビュルォキシァダマンタ ン、 1, 3 ビス（ビュルォキシ）ァダマンタン、 1—ビュルォキシァダマンタノール、 3— ビュルォキシ 1—ァダマンタノール、 1, 3, 5 トリス（ビュルォキシ）ァダマンタン、 3, 5 ビス（ビュルォキシ）一1 ァダマンタノール、 5 ビュルォキシ 1, 3 ァダ マンタンジオール、 1, 3, 5, 7—テトラキス（ビュルォキシ）ァダマンタン、 3, 5, 7 ト リス（ビュルォキシ） 1 ァダマンタノール、 5, 7 ビス（ビュルォキシ） 1 , 3 ァ ダマンタンジオール、 7 ビュルォキシ 1, 3, 5 ァダマンタントリオール、 1, 3 ジ メチル 5 ビュルォキシァダマンタン、 1, 3 ジメチルー 5, 7 ビス（ビュルォキシ )ァダマンタン、 3, 5 ジメチルー 7 ビュルォキシ 1—ァダマンタノール、 1—カル ボキシ 3 ビュルォキシァダマンタン、 1 ァミノ 3 ビュルォキシァダマンタン、 1 -トロー 3 ビ-ノレオキシァダマンタン、 1ースノレホ 3 ビニノレオキシァダマンタ ン、 1 t—ブチルォキシカルボ-ルー 3 ビュルォキシァダマンタン、 4 ォキソ 1 ビュルォキシァダマンタン、 1 ビュルォキシ 3—（1ーメチルー 1 ビュルォキシ ェチル）ァダマンタン、 1 （ビュルォキシメチル）ァダマンタン、 1 1—メチルー 1 ビュルォキシェチル）ァダマンタン、 1 1 ェチル 1 ビュルォキシェチル）ァダ マンタン、 1, 3 ビス（1—メチル 1—ビュルォキシェチル）ァダマンタン、 1— (1— (ノルボルナン— 2—ィル）—1—ビュルォキシェチル）ァダマンタン、 2, 5 ビス（ビ -ルォキシ）ノルボルナン、 2, 3 ビス（ビュルォキシ）ノルボルナン、 5—メトキシカル ボ-ルー 2—ビュルォキシノルボルナン、 2—（1 （ノルボルナン 2—ィル） 1 ビュルォキシェチル）ノルボルナン、 2—（ビュルォキシメチル）ノルボルナン、 2—（1 -メチル— 1—ビュルォキシェチル）ノルボルナン、 2— ( 1—メチル— 1—ビュルォキ シペンチル）ノルボルナン、 3 ヒドロキシ一 4 ビュルォキシテトラシクロ [4. 4. 0. 1 2, 5. 17, 10]ドデカン、 3, 4 ビス（ビュルォキシ）テトラシクロ [4. 4. 0. 12, 5. 17 , 10]ドデカン、 3 ヒドロキシ— 8 ビュルォキシテトラシクロ [4. 4. 0. 12, 5. 17, 1 0]ドデカン、 3, 8 ビス（ビュルォキシ）テトラシクロ [4. 4. 0. 12, 5. 17, 10]ドデカ ン、 3—メトキシカルボ-ルー 8 ビュルォキシテトラシクロ [4. 4. 0. 12, 5. 17, 10] ドデカン、 3—メトキシカルボ二ルー 9ービニルォキシテトラシクロ [4. 4. 0. 12, 5. 1 7, 10]ドデカン、 3— (ビュルォキシメチル）テトラシクロ [4. 4. 0. 12, 5. 17, 10]ド デカン、 3 ヒドロキシメチル一 8 ビニルォキシテトラシクロ [4. 4. 0. 12, 5. 17, 1 0]ドデカン、 3 ヒドロキシメチル一 9 ビュルォキシテトラシクロ [4. 4. 0. 12, 5. 1 7, 10]ドデカン、 8 ヒドロキシ一 3— (ビュルォキシメチル）テトラシクロ [4. 4. 0. 12 , 5. 17, 10]ドデカン、 9 ヒドロキシ一 3— (ビュルォキシメチル）テトラシクロ [4. 4. 0. 12, 5. 17, 10]ドデカン、 8 ビュルォキシ—4—ォキサトリシクロ [5. 2. 1. 02, 6]デカン一 3, 5 ジオン、 4 ビュルォキシ 11—ォキサペンタシクロ [6. 5. 1. 13 , 6. 02, 7. 09, 13]ペンタデカン— 10, 12 ジオン、 ビュルォキシ—γ , γ - ジメチルー γ ブチロラタトン、 α , γ , γ トリメチルー α ビニルォキシ γ—ブ チロラタトン、 γ , γ—ジメチル一 /3—メトキシカルボ-ルー (X—ビニルォキシ一 γ - ブチロラタトン、 8 ビュルォキシ 4—ォキサトリシクロ [5. 2. 1. 02, 6]デカン一 3 —オン、 9 ビュルォキシ 4—ォキサトリシクロ [5. 2. 1. 02, 6]デカン一 3—オン、 8, 9 ビス（ビュルォキシ）一4—ォキサトリシクロ [5. 2. 1. 02, 6]デカン一 3—オン 、4 ビュルォキシ 2, 7 ジォキサビシクロ [3. 3. 0]オクタン一 3, 6 ジオン、 5 —ビュルォキシ 3—ォキサトリシクロ [4. 2. 1. 04, 8]ノナン一 2—オン、 5—メチル —5 ビュルォキシ 3—ォキサトリシクロ [4. 2. 1. 04, 8]ノナン一 2—オン、 9—メ チル一 5 ビュルォキシ 3—ォキサトリシクロ [4. 2. 1. 04, 8]ノナン一 2—オン、 6 —ビュルォキシ 3—ォキサトリシクロ [4. 3. 1. 14, 8]ゥンデカン一 2—オン、 6, 8 —ビス（ビュルォキシ）一3—ォキサトリシクロ [4. 3. 1. 14, 8]ゥンデカン一 2—オン 、 6 ヒドロキシ一 8 ビュルォキシ 3—ォキサトリシクロ [4. 3. 1. 14, 8]ゥンデ力 ン一 2—オン、 8 ヒドロキシ一 6 ビュルォキシ 3—ォキサトリシクロ [4. 3. 1. 14, 8]ゥンデカン 2 オン、及びこれらに対応するイソプロぺニルエーテル類などが例 示される。 (H) The butyl ether monomer includes 2 hydroxyethyl vinyl ether, 4 hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, cis 1,1,3 trimethyl 5 vinyloxycyclohexane, trans 1, 1, 3 Trimethyl mono 5 -Buroxycyclohexane, 1—Isopropyl-4 methyl-2-Buroxy chlorohexane, 2 Buroxy 7—Oxabicyclo [3.2.1] octane-6one, 2 Methyl 2— Buloxiadamantane, 2-Ethyl 2—Buloxiadamantane, 1, 3 Bis (Buroxy) adamantane, 1—Buroxiadamantanol, 3—Buroxydamantanol, 1, 3 , 5 Tris (Buroxy) adamantane, 3, 5 Bis (Buroxy), 1 Adamantanol, 5 Buruoxy 1, 3 Ada Manta Diol, 1, 3, 5, 7-tetrakis (buloxy) adamantane, 3, 5, 7 tris (buroxy) 1 adamantanol, 5, 7 bis (buroxy) 1,3 adamantanediol, 7 buroxy 1, 3,5 adamantanetriol, 1,3 dimethyl 5 buraxadamantane, 1,3 dimethyl-5,7 bis (buloxy) adamantane, 3,5 dimethyl-7 buroxy 1-adamantanol, 1-cal Boxy 3 buroxadamantane, 1 Amano 3 Buroxy damantane, 1 -Trow 3 Binoleoxy damantane, 1 Snorejo 3 Vininoreoxy damantane, 1 t-Butyloxycarbo- Lou 3 Buruxadamantane, 4 oxo 1 Bruxia damantane, 1 Buruoxy 3— (1-methyl-1 buruoxyethyl) adamantane, 1 (Buloxymethyl) adamantane, 1 1—Methyl-1 buroxie Chill) adamantane, 1 1 ethyl 1 buhlochetyl) adamantane, 1, 3 bis (1-methyl-1-buruoxychetil) adamantane, 1— (1— (norbornane—2-yl) — 1-Burowuchetyl) adamantane, 2,5 Bis (bioxy) norbornane, 2,3 Bis (Buoxy) norbornane, 5-Methoxycarboru 2 Buruoxynorbornane, 2— (1 (Norbornane 2—yl) 1 Buruoxychetyl) norbornane, 2— (Buroxymethyl) norbornane, 2— (1 -Methyl—1—Bulucetil) Norbornane, 2— (1-Methyl—1-Buloxycypentyl) norbornane, 3 Hydroxy 4-Buroxytetracyclo [4. 4. 0. 1 2, 5. 17, 10] Dodecane, 3, 4 Bis (Buloxy) Tetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 3 hydroxy-8 butyloxytetracyclo [4. 4. 0. 12, 5. 17, 1 0] dodecane, 3, 8 bis ( (Buloxy) tetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 3-methoxycarboro 8 Buroxytetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 3—Methoxycarbonyl 9-vinyloxytetracyclo [4. 4. 0. 12, 5. 1 7, 10] dodecane, 3— (Bule Oxymethyl) tetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 3 hydroxymethyl mono8 vinyloxytetracyclo [4. 4. 0. 12, 5. 17, 1 0] dodecane, 3 Hydroxymethyl mono 9 -Buroxytetracyclo [4. 4. 0. 12, 5. 1 7, 10] Dodecane, 8 Hydroxy mono 3- (Buroxymethyl) tetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 9 hydroxy-l 3-(Buroxymethyl) tetracyclo [4. 4. 0. 12, 5. 17, 10] dodecane, 8 buloxy-4-oxatricyclo [5. 2. 1. 02, 6] Decane 3,5 dione, 4 Buroxy 11-Oxapentacyclo [6. 5. 1. 13, 6. 02, 7. 09, 13] Pentadecane-10, 12 Dione, Buroxy-γ, γ-Dimethyl gamma Buchirorataton, α, γ, γ trimethyl-alpha Biniruokishi γ- Bed Chirorataton, gamma, gamma - dimethyl one / 3-methoxycarbonyl - Lu (X- Biniruo Shi one γ - Butyrolataton, 8 buroxy 4-oxatricyclo [5. 2. 1. 02, 6] decane 3-one, 9 buroxy 4-oxatricyclo [5. 2. 1. 02, 6] decane 3-one, 8, 9 bis (Buloxy) 1-Oxatricyclo [5. 2. 1. 02, 6] Decan 1-3-, 4 Buloxy 2, 7 Dioxabicyclo [3. 3. 0] Octane 1,3 Dione, 5 —Buloxy 3-Oxatricyclo [4. 2. 1. 04, 8] Nonane-2-one, 5-methyl-5-Buloxy 3-oxatricyclo [4. 2. 1. 04, 8] Nonane-2-2-one, 9-Methyl-5-Buroxy 3-Oxatricyclo [4. 2. 1. 04, 8] Nonane-2-one, 6-Buloxy 3-Oxatricyclo [4. 3. 1. 14, 8] Undecane-2-one, 6, 8—Bis (Buloxy ) 1-Oxatricyclo [4. 3. 1. 14, 8] undecane 1 2-one, 6 hydroxy 1 8 buroxy 3 Oxatricyclo [4. 3. 1. 14, 8] unde force 2-one, 8-hydroxy-6 buroxy 3-buxatricyclo [4. 3. 1. 14, 8] undecane 2 on and the corresponding isoprop Examples include nyl ethers.
[0063] (0 ォキセタン系モノマーは、 1,4 ビス {[(3—ェチルー 3—ォキセタ -ル)メトキシ]ェ チル }ベンゼン（東亞合成製ァロンォキセタン OXT - 121) , 3-ェチル 3—ヒドロキシ メチルォキセタン (東亞合成製ァロンォキセタン OXT— 101)などが例示される。  [0063] (0 oxetane-based monomers are 1,4 bis {[(3-ethyl-3-oxeta-l) methoxy] ethyl} benzene (Aronoxetane OXT-121) manufactured by Toagosei Co., Ltd., 3-ethyl 3-hydroxymethyloxetane ( Examples include Tolonsei Alonoxetane OXT-101).
[0064] また、フッ素系ポリマー中に酸が含まれる場合は、架橋剤に酸架橋剤を用いても良 い。酸架橋剤は、一分子中に酸性基と架橋する複数 (例えば 2〜10)の反応基 (例え ば、カルボン酸、水酸基、アミノ基、イソシァネート基、 N—メチロール基、アルキルェ ーテルイ匕した N—メチロール基、エポキシ基など）を有する化合物、あるいは、酢酸の 多価金属塩であり、アミノ榭脂、エポキシィ匕合物、ォキサゾリンィ匕合物、酢酸アルミ- ゥムなどが例示される。  [0064] When an acid is contained in the fluoropolymer, an acid crosslinking agent may be used as the crosslinking agent. The acid crosslinking agent includes a plurality of (for example, 2 to 10) reactive groups (for example, carboxylic acid, hydroxyl group, amino group, isocyanate group, N-methylol group, alkyl ether group N—) that crosslink with an acidic group in one molecule. A compound having a methylol group, an epoxy group, or the like) or a polyvalent metal salt of acetic acid, and examples thereof include amino resins, epoxy compounds, oxazoline compounds, aluminum acetate, and the like.
[0065] アミノ榭脂としては、メラミン系化合物、グアナミン系化合物、尿素系化合物等のアミ ノ基の一部もしくはすべてをヒドロキシメチルイ匕したィ匕合物、または該ヒドロキシメチル 化した化合物の水酸基の一部もしくはすべてをメタノール、エタノール、 n—ブチルァ ルコール、 2—メチルー 1 プロパノール等でエーテル化した化合物、例えば、へキ サメトキシメチルメチロールメラミンであり、 日本サイテックインダストリーズ製のアルキ ル型、メチロール型、ィミノ型の各種アミノ榭脂などが挙げられる。 [0066] エポキシ化合物としては、ビスフエノール A型エポキシ榭脂、ビスフエノール F型ェ ポキシ榭脂、フエノール'ノボラック型エポキシ榭脂、タレゾール 'ノボラック型エポキシ 榭脂、トリスフエノールメタン型エポキシ榭脂、臭素化エポキシ榭脂等のグリシジルェ ーテノレ類、 3, 4 エポキシシクロへキシノレメチノレー 3, 4—エポキシシクロへキサン力 ルボキシレート、ビス（2, 3 エポキシシクロペンチル）エーテルなどの脂環式ェポキ シ榭月旨、ジグリシジノレへキサヒドロフタレート、ジグリシジルテトラヒドロフタレート、ジグ リシジルフタレート等のグリシジルエステル類、テトラグリシジルジアミノジフエニルメタ ン、トリグリシジルバラァミノフエノール等のグリシジルァミン類、トリグリシジルイソシァ ヌレートなどの複素環式エポキシ榭脂などが挙げられる。 [0065] Examples of amino succinic acid include compounds obtained by hydroxymethylating a part or all of amino groups such as melamine compounds, guanamine compounds and urea compounds, or hydroxyl groups of the hydroxymethylated compounds. A compound obtained by etherifying a part or all of this with methanol, ethanol, n-butyl alcohol, 2-methyl-1 propanol, etc., for example, hexamethoxymethyl methylol melamine, an alkyl type or a methylol type made by Nippon Cytec Industries. And various amino coffins of imino type. [0066] Epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol 'novolac type epoxy resin, talesol' novolac type epoxy resin, trisphenol methane type epoxy resin, bromine Glycidyl etherols such as epoxidized epoxy resin, 3, 4 epoxycyclohexenolemethinole 3, 4-epoxycyclohexane strength ruboxylate, bis (2, 3 epoxycyclopentyl) ether, etc. Glycidyl esters such as diglycidinolehexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate, glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylvalaminophenol, triglycidyl isocyanurate, etc. Such as heterocyclic type epoxy 榭脂 the like.
ォキサゾリン化合物としては、 2 ビ-ルー 2—ォキサゾリン、 2 ビ-ルー 4ーメチ ルー 2—ォキサゾリン、 2 ビニルー 5—メチルー 2—ォキサゾリン、 2 イソプロぺニ ルー 2 ォキサゾリン、 2 イソプロべ-ル 4 メチル 2 ォキサゾリン等の重合 性単量体の共重合体を挙げることができる。  The oxazoline compounds include 2-bi-ro 2-oxazoline, 2-bi-ro 4-methyl lu 2--oxazoline, 2-vinyl 5--methyl-2-oxazoline, 2-isopropenyl lu 2-oxazoline, 2-iso-probe 4 methyl 2-oxazoline And a copolymer of polymerizable monomers such as
本発明の架橋剤に 1,4—ビス (3—メルカプトブチリルォキシ)ブタン、ペンタエリスリト ールテトラキス (3—メルカプトプチレート)のような多感能チオールを併用すると、硬化 速度が向上する。多感能チオールの量は、たとえば、架橋剤 100重量部に対して 0. 1〜20重量部、例えば 1〜 10重量部であってよい。  When a multi-sensitive thiol such as 1,4-bis (3-mercaptobutyryloxy) butane or pentaerythritol tetrakis (3-mercaptopropylate) is used in combination with the crosslinking agent of the present invention, the curing speed is improved. The amount of the multi-sensitive thiol may be, for example, 0.1 to 20 parts by weight, for example 1 to 10 parts by weight with respect to 100 parts by weight of the crosslinking agent.
[0067] 架橋剤は、フッ素系モノマーと併用する場合はフッ素系モノマー 100重量部に対し て、 1〜： LOO, 000重量咅^特に 10〜： L00, 000重量咅である。また、フッ素系ポジマ 一と併用する場合はフッ素系ポリマー 100重量部に対して、 1〜： L00重量部、特に 1 〜 20重量部である。  [0067] When used in combination with a fluorinated monomer, the cross-linking agent is 1 to LOO, 000 parts by weight, particularly 10 to L00, 000 parts by weight with respect to 100 parts by weight of the fluorinated monomer. When used in combination with a fluorine-based polymer, it is 1 to L00 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the fluorine-based polymer.
[0068] · 娜體 (D)  [0068] · 娜 體 (D)
光架橋触媒はラジカル光重合開始剤と光酸発生剤が例示される。ラジカル光重合 開始剤は、光によりラジカルを発生する化合物であり、例えば、ベンジル、ジァセチル 等の OC—ジケトン類、ベンゾイン等のァシロイン類、ベンゾインメチルエーテル、ベン ゾインェチルエーテル、ベンゾインイソプロピルエーテル等のァシロインエーテル類、 チォキサントン、 2, 4 ジェチルチオキサントン、チォキサントン 4ースルホン酸等 のチォキサントン類、ベンゾフエノン、 4, 4， 一ビス（ジメチルァミノ）ベンゾフエノン、 4, 4，一ビス（ジェチルァミノ）ベンゾフエノン等のベンゾフエノン類、ァセトフエノン、 2— ( 4 トルエンスルホ -ルォキシ） 2 フエ-ルァセトフエノン、 p ジメチルアミノアセト フエノン、 2, 2，ージメトキシー 2—フエ-ルァセトフエノン、 p—メトキシァセトフエノン、 2 メチル [4 （メチルチオ）フエ-ル ] 2 モルフオリノー 1 プロパノン、 2 ベン ジル一 2—ジメチルァミノ一 1— (4—モルフォリノフエ-ル）一ブタン一 1—オン等のァ セトフエノン類、アントラキノン、 1, 4 ナフトキノン等のキノン類、 2 ジメチルァミノ安 息香酸ェチル、 4ージメチルァミノ安息香酸ェチル、 4ージメチルァミノ安息香酸 (n— ブトキシ)ェチル、 4ージメチルァミノ安息香酸イソァミル、 4ージメチルァミノ安息香酸 2—ェチルへキシル等のアミノ安息香酸類、フエナシルクロライド、トリハロメチルフエ ニルスルホン等のハロゲン化合物、ァシルホスフィンォキシド類、ジー t—ブチルパー オキサイド等の過酸ィ匕物等が挙げられる。市販品としては、 IRGACURE— 184、同 261、同 369、同 500、同 651、同 907 (以上、チノく—ガイギー製）、 Darocur— 117 3、同 1116、同 2959、同 1664、同 4043 (以上、メノレクジヤノン製）など力 ^挙げゝられ る。 Examples of the photocrosslinking catalyst include a radical photopolymerization initiator and a photoacid generator. Radical photopolymerization initiators are compounds that generate radicals by light, such as OC-diketones such as benzyl and diacetyl, acyloines such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Thiaxanthones such as thixanthone, 2, 4 jetylthioxanthone, thixanthone 4-sulfonic acid, benzophenone, 4, 4, monobis (dimethylamino) benzophenone, 4, Benzophenones such as 4, 1-bis (jetylamino) benzophenone, acetophenone, 2- (4 toluenesulfo-ruxoxy) 2 pheulacetophenone, p dimethylaminoacetophenone, 2, 2, -dimethoxy 2-phenol-lucacetophenone, p-methoxya Cetofenones such as cetophenone, 2 methyl [4 (methylthio) phenol] 2 morpholino 1 propanone, 2 benzil 2-dimethylamino 1- (4-morpholinophenol) 1-butane 1-one, To quinones such as anthraquinone and 1,4 naphthoquinone, 2 ethyl dimethylaminobenzoate, 4-dimethylaminobenzoyl ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethyl Aminobenzoic acids such as xylyl, No chloride, halogen compounds such as trihalomethyl Hue vinyl sulfonic, § sill phosphine O nitroxide compound, peracids I 匕物 such as di-t- Buchirupa oxide. Commercially available products include IRGACURE-184, 261, 369, 500, 651, 907 (above, manufactured by Chinoku-Geigy), Darocur-117 3, 1116, 2959, 1664, 4043 ( As mentioned above, the power of MenorekJianon) is raised.
[0069] 光酸発生剤 [Photochemical acid generator(PAG)]は光をあてることによって反応し 酸を発生する材料である。 PAGは、光を吸収する発色団と分解後に酸となる酸前駆 体より構成されており、このような構造の PAGに特定波長の光を照射することで、 PAG が励起し酸前駆体部分から酸を発生する。 PAGは、例えば、ジァゾニゥム塩、ホスホ -ゥム塩、スルホ -ゥム塩、ョードニゥム塩、 CF SO p— CH PhSO p— NO PhSO  [0069] A photoacid generator (PAG) is a material that generates acid by reacting with light. PAG is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating light of a specific wavelength to PAG with such a structure, PAG is excited and the acid precursor part begins. Generates acid. PAG is, for example, diazonium salt, phospho-um salt, sulfo-um salt, iodonium salt, CF SO p—CH PhSO p—NO PhSO
3 3、 3 3、 2 3 3, 3 3, 2
(ただし、 phはフエ-ル基)等の塩、有機ハロゲンィ匕合物、オルトキノンージアジドス(Where ph is a phenyl group), etc., organic halogen compounds, orthoquinone-diazidos
3 Three
ルホニルクロリド、またはスルホン酸エステル等を挙げることができる。  Examples thereof include sulfonyl chloride or sulfonic acid ester.
[0070] 前記有機ハロゲン化合物は、ハロゲンィ匕水素酸を形成する化合物であり、かかる化 合物は、米国特許第 3, 515, 551号、米国特許第 3, 536, 489号、米国特許第 3, 779, 778号および西ドイツ特許公開公報第 2, 243, 621号等に開示されたものが挙げられ る（これらの開示を本明細書の一部とする）。 [0070] The organic halogen compound is a compound forming a halogen hydrohydroacid, and such compounds are disclosed in US Pat. No. 3,515,551, US Pat. No. 3,536,489, US Pat. , 779, 778 and West German Patent Publication No. 2,243,621, etc. (the disclosures of which are incorporated herein).
前記記載の他の光の照射により酸を発生する化合物は、特開昭 54— 74728号、特 開昭 55— 24113号、特開昭 55— 77742号、特開昭 60— 3626号、特開昭 60— 138539 号、特開昭 56— 17345号および特開昭 56— 36209号に開示されている（これらの開示 を本明細書の一部とする)。 Other compounds that generate an acid upon irradiation with light described above are disclosed in JP 54-74728, JP 55-24113, JP 55-77742, JP 60-3626, JP Disclosed in Sho 60-138539, Sho 56-17345 and Sho 56-36209 (disclosures thereof) As part of this specification).
[0071] PAGの市販品として、和光純薬製の WPAG— 145[Bis(cyclohexylsulfonyl)diazometh ane]、 WPAG - 170[Bis(t - butylsulfonyl)diazomethane] , WPAG— 199[Bis(p— toluene sulfonyOdiazomethane]、 WPA 281 [Triphenylsulfonium trifluoromethanesulfonate] 、 WPAG― 336[Diphenyl— 4— methylphenylsulfonium trifluoromethanesulfonate]、 WP AG— 367[Diphenyl— 2,4,6— trimethylphenylsulfonium p— toluenesulfonate]、チバ · スぺシャリティ ·ケミカルズ社製の CGI— 1397 [(5 プロピルスルフォ -ルォキシィミノ — 5H チォフェン— 2—イリデン)―（2—メチルフエ-ル)ァセトニトリル]、三和ケミカ ル製の TFE -トリァジン [2— [2— (Furan— 2— yl)ethenyl]— 4,6— bis(trichloromethyl) - s - triazine]、 TME -トリァジン [2— [2— (5— Methylluran— 2— yl)ethenyl]— 4,6— b is(tnchloromethyl)― s— triazinej MP—トリ ,ソン [2― (Methoxyphenyl)— 4,6— bis (trie hloromethyl) - s—triazine]、ジメトキシトリアジン [2— [2— (3,4 - Dimethoxyphenyl)eth enyl]— 4,6— bis(trichloromethyl)― s— triazine]などを使用することができる。  [0071] PAG commercially available from Wako Pure Chemical Industries, Ltd. WPAG—145 [Bis (cyclohexylsulfonyl) diazometh ane], WPAG-170 [Bis (t-butylsulfonyl) diazomethane], WPAG—199 [Bis (p-toluene sulfonyOdiazomethane] , WPA 281 [Triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [Diphenyl—4-methylphenylsulfonium trifluoromethanesulfonate], WP AG—367 [Diphenyl— 2,4,6-trimethylphenylsulfonium p-toluenesulfonate], CGI manufactured by Ciba Specialty Chemicals — 1397 [(5 Propylsulfo-Luoxyimino — 5H Thiophene-2-ylidene)-(2-Methylphenol) acetonitrile], Sanwa Chemical TFE-Triazine [2— [2— (Furan— 2— yl ) ethenyl] — 4,6—bis (trichloromethyl) -s-triazine], TME-triazine [2— [2— (5— Methylluran— 2— yl) ethenyl] — 4,6— b is (tnchloromethyl) — s — Triazinej MP—Tri, Son [2― (Methoxyphenyl) — 4,6— bis (trie hloromethyl)-s—triazine] Dimethoxytriazine [2- [2— (3,4-Dimethoxyphenyl) ethenyl] —4,6-bis (trichloromethyl) -s-triazine] can be used.
[0072] 光架橋触媒の量は、フッ素系モノマーと架橋剤、または、フッ素系ポリマー、または 、フッ素系ポリマーと架橋剤の合計 100重量部に対して、 0. 1〜20重量部、特に 1〜 10重量部である。  [0072] The amount of the photocrosslinking catalyst is 0.1 to 20 parts by weight, particularly 1 to 100 parts by weight of the fluorine monomer and the crosslinking agent, or the fluorine polymer, or the fluorine polymer and the crosslinking agent in total. ~ 10 parts by weight.
[0073] 光架橋触媒と併用するときのフッ素系ポリマー (B)は、架橋性官能基 (E)、酸性基（ F)、酸の作用によって酸性基に変換する酸解離性官能基 (H)からなる群から選択さ れた少なくとも一つの基を有することが好ましい。フッ素系ポリマー（B)は、さらにシリ コーン鎖（G)を有して 、てもよ ヽ。 [0073] When used in combination with a photocrosslinking catalyst, the fluoropolymer (B) comprises a crosslinkable functional group (E), an acidic group (F), and an acid dissociable functional group (H) that is converted into an acidic group by the action of an acid. It preferably has at least one group selected from the group consisting of The fluoropolymer (B) may further have a silicone chain (G).
Figure imgf000026_0001
Figure imgf000026_0001
フッ素系ポリマーに付与する架橋性官能基は、ラジカル重合反応により硬化するタ イブとしては、アタリロイル基ゃビュル基などの不飽和二重結合基であり、カチオン重 合反応により硬化するタイプとしてはエポキシ基、ォキセタン基などが例示される。ま た、酸性基と架橋する反応基、例えば、カルボン酸、水酸基、アミノ基、イソシァネート 基、 N—メチロール基、アルキルエーテル化した N—メチロール基などであっても良い [0075] フッ素系ポリマーに架橋性官能基を付与する方法は、 (1)架橋性官能基を有するモノマーを予め合成し、それをフッ素系モノマーと共重合 する方法 The crosslinkable functional group imparted to the fluorine-based polymer is an unsaturated double bond group such as an allyloyl group or a buyl group as a type that cures by radical polymerization reaction, and an epoxy type that cures by a cationic polymerization reaction. Group, oxetane group and the like are exemplified. It may also be a reactive group that crosslinks with an acidic group, for example, a carboxylic acid, a hydroxyl group, an amino group, an isocyanate group, an N-methylol group, an alkyl etherified N-methylol group, etc. [0075] The method of imparting a crosslinkable functional group is: (1) A method in which a monomer having a crosslinkable functional group is synthesized in advance and copolymerized with a fluorinated monomer.
(2)—旦、他の官能基を有するフッ素系ポリマーを合成してから、その官能基を架橋 性官能基に変換する方法  (2) —Method of synthesizing a fluoropolymer having another functional group and then converting the functional group to a crosslinkable functional group
のいずれであっても良い。  Either may be sufficient.
[0076] フッ素系ポリマー中の架橋性官能基の量は、ポリマー中の繰り返し単位の合計に対 して、架橋性官能基含有繰り返し単位の量力 一般に 0. l〜20mol%、特に 1〜： LOm ol%である。 [0076] The amount of the crosslinkable functional group in the fluoropolymer is generally from 0.1 to 20 mol%, particularly from 1 to LOm, based on the total number of the repeat units in the polymer. ol%.
[0077] 參酸性某 (F) [0077] 參 Acid 某 (F)
酸性基の例は、カルボキシル基、水酸基 (特に、フエノール性水酸基）、およびスル ホン酸基などである。  Examples of acidic groups are carboxyl groups, hydroxyl groups (particularly phenolic hydroxyl groups), and sulfonic acid groups.
[0078] フッ素系ポリマーに酸性基を付与する方法は、 [0078] A method for adding an acidic group to a fluorine-based polymer includes:
(1)酸性基を有するモノマーを予め合成し、それをフッ素系モノマーと共重合する方 法  (1) A method in which a monomer having an acidic group is synthesized in advance and copolymerized with a fluorine-based monomer
(2)—旦、他の官能基を有するフッ素系ポリマーを合成してから、その官能基を酸性 基に変換する方法  (2) —Method of synthesizing a fluoropolymer having other functional groups and then converting the functional groups to acidic groups
のいずれであっても良い。  Either may be sufficient.
[0079] (1)の場合、酸性基を有するモノマーとして以下のものが例示される。カルボキシル 基を有するモノマーとしては、アクリル酸、メタクリル酸、ビュル酢酸、クロトン酸、イタ コン酸、マレイン酸、フマル酸、ケィ皮酸、およびそれらの塩が挙げられる。水酸基を 有するモノマーとしては、 o—ヒドロキシスチレン、 m—ヒドロキシスチレン、 p—ヒドロキ シスチレン、 2—ヒドロキシェチル (メタ）アタリレート、 2—ヒドロキシプロピル (メタ）ァク リレートなどが挙げられる。またこれらのベンゼン環の 1個以上の水素原子力、メチル 、ェチル、 n—ブチル等のアルキル基、メトキシ、エトキシ、 n—ブトキシ等のアルコキ シ基、ハロゲン原子、アルキル基の 1個以上の水素原子がハロゲン原子に置換され たハロアルキル基、ニトロ基、シァノ基、アミド基に置換されたィ匕合物などが挙げられ る。スルホン酸基を有するモノマーとしては、ビュルスルホン酸、スチレンスルホン酸、 (メタ）ァリルスルホン酸、 2—ヒドロキシ— 3— (メタ）ァリルォキシプロパンスルホン酸、 (メタ）アクリル酸— 2—スルホェチル、（メタ）アクリル酸— 2—スルホプロピル、 2—ヒド 口キシ— 3— (メタ）アタリロキシプロパンスルホン酸、 2— (メタ）アクリルアミド— 2—メ チルプロパンスルホン酸、およびそれらの塩が挙げられる。これらは単独で用いても よいし、 2種以上を併用してもよい。 [0079] In the case of (1), examples of the monomer having an acidic group include the following. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. Examples of the monomer having a hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. In addition, one or more hydrogen atoms of these benzene rings, alkyl groups such as methyl, ethyl and n -butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms and one or more hydrogen atoms of alkyl groups Haloalkyl group substituted with a halogen atom, nitro group, cyano group, and compounds substituted with amide group. Examples of monomers having a sulfonic acid group include butyl sulfonic acid, styrene sulfonic acid, (meth) aryl sulfonic acid, 2-hydroxy-3- (meth) aryloxypropane sulfonic acid, (Meth) acrylic acid—2-sulfoethyl, (meth) acrylic acid—2-sulfopropyl, 2-hydroxy-3— (meth) talyloxypropane sulfonic acid, 2 -— (meth) acrylamide—2-methylpropane Examples include sulfonic acids and their salts. These may be used alone or in combination of two or more.
[0080] (1)の場合、フッ素系モノマーと酸性基を有するモノマーの反応性の違いから共重 合体に組成分布が生じ、それがパターユングに悪影響を及ぼすことがある。これが問 題となる場合は、フッ素系モノマーのビュル基の構造と、酸性基を有するモノマーの ビュル基の構造が同じものを用いることが好ましい。例えば、 Rf基を含有する a—C1 アタリレートをフッ素系モノマーに用いる場合は、 a—C1アクリル酸を、酸性基を有す るモノマーとして用いることが好まし 、。 フッ素系ポリマー中の酸性基の量は、ポリマー中の繰り返し単位の合計に対して、 酸性基含有繰り返し単位の量力 一般に 0. l〜20mol%、特に 1〜： LOmol%である。  [0080] In the case of (1), a composition distribution occurs in the copolymer due to the difference in reactivity between the fluorine-based monomer and the monomer having an acidic group, which may adversely affect the patterning. When this becomes a problem, it is preferable to use a structure in which the structure of the bull group of the fluorinated monomer is the same as that of the monomer having an acidic group. For example, when a-C1 acrylate containing an Rf group is used as a fluorine-based monomer, it is preferable to use a-C1 acrylic acid as a monomer having an acidic group. The amount of acidic groups in the fluoropolymer is generally 0.1 to 20 mol%, particularly 1 to LOmol%, based on the total number of repeating units in the polymer.
[0081] 鲁シリコーン鎖（G) [0081] 鲁 Silicone chain (G)
シリコーン鎖（G)は分子量 1,000〜10,000のジメチルポリシロキサンである。 フッ素系ポリマーにシリコーン鎖を付与する方法は、  The silicone chain (G) is dimethylpolysiloxane having a molecular weight of 1,000 to 10,000. The method of adding a silicone chain to the fluoropolymer is as follows:
(1)シリコーン鎖を有するモノマーあるいは重合開始剤を予め合成し、それをフッ素 系モノマーと共重合する方法  (1) A method in which a monomer having a silicone chain or a polymerization initiator is synthesized in advance and copolymerized with a fluorine-based monomer.
(2)—旦、他の官能基を有するフッ素系ポリマーを合成してから、その官能基にシリコ 一ン鎖を結合させる方法  (2) —Method of synthesizing a fluorine-based polymer having other functional groups and then bonding a silicone chain to the functional groups
のいずれであっても良い。方法（1)の場合、架橋剤（C)に記述したシリコーン (メタ)ァ タリレートを用いても良い。  Either may be sufficient. In the case of the method (1), the silicone (meth) phthalate described in the crosslinking agent (C) may be used.
フッ素系ポリマー中のシリコーン鎖の量は、ポリマー中の繰り返し単位の合計に対し て、シリコーン鎖含有繰り返し単位の量力 一般に 0. l〜50mol%、特に 1〜： LOmol% である。  The amount of silicone chain in the fluoropolymer is generally 0.1 to 50 mol%, especially 1 to LOmol%, based on the total number of repeating units in the polymer.
[0082] 鲁酸の作用によって酸件某に栾椽する酸解離件官能某 (H)  [0082] Acid dissociation sensory function (H)
酸の作用によって酸性基に変換する酸解離性官能基は、 t ブトキシカルボ-ル基 (t— BOC)、イソプロポキシカルボ-ル基、テトラヒドロビラ-ル基、トリメチルシリル基 、 t—ブトキシカルボ-ルメチル基、あるいは、これらの酸解離性官能基で保護された フエノール性水酸基が例示される。 Acid-dissociable functional groups that can be converted to acidic groups by the action of acid are t-butoxycarbol (t-BOC), isopropoxycarbol, tetrahydrobiral, trimethylsilyl, t-butoxycarboromethyl Group or protected with these acid-dissociable functional groups Examples include phenolic hydroxyl groups.
[0083] フッ素系ポリマーに酸解離性官能基を付与する方法は、  [0083] A method for imparting an acid-dissociable functional group to a fluoropolymer is as follows.
(1)酸解離性官能基を有するモノマーを予め合成し、それをフッ素系モノマーと共重 合する方法  (1) A method of previously synthesizing a monomer having an acid-dissociable functional group and co-polymerizing it with a fluorinated monomer
(2)—旦、他の官能基を有するフッ素系ポリマーを合成してから、その官能基を酸解 離性官能基に変換させる方法  (2) —Method of synthesizing a fluoropolymer having other functional groups and then converting the functional groups to acid-releasable functional groups
のいずれであっても良い。方法（1)の場合、 t—ブチル (メタ)アタリレートを用いても良 い。  Either may be sufficient. In the case of method (1), t-butyl (meth) acrylate may be used.
フッ素系ポリマー中の酸解離性官能基の量は、ポリマー中の繰り返し単位の合計に 対して、酸解離性官能基含有繰り返し単位の量力 一般に 0. l〜50mol%、特に 1〜 10mol%である。  The amount of acid-dissociable functional groups in the fluoropolymer is generally 0.1 to 50 mol%, particularly 1 to 10 mol%, based on the total number of repeating units in the polymer. .
[0084] 鲁光酴 ^ii m  [0084] 鲁 光 酴 ^ ii m
光架橋触媒 (D)で説明した光酸発生剤と同じものである。酸解離性官能基 (H)を 有するフッ素系ポリマー (B)の膜に光酸発生剤存在下で電磁波を照射すると、酸性 基が生成し、膜の照射領域が親液性になる。また、この酸性基はアルカリ水溶液に 溶解性があるために、膜の照射領域をアルカリ水溶液で現像することが可能となる。  This is the same as the photoacid generator described in the photocrosslinking catalyst (D). When a film of a fluoropolymer (B) having an acid-dissociable functional group (H) is irradiated with electromagnetic waves in the presence of a photoacid generator, acidic groups are generated and the irradiated region of the film becomes lyophilic. In addition, since this acidic group is soluble in an alkaline aqueous solution, the irradiated region of the film can be developed with the alkaline aqueous solution.
[0085] ·希釈握 [0085] · Dilution grip
本発明のフォトリソグラフィー用表面処理剤には必要に応じて希釈剤 Q)として溶媒 In the surface treatment agent for photolithography of the present invention, if necessary, a solvent as a diluent Q)
(特に、水溶性有機溶媒、有機溶媒 (特に、油溶性有機溶媒)、水)を加えても良い。 希釈剤は、フッ素系ポリマーを製造するために用いるものと同様である。希釈剤は、 フッ素系モノマー (A)またはフッ素系ポリマー（B)に不活性でこれらを溶解するもの である。希釈剤の例は、水溶性有機溶媒としては、アセトン、メチルェチルケトン、メチ ルアミルケトン、酢酸ェチル、プロピレングリコール、プロピレングリコールモノメチルェ 一テル、プロピレングリコーノレモノメチノレエーテノレアセテート、ジプロピレングリコーノレ モノメチノレエーテル、ジプロピレングリコーノレモノメチノレエーテノレアセテート、ジプロピ レングリコール、トリプロピレングリコール、 3—メトキシブチルアセテート、ジメチルホル ムアミド、ジメチルスルホキシド、メチルセ口ソルブ、セロソルブアセテート、ブチルセ口 ソルブ、ブチルカルビトール、カルビトールアセテート、乳酸ェチル、イソプロピルアル コール、メタノール、エタノールなど力 有機溶媒としては、クロ口ホルム、 HFC141b 、 HCHC225、ハイド口フルォロエーテル、ペンタン、へキサン、ヘプタン、オクタン、 シクロへキサン、ベンゼン、トルエン、キシレン、石油エーテル、テトラヒドロフラン、 1,4 ジォキサン、メチルイソブチルケトン、酢酸ブチル、 1,1, 2, 2—テトラクロロェタン、 1, 1, 1 トリクロロェタン、トリクロロエチレン、パークロロエチレン、テトラクロ口ジフノレオ口 ェタン、トリクロ口トリフルォロェタンなどが挙げられる。これらの溶媒は単独で使用し ても 2種以上を混合しても良い。希釈剤はフッ素系モノマー (A)またはフッ素系ポリマ 一（B)の合計 100重量部に対して、 50〜2000重量部、例えば、 50〜： L000重量部 の範囲で用いられる。 (In particular, a water-soluble organic solvent, an organic solvent (especially an oil-soluble organic solvent), water) may be added. The diluent is the same as that used for producing the fluoropolymer. The diluent is inert and dissolves in the fluorinated monomer (A) or the fluorinated polymer (B). Examples of diluents include water-soluble organic solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ethenore acetate, dipropylene glycol. Monomethylol ether, Dipropylene glycol Nole monomethylol etherate acetate, Dipropylene glycol, Tripropylene glycol, 3-Methoxybutyl acetate, Dimethylformamide, Dimethyl sulfoxide, Methyl sorb sorb, Cello solv acetate, Butyl sulf sorb, Butyl carbitol , Carbitol acetate, Ethyl lactate, Isopropyl alcohol Power organic solvents such as coal, methanol, ethanol include black mouth form, HFC141b, HCHC225, hide mouth fluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1, 4 Dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1 trichloroethane, trichlorethylene, perchloroethylene, tetrachlorodiphnoleodiethane, trichlorodifluoroethane Etc. These solvents may be used alone or in combination of two or more. The diluent is used in a range of 50 to 2000 parts by weight, for example, 50 to L000 parts by weight, with respect to 100 parts by weight of the total of the fluorine-based monomer (A) or fluorine-based polymer (B).
[0086] 鲁フッ素系ポリマーの製诰  [0086] 诰 Fluoropolymer production
フッ素系ポリマーは、以下のようにして製造することができる。単量体および必要な 成分を溶媒に溶解させ、窒素置換後、重合触媒を加えて 20〜120°Cの範囲で 1〜2 0時間、撹拌する方法が採用される。  A fluorine-type polymer can be manufactured as follows. A method is adopted in which a monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization catalyst is added and the mixture is stirred in the range of 20 to 120 ° C. for 1 to 20 hours.
[0087] 溶媒は有機溶媒、水溶性有機溶媒、水などが使用でき、希釈剤 ωと同様である。  [0087] As the solvent, an organic solvent, a water-soluble organic solvent, water or the like can be used, and it is the same as the diluent ω.
溶媒は単量体の合計 100重量部に対して、 50〜2000重量部、例えば、 50-1000 重量部の範囲で用いられる。  The solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of monomers.
[0088] フッ素系ポリマーの分子量を調整するためにメルカプタン類、ハロゲン化アルキル 類などの連鎖移動剤を添カ卩しても良い。メルカプタン類としては、 η—ブチルメルカプ タン、 η—ドデシルメルカプタン、 tーブチルメルカプタン、チォグリコール酸ェチル、 チォグリコール酸 2—ェチルへキシル、 2—メルカプトエタノール、メルカプト酸イソォ クチル、チォグリコール酸、 3—メルカプトプロピオン酸、チォグリコール酸メトキシブ チル、シリコーンメルカプタン（信越化学製 KF— 2001)など力 ハロゲン化アルキ ル類としては、クロ口ホルム、四塩化炭素、四臭化炭素等が挙げられる。これらは単 独で用いてもよいし、 2種以上を併用してもよい。  [0088] In order to adjust the molecular weight of the fluoropolymer, a chain transfer agent such as mercaptans and alkyl halides may be added. Mercaptans include η-butyl mercaptan, η-dodecyl mercaptan, t-butyl mercaptan, thioglycolic acid ethyl, 2-glycolyl thioglycolate, 2-mercaptoethanol, isooctyl mercapto acid, thioglycolic acid, 3- Examples of the halogenated alkyls such as mercaptopropionic acid, methoxybutyl thioglycolate, and silicone mercaptan (KF-2001, manufactured by Shin-Etsu Chemical) include black mouth form, carbon tetrachloride, and carbon tetrabromide. These may be used alone or in combination of two or more.
[0089] フッ素系ポリマーの重量平均分子量は、例えば 1, 000〜500, 000、特に 2, 000 〜100, 000、特另 IJに 3, 000〜20, 000であってよい。フッ素系ポジマーの重量平均 分子量は、 GPC (ゲルパーミエーシヨンクロマトグラフィー）により求めたものである（標 準ポリスチレン換算)。 [0090] 參炭素数 8〜 12のフルォロアルキル某を有するモノマー、および、ポリマー [0089] The weight average molecular weight of the fluoropolymer may be, for example, 1,000 to 500,000, particularly 2,000 to 100,000, and the special IJ may be 3,000 to 20,000. The weight average molecular weight of the fluorinated positive mer is determined by GPC (gel permeation chromatography) (standard polystyrene conversion). [0090] Monomers and polymers having a fluoroalkyl cage having 8 to 12 carbon atoms
本発明のフォトリソグラフィー用表面処理剤には必要に応じて炭素数 8〜12のフル ォロアルキル基を有するモノマー（例えば、パーフルォロォクチルェチルアタリレート） In the surface treatment agent for photolithography of the present invention, a monomer having a fluoroalkyl group having 8 to 12 carbon atoms as required (for example, perfluorooctylethyl acrylate)
、および、このモノマーを繰り返し単位とするポリマーを配合しても良い。 , And a polymer having this monomer as a repeating unit may be blended.
[0091] 參非フッ素系ポリマー  [0091] Non-fluorine polymer
本発明のフォトリソグラフィー用表面処理剤には必要に応じて非フッ素系ポリマーを 併用しても良い。非フッ素系ポリマーは、例えば、アルカリ可溶性榭脂であり、特許第 2505033号、特開平 3— 170554号、特開平 6— 118646のノボラック型フエノール 榭脂、特開平 7— 311463号、特開平 8— 292559号の分子量分布を狭めたポリビ ユルフェノール榭脂、特開平 3— 87746号、特開平 8— 44061号の水素添カ卩により 一部環状アルコール構造に変換したフ ノール榭脂、特開平 7— 295200号、特開 平 8— 152717号のポリビュルフエノールの OH基の一部をアルキル基で保護した榭 脂、特開平 8— 339086号のァシル基等の酸に不活性な保護基を有するポリビニル フエノール榭脂、特開平 6-67431号、特開平 10— 10733号のスチレンと共重合し たポリビュルフエノール榭脂、特開平 9 166870号の（メタ）アタリレートモノマー類と 共重合したポリビニルフエノール榭脂、更に特開平 8— 240911号のカルボキシ基を 有する榭脂などである (これら公報の開示を本明細書の一部とする。）。  If necessary, a non-fluorine polymer may be used in combination with the surface treatment agent for photolithography of the present invention. Non-fluorinated polymers are, for example, alkali-soluble resins, such as Japanese Patent No. 2505033, Japanese Patent Application Laid-Open No. 3-170554, Japanese Patent Application Laid-Open No. 6-118646, Novolak type phenol resin, Japanese Patent Application Laid-Open No. No. 292559 Polyvinylphenol resin with a narrowed molecular weight distribution, phenolic resin partially converted into a cyclic alcohol structure by hydrogenation catalysts disclosed in JP-A-3-87746 and JP-A-8-44061, JP-A-7- Polyvinylphenol having a protective group that is inactive to an acid such as a resin in which a part of the OH group of polybuhlphenol in JP-A-8-152717 is protected with an alkyl group, and an acyl group in JP-A-8-339086 Phenol resin, polybutanol resin copolymerized with styrene in JP-A-6-67431, JP-A-10-10733, and polyvinylphenol copolymerized with (meth) acrylate monomers in JP-A-9 166870 Fat, and further , Etc. 榭脂 having a carboxyl group No. 8 240 911 (incorporated herein disclosures of these publications.).
[0092] 鲁顔料  [0092] Amber pigment
本発明のフォトリソグラフィー用表面処理剤には必要に応じて各種顔料を添加して も良い。例えば、黒色顔料としてはカーボンブラック、グラフアイト、チタンブラック、酸 化鉄、硫化ビスマス、ペリレンブラックなどである。  Various pigments may be added to the surface treatment agent for photolithography of the present invention as necessary. For example, black pigments include carbon black, graphite, titanium black, iron oxide, bismuth sulfide, and perylene black.
[0093] ·酸捕 l [0093] · Acid capture l
本発明のフォトリソグラフィー用表面処理剤には必要に応じて酸捕捉剤を添加する ことにより、膜中で酸発生剤から発生した酸の拡散を制御しても良い。酸捕捉剤とし ては、有機ァミン、塩基性のアンモ-ゥム塩、塩基性のスルホ -ゥム塩などが用いら れ、昇華やレジスト性能を劣化させないものであればよい。これらの酸捕捉剤の中で も、有機ァミンが画像性能が優れる点で好ましい。例えば特開昭 63— 149640号、特 開平 5— 249662号、特開平 5— 127369号、特開平 5— 289322号、特開平 5— 249683 号、特開平 5— 289340号、特開平 5— 232706号、特開平 5— 257282号、特開平 6— 24 2605号、特開平 6— 242606号、特開平 6— 266100号、特開平 6— 266110号、特開平 6 317902号、特開平 7— 120929号、特開平 7— 146558号、特開平 7— 319163号、特 開平 7— 508840号、特開平 7— 333844号、特開平 7— 219217号、特開平 7— 92678号 、 特開平 7— 28247号、特開平 8— 22120号、特開平 8— 110638号、特開平 8— 123030 号、特開平 9 274312号、特開平 9 166871号、特開平 9 292708号、特開平 9 32 5496号、特表平 7— 508840号、 USP5525453号、 USP5629134号、 USP5667938号等に 記載の塩基性ィ匕合物を用いることができる (これら開示を本明細書の一部とする。 ) o 酸捕捉剤としては、好ましくは、 1, 5 ジァザビシクロ [4. 3. 0]— 5 ノネン、 1 , 8 - ジァザビシクロ [5. 4. 0]— 7 ゥンデセン、 1, 4 ジァザビシクロ [2. 2. 2]オクタン 、 4ージメチルァミノピリジン、 1 ナフチルァミン、ピぺリジン、へキサメチレンテトラミ ン、イミダゾール類、ヒドロキシピリジン類、ピリジン類、 4, 4，ージアミノジフエ-ルエー テル、ピリジ-ゥム p トルエンスルホナート、 2, 4, 6 トリメチルピリジ-ゥム p トル エンスルホナート、テトラメチルアンモ -ゥム p トルエンスルホナート、及びテトラプチ ルアンモ-ゥムラクテート、トリェチルァミン、トリブチルァミン等が挙げられる。これら の中でも、 1, 5 ジァザビシクロ [4. 3. 0]—5 ノネン、 1, 8 ジァザビシクロ [5. 4 . 0]— 7 ゥンデセン、 1, 4 ジァザビシクロ [2. 2. 2]オクタン、 4 ジメチルアミノビ リジン、 1 ナフチルァミン、ピぺリジン、へキサメチレンテトラミン、イミダゾール類、ヒ ドロキシピリジン類、ピリジン類、 4, 4'ージアミノジフエニルエーテル、トリェチルァミン 、トリブチルァミン等の有機ァミンが好ましい。 If necessary, an acid scavenger may be added to the photolithography surface treatment agent of the present invention to control the diffusion of the acid generated from the acid generator in the film. As the acid scavenger, organic amines, basic ammonium salts, basic sulfo salt, etc. are used, so long as they do not sublimate or deteriorate the resist performance. Of these acid scavengers, organic amines are preferred because of their excellent image performance. For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683 JP-A-5-289340, JP-A-5-232706, JP-A-5-257282, JP-A-6-24 2605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110. JP-A-6 317902, JP-A-7-120929, JP-A-7-146558, JP-A-7-319163, JP 7-508840, JP-A-7-333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-110638, JP-A-8-123030, JP-A-9 274312, JP-A-9 166871, and JP-A-9 292708, JP-A-9 32 5496, JP-T 7-508840, USP5525453, USP5629134, USP5667938, etc. can be used (the disclosure of which is incorporated herein by reference) O The acid scavenger is preferably 1,5 diazabicyclo [4. 3. 0] — 5 nonene, 1, 8-diazabicyclo [5. 4. 0] — 7 undecene, 1, 4 diazabici [2. 2. 2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4, 4, diaminodiphenyl ether, Pyridinium p-toluenesulfonate, 2, 4, 6 trimethylpyridium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine, etc. Can be mentioned. Among these, 1,5 diazabicyclo [4. 3. 0] —5 nonene, 1, 8 diazabicyclo [5. 4.0 .0] — 7 undecene, 1, 4 diazabicyclo [2.2.2] octane, 4 dimethylamino Organic amines such as pyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine, and tributylamine are preferred.
[0094] 參その他の添加剤  [0094] 參 Other additives
本発明のフォトリソグラフィー用表面処理剤には必要に応じてその他の各種添加剤 が用いられる。例えば、膜の平滑性を向上させるためのフッ素系、シリコーン系、炭化 水素系界面活性剤や、膜の密着性を向上させるためのシランカップリング剤ゃチタネ ートカップリング剤、その他、暗反応抑制のための熱重合禁止剤や紫外線吸収剤、 酸化防止剤、消泡剤などが挙げられる。  Various other additives are used in the surface treatment agent for photolithography of the present invention as necessary. For example, fluorine-based, silicone-based, hydrocarbon-based surfactants for improving film smoothness, silane coupling agents for improving film adhesion, titanate coupling agents, etc., for suppressing dark reactions Heat polymerization inhibitors, UV absorbers, antioxidants and antifoaming agents.
[0095] 參某材  [0095] Wood
本発明の基板に用いる基材は、シリコン、合成樹脂、ガラス、金属、セラミックスなど である。 The base material used for the substrate of the present invention is silicon, synthetic resin, glass, metal, ceramics, etc. It is.
[0096] 合成樹脂としては、熱可塑性榭脂、熱硬化性榭脂のいずれでもよぐ例えば、ポリ エチレン、ポロプロピレン、エチレン プレピレン共重合体、エチレン 酢酸ビュル共 重合体 (EVA)等のポリオレフイン、環状ポリオレフイン、変性ポリオレフイン、ポリ塩化 ビュル、ポリ塩ィ匕ビユリデン、ポリスチレン、ポリアミド、ポリイミド、ポリアミドイミド、ポリ カーボネート、ポリ一（4 メチルベンテン 1)、アイオノマー、アクリル系榭脂、ポリメ チルメタタリレート、アクリル スチレン共重合体 (AS榭脂）、ブタジエン スチレン共 重合体、ポリオ共重合体 (EVOH)、ポリエチレンテレフタレート（PET)、ポリプチレン テレフタレート（PBT)、プリシクロへキサンテレフタレート（PCT)等のポリエステル、ポ リエ一テル、ポリエーテルケトン（PEK)、ポリエーテルエーテルケトン（PEEK)、ポリ エーテルイミド、ポリアセタール（POM)、ポリフエ-レンォキシド、変性ポリフエ-レン ォキシド、ポリアリレート、芳香族ポリエステル (液晶ポリマー）、ポリテトラフルォロェチ レン、ポリフッ化ビ-リデン、その他フッ素系榭脂、スチレン系、ポリオレフイン系、ポリ 塩化ビニル系、ポリウレタン系、フッ素ゴム系、塩素化ポリエチレン系等の各種熱可塑 性エラストマ一、エポキシ榭脂、フエノール榭脂、ユリア榭脂、メラミン榭脂、不飽和ポ リエステル、シリコーン榭脂、ポリウレタン等、またはこれらを主とする共重合体、ブレ ンド体、ポリマーァロイ等が挙げられ、これらのうちの 1種または 2種以上を組み合わ せて (例えば 2層以上の積層体として)用いることができる。合成樹脂製の基板を用い れば、軽量、透明、安価、曲げられるなどの特徴を基板に付与できる。  [0096] The synthetic resin may be either a thermoplastic resin or a thermosetting resin, for example, polyolefins such as polyethylene, polypropylene, ethylene prepylene copolymer, ethylene butyl acetate copolymer (EVA), Cyclic polyolefin, modified polyolefin, polychlorinated butyl, polychlorinated polyvinylidene, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly (4 methylbenten 1), ionomer, acrylic resin, polyethylene methacrylate, Acrylic styrene copolymer (AS resin), butadiene styrene copolymer, Polio copolymer (EVOH), Polyethylene terephthalate (PET), Polypropylene terephthalate (PBT), Polycyclohexane terephthalate (PCT), etc. TEL, polyetherketone (PEK), Reether ether ketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride Other fluoroelastomers, styrenes, polyolefins, polyvinyl chlorides, polyurethanes, fluororubbers, chlorinated polyethylenes, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, Melamine resin, unsaturated polyester, silicone resin, polyurethane, etc., or their main copolymers, blends, polymer alloys, etc. are mentioned, and one or more of these are combined. (For example, as a laminate of two or more layers). If a synthetic resin substrate is used, the substrate can be provided with features such as light weight, transparency, low cost, and bending.
[0097] ガラスとしては、例えば、ケィ酸ガラス (石英ガラス）、ケィ酸アルカリガラス、ソーダ石 灰ガラス、カリ石灰ガラス、鉛 (アルカリ）ガラス、ノ リウムガラス、ホウケィ酸ガラス等が 挙げられる。  [0097] Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda ash glass, potassium lime glass, lead (alkali) glass, norium glass, borosilicate glass, and the like.
金属としては、金、銀、銅、鉄、ニッケル、アルミニウム、白金等が挙げられる。 セラミックとしては、酸化物（例えば、酸ィ匕アルミニウム、酸化亜鉛、酸化チタン、酸 化ケィ素、ジルコニァ、チタン酸バリウム）、窒化物（例えば、窒化ケィ素、窒化ホウ素 )、硫ィヒ物 (例えば、硫ィヒカドミウム)、炭化物 (例えば、炭化ケィ素)等が挙げられ、こ れらの混合物を使用して良い。  Examples of the metal include gold, silver, copper, iron, nickel, aluminum, and platinum. Ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), sulfites ( Examples thereof include carbide (eg, cadmium sulfate), carbide (eg, carbide), and a mixture thereof may be used.
[0098] V、ずれの基板を用いる場合でも、プラズマ処理や UVオゾン処理などの前処理を行 つても良い。これらの前処理により、基板表面に親液性の官能基 (例えば、 OH基、 C OOH基、 NH基)を導入できる。 [0098] Even when a substrate with a V or misalignment is used, pretreatment such as plasma treatment or UV ozone treatment is performed. It is okay. By these pretreatments, lyophilic functional groups (for example, OH groups, COOH groups, NH groups) can be introduced on the substrate surface.
パターン表面の形状は、最終的に製造する素子の目的に応じて適当なものを選択 すれば良ぐ円、四角形、三角形、直線、曲線などが例示される。互いのパターンは 接していても離れていても良い。例えば、ライン &スペースの場合、ライン幅およびラ イン間隔は、 0. 5〜： LOO m、例えば、 1 20 mであって良い。ライン幅は等間隔 であっても良いし、幅が変化しても良い。ラインの形状は直線でも曲線でも良い。  The shape of the pattern surface may be a circle, a rectangle, a triangle, a straight line, a curve, etc., as long as an appropriate one is selected according to the purpose of the element to be finally manufactured. The patterns can be touching or distant. For example, in the case of line & space, the line width and line spacing may be 0.5 to: LOO m, for example, 120 m. The line widths may be equally spaced or the widths may vary. The shape of the line may be a straight line or a curve.
[0099] これら基材の表面に、表面処理剤 (含フッ素化合物）を液相または気相中で均一に 処理する。液相での処理は、膜厚を制御できるものであれば公知の塗布法を採用す ることができる。例えば、ロールコート法、グラビアコート法、マイクログラビアコート法、 フローコート法、バーコート法、スプレーコート法、ダイコート法、スピンコート法、ディ ップコート法などが採用でき、基材の種類、形状、生産性、膜厚の制御性などを考慮 して選択できる。例えば、基板を含フッ素化合物溶液にスピンコート法で塗布した後 70 150°Cで 1秒間〜 10分間（例えば 110°Cで 1分間）加熱して含フッ素化合物の 膜から溶媒を乾燥することによって行える。この簡便なプロセスで基材の表面に、含 フッ素化合物の膜が形成される。含フッ素化合物の膜の厚さは、一般に 0.5 100 0 m、例えば 10nm 200 μ m、特に 50nm 100 μ mであって良い。パターン基板の作 製方法 (1 （11)〜(14)においては、光を照射することなしで、対水接触角 60° 以上、 特に 80° 以上の均一な撥液性表面が得られる。一方、パターン基板の作製方法 (2) 〜(10)においては光を照射することにより、照射領域に対水接触角 60° 以上、特に 8 0° 以上の撥液性表面が形成される。 [0099] The surface treatment agent (fluorine-containing compound) is uniformly treated on the surface of these substrates in a liquid phase or a gas phase. For the treatment in the liquid phase, a known coating method can be adopted as long as the film thickness can be controlled. For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected considering the controllability and controllability of film thickness. For example, after applying the substrate to the fluorine-containing compound solution by spin coating, the substrate is heated at 150 ° C for 1 second to 10 minutes (eg, 110 ° C for 1 minute) to dry the solvent from the fluorine-containing compound film. Yes. With this simple process, a film of a fluorine-containing compound is formed on the surface of the substrate. The film thickness of the fluorine-containing compound may generally be 0.51000 m, for example 10 nm 200 μm, in particular 50 nm 100 μm. Pattern substrate production method (1 (11) to (14) provides a uniform liquid-repellent surface with a water contact angle of 60 ° or more, particularly 80 ° or more, without irradiation with light. In the pattern substrate manufacturing methods (2) to (10), by irradiating with light, a liquid repellent surface having a water contact angle of 60 ° or more, particularly 80 ° or more is formed in the irradiated region.
[0100] 次にフォトリソグラフィ一法を用いて、親液領域の対水接触角が 50° 以下となるよう にパターユングを行う。表面自由エネルギーが異なる複数の領域 [ (1)対水接触角 6 0° 以上の領域、特に対水接触角 80° 以上の領域と、（2)対水接触角 50° 以下の 領域、特に対水接触角 30° 以下の領域]から構成されるパターン基板を調製する。 領域 ( 1)と領域 (2)は隣接する。 [0100] Next, using a photolithography method, patterning is performed so that the contact angle with water in the lyophilic region is 50 ° or less. Multiple regions with different surface free energies [(1) Water contact angle of 60 ° or more, especially water contact angle of 80 ° or more, and (2) Water contact angle of 50 ° or less, especially Prepare a pattern substrate composed of a region with a water contact angle of 30 ° or less. Region (1) and region (2) are adjacent.
含フッ素化合物の膜をフォトリソグラフィ一法でパターユングするためには、電磁波 を照射する。 [oioi] m m In order to pattern a fluorine-containing compound film by a photolithography method, an electromagnetic wave is irradiated. [oioi] mm
本発明で膜に照射する電磁波は、波長 10〜400nmの光であり、紫外線 (UV, 200〜 400nm)、真空紫外光 (VUV, 150〜200nm)、極端紫外線 (EUV, 10〜120nm)などが例 示される。 VUVを用いる場合、光源は波長 172nmの VUVを発光できる巿販のキセノン エキシマランプが使用できる。また UVを用いる場合、光源は水銀キセノンランプ、水 銀ランプ、キセノンランプ、キセノンエキシマランプが使用できる。さらに、 248nmの Kr Fエキシマレーザー、 193nmの ArFエキシマレーザー、 157nmの F2エキシマレーザー を使用しても良い。露光量は l〜10,000mj/cm2、特に 1〜： L000mj/cm2であってよい。 また、光以外に、波長 0.1〜10nmの X線、波長 0.001〜0.01nmの電子線、波長 10〜3 OOnmのレーザー光線の電磁波を用いても良!、。 The electromagnetic wave irradiated to the film in the present invention is light having a wavelength of 10 to 400 nm, such as ultraviolet (UV, 200 to 400 nm), vacuum ultraviolet (VUV, 150 to 200 nm), extreme ultraviolet (EUV, 10 to 120 nm), etc. An example is shown. When using VUV, a commercially available xenon excimer lamp that can emit VUV with a wavelength of 172 nm can be used. When UV is used, a mercury xenon lamp, mercury-silver lamp, xenon lamp, or xenon excimer lamp can be used as the light source. Furthermore, a 248 nm Kr F excimer laser, a 193 nm ArF excimer laser, and a 157 nm F2 excimer laser may be used. The exposure dose may be from 1 to 10,000 mj / cm 2 , in particular from 1 to L000 mj / cm 2 . In addition to light, X-rays with a wavelength of 0.1 to 10 nm, electron beams with a wavelength of 0.001 to 0.01 nm, and electromagnetic waves of a laser beam with a wavelength of 10 to 3 OO nm may be used!
[0102] 光や X線でフォトリソグラフィーを行う場合は、フォトマスクを介して膜に光を照射して も良いし、米国テキサス ·インスツルメンッ社が開発した DMD (デジタル ·マイクロミラー •デバイス)のような半導体を使用して、マスクレスでパターン状に光を照射しても良い 。 DMDは、ミクロンサイズの超微小な鏡 (マイクロミラー)を 48万〜 131万個敷き詰め、ミ ラーにランプ光を反射させて膜にパターン状に光を照射する。  [0102] When photolithography is performed using light or X-rays, the film may be irradiated with light through a photomask, or a DMD (digital micromirror device) developed by Texas Instruments, Inc. A simple semiconductor may be used to irradiate light in a pattern without a mask. DMD lays out 480,000 to 1,130,000 micron-sized ultra-fine mirrors, reflects the lamp light to the mirror, and irradiates the film with light in a pattern.
[0103] 一方、電子線、レーザー光線では、市販の描画装置を用いてフォトマスクなしで直 接、均一に表面処理された基板にパターンを描画する。電子線の露光量はラスター 描画では 10〜10,000 μ
Figure imgf000035_0001
ショット描画では 100〜100 ,0001C/dot、特に l ,000〜10,000fC/dotであってよい。 [0103] On the other hand, with an electron beam and a laser beam, a pattern is drawn directly and uniformly on a surface-treated substrate without using a photomask using a commercially available drawing apparatus. Electron beam exposure is 10 to 10,000 μ for raster drawing
Figure imgf000035_0001
In shot drawing, it may be 100 to 100,0001 C / dot, particularly l, 000 to 10,000 fC / dot.
[0104] 參現像  [0104] 參 Develop
本発明では、上記の電磁波を照射後に溶媒に対する溶解性のコントラストを利用し て、溶媒可溶な領域を除去、いわゆる「現像」を行っても良い。現像に使用される溶 媒 (現像液）は、フッ素系ポリマーの製造に用いたものやアルカリ水溶液を用いる。ァ ルカリ水溶液は、炭酸ナトリウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化力リウ ム、ケィ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水などの無機アルカリ水溶液や 、ェチルァミン、 n—プロピルァミンなどの第一級ァミン類；ジェチルァミン、ジ— n—プ 口ピルァミンなどの第二級ァミン類；トリェチルァミン、メチルジェチルァミン、 N—メチ ルピロリドンなどの第三級ァミン類；ジメチルエタノールァミン、トリエタノールァミンな どのアルコールアミン類；テトラメチルアンモ-ゥムヒドロキシド、テトラエチルアンモ- ゥムヒドロキシド、コリンなどの第四級アンモ-ゥム塩；ピロール、ピぺリジン等の環状 ァミン類のアルカリ類カゝらなる有機アルカリ水溶液を用いる。これらは単独で用いても 良 、し二種類以上を混合しても良!、。また、界面活性剤を添加しても良 、。 In the present invention, the solvent-soluble region may be removed, that is, so-called “development” may be performed using the contrast of solubility in the solvent after irradiation with the electromagnetic wave. As the solvent (developer) used for development, the one used for the production of a fluoropolymer or an alkaline aqueous solution is used. Alkaline aqueous solutions include inorganic alkaline aqueous solutions such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as jetylamine and di-n-pylamine; tertiary amines such as triethylamine, methyljetylamine and N-methylpyrrolidone; dimethylethanolamine and triethanolamine Any alcohol amines; quaternary ammonium salts such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, etc .; using an organic alkaline aqueous solution consisting of alkalis of cyclic amines such as pyrrole and piperidine . These can be used alone or in combination of two or more! Also, a surfactant may be added.
現像方法は、浸漬法、液盛り法などで 10秒〜 10分の範囲で行って良い。  The developing method may be performed in the range of 10 seconds to 10 minutes by an immersion method, a liquid filling method, or the like.
[0105] 第 2の要旨によれば、本発明においては、次のようなパターン基板の作製方法を用 いることがでさる。 [0105] According to the second aspect, in the present invention, the following method for producing a patterned substrate can be used.
鲁パターン某板の作製方法  鲁 Pattern plate making method
本発明では、フルォロアルキル基を含有するフッ素系モノマー (A)、架橋剤 (B)、 光架橋触媒 (C)を含んでなる電磁波硬化組成物を非接触な微量液滴吐出法により 、基板上に吐出して微小構造を有する膜を形成し、電磁波を照射して膜を硬化させ る。非接触な微量液滴吐出法の例としては、例えばインクジェット法、マイクロデイス ペンサ一法などが挙げられる。  In the present invention, an electromagnetic wave curable composition comprising a fluoromonomer-containing fluoromonomer (A), a crosslinking agent (B), and a photocrosslinking catalyst (C) is applied onto a substrate by a non-contact microdroplet discharge method. A film having a microstructure is formed by discharging, and the film is cured by irradiation with electromagnetic waves. Examples of the non-contact minute droplet discharge method include an ink jet method and a microdispenser method.
[0106] インクジェット法として、ピエゾ方式を用いることができる。ピエゾ方式は、液滴の制 御性に優れインク選択の自由度の高いことからインクジェットプリンターでも利用され ている。なお、ピエゾ方式には、 MLP (Multi Layer Piezo)タイプと MLChip (Mult l Layer Ceramic Hyper Integrated Piezo segmentsノタイフ力ある。免熱体を 発熱させ気泡を生じさせインク液体を押し出す、サーマル方式を用いたインクジェット 法でもよい。インクジェット法で吐出される液滴の一滴当たりの容量は 0.1pL〜lnLで ある。本発明で、インクジェット法に適した電磁波硬化組成物 (インク）の 25°Cにおけ る物性は、粘度 l〜50mPa's、表面張力 19〜30mN/m、沸点 100〜250°Cである。 [0106] As an inkjet method, a piezo method can be used. The piezo method is also used in inkjet printers because of its excellent droplet controllability and high degree of freedom in ink selection. The piezo method has MLP (Multi Layer Piezo) type and MLChip (Multi Layer Ceramic Hyper Integrated Piezo segments). The thermal method ink jet generates heat and generates bubbles to push out ink liquid. The volume per droplet discharged by the ink jet method is 0.1 pL to ln L. In the present invention, the physical properties at 25 ° C. of the electromagnetic wave curable composition (ink) suitable for the ink jet method are as follows. Viscosity: 1-50 mPa's, surface tension: 19-30 mN / m, boiling point: 100-250 ° C.
[0107] マイクロディスペンサー法としては、チュービング方式、エアー圧縮方式を用いるこ とができる。マイクロディスペンサー法で吐出される液滴の一滴当たりの容量は、一般 【こ Inし〜 1 μしである。 [0107] As the microdispenser method, a tubing method or an air compression method can be used. The volume per droplet discharged by the microdispenser method is generally [In 1 to 1 μm].
[0108] 電磁波を照射する前 (プリベータ)や後（ポストベータ）に、撥液性の膜に対して 50 [0108] Before (pre-beta) and after (post-beta) irradiation of electromagnetic waves, 50
〜250°C程度の熱処理を行っても良い。酸素により硬化が阻害される場合は、窒素、 アルゴンのような不活性ガスの雰囲気で電磁波を照射しても良い。 You may heat-process at about -250 degreeC. When curing is inhibited by oxygen, electromagnetic waves may be irradiated in an atmosphere of an inert gas such as nitrogen or argon.
この簡便なプロセスで基板の表面に、撥液性の膜が形成され、表面自由エネルギ 一が異なる複数 (少なくとも 2つ）の領域力 構成されるパターン基板、言い換えると、 ノターン化された少なくとも 1つの撥液領域と少なくとも 1つの親液領域力も成るバタ ーン基板 (以下、単に「パターン基板」と省略する）が作製できる。 With this simple process, a liquid-repellent film is formed on the surface of the substrate, and the surface free energy A pattern substrate composed of a plurality of (at least two) different region forces, in other words, a pattern substrate composed of at least one lyophobic region that has been turned into one and at least one lyophilic region force (hereinafter simply referred to as “pattern”). Abbreviated as “substrate”).
[0109] 撥液性の膜の厚さは、一般に lnm〜1000 μ m、例えば 10nm〜200 μ m、特に 50nm 〜100 /ζ πιであって良い。撥液領域は例えば、対水接触角 70° 以上、特に 80° 以上 の撥液性を示す。撥液領域のパターンの形状は、最終的に製造する素子の目的に 応じて適当なものを選択すれば良ぐ直線、曲線、円、四角形、三角形などが例示さ れる。互いのパターンは接していても離れていても良い。例えば、ライン &スペースの 場合、ライン（撥液性の領域）の幅は、 10〜： LOOO /z m 例えば、 100〜500 /ζ πιであ つて良い。ラインとスペースの比率は任意であり、例えば、 1/10〜10/1である。ライン の形状は直線でも曲線でも良 、。  [0109] The thickness of the liquid repellent film may generally be from lnm to 1000 μm, such as from 10 nm to 200 μm, in particular from 50 nm to 100 / ζ πι. The liquid repellent region exhibits liquid repellency of, for example, a water contact angle of 70 ° or more, particularly 80 ° or more. Examples of the shape of the pattern of the liquid repellent region include straight lines, curves, circles, squares, triangles, and the like that can be selected according to the purpose of the element to be finally manufactured. Mutual patterns may be in contact or separated. For example, in the case of line & space, the width of the line (liquid-repellent region) may be 10 to: LOOO / zm, for example, 100 to 500 / ζ πι. The ratio of the line and the space is arbitrary, for example, 1/10 to 10/1. The shape of the line can be straight or curved.
[0110] 鲁パターン 形成した某板に針する機能件化合物溶液の途布  [0110] Straw pattern Dissemination of functional compound solution to needle on the formed slat
本発明では、パターンを形成した基板に機能性ィ匕合物の溶液または分散液を塗布 する。機能性ィ匕合物溶液を塗布する方法は、スピンコート法、ディップコート法、キヤ スト法、ロールコート法、印刷法、転写法、インクジェット法 [P.Calvert, Chem.Mater., 13, 3299(2001)]、バーコード法、キヤビラリ一法などが挙げられる。  In the present invention, the functional compound solution or dispersion is applied to the substrate on which the pattern is formed. The functional compound solution can be applied by spin coating, dip coating, casting, roll coating, printing, transfer, ink jet [P. Calvert, Chem. Mater., 13, 3299 (2001)], the bar code method, the one-way method.
[0111] パターン化された含フッ素化合物の膜の上に、機能性ィ匕合物の層が形成される。  [0111] A layer of the functional compound is formed on the patterned fluorine-containing compound film.
機能性ィ匕合物の層は、パターン表面の上に、機能性化合物を溶媒に溶解した溶液 を塗布し、溶媒を除去することによって形成することができる。表面自由エネルギー が異なる複数の領域に機能性化合物溶液を塗布すると、機能性化合物溶液は、対 水接触角 60° 以上、特に 80° 以上の領域を避けて、対水接触角 50° 以下、特に 3 0° 以下の領域のみに付着する。こうして、機能性ィ匕合物の層が基板にパターン化さ れた親液領域上に形成される。  The layer of the functional compound can be formed by applying a solution obtained by dissolving a functional compound in a solvent on the pattern surface and removing the solvent. When a functional compound solution is applied to multiple areas with different surface free energies, the functional compound solution avoids areas with a water contact angle of 60 ° or more, especially 80 ° or more, and has a water contact angle of 50 ° or less, especially 3 Adheres only to areas below 0 °. Thus, a layer of functional compound is formed on the lyophilic region patterned on the substrate.
[0112] 機能性ィ匕合物の例は、半導体化合物、導電性化合物、ディスプレイ用画素を形成 するための色素または顔料、フォトクロミック化合物、サーモク口ミック化合物、レンズ 材料、生命科学薬剤などである。  [0112] Examples of the functional compound include a semiconductor compound, a conductive compound, a dye or pigment for forming a display pixel, a photochromic compound, a thermochromic compound, a lens material, a life science drug, and the like.
半導体ィ匕合物としては、有機系が好ましぐ例えば、ペンタセン誘導体、ポリチオフ ヱン誘導体、フタロシアニン誘導体、ポリフルオレン誘導体、ポリ p—フヱ-レンビ-レ ン、層状へロブスカイトイ匕合物などが挙げられる。 Organic compounds are preferred as semiconductor compounds, for example, pentacene derivatives, polythiophene derivatives, phthalocyanine derivatives, polyfluorene derivatives, poly (p-fluoro-lenbi-re). And layered herosky toy compounds.
導電性ィ匕合物としては、室温で 102 S/cm以上の導電性を有するものである。例え ば、有機系ではポリアセチレン誘導体、ポリチォフェン誘導体、ポリピロール、ポリ p— フエ-レンビ-レン、ポリア-リンなどが挙げられる。これらの化合物をドーピングする ことにより導電性を向上しても良い。金属系では金、銀、銅などのナノ粒子を液体に 分散したものが挙げられる。 The conductive compound has a conductivity of 10 2 S / cm or more at room temperature. For example, in the case of organic systems, polyacetylene derivatives, polythiophene derivatives, polypyrrole, poly p-phenylene vinylene, polyarine and the like can be mentioned. Conductivity may be improved by doping these compounds. In the metal type, nanoparticles in which nanoparticles such as gold, silver and copper are dispersed in a liquid can be mentioned.
[0113] フォトクロミック化合物としては、有機系が好ましぐ例えば、ァゾベンゼン誘導体、ス ピロピラン誘導体、フルギド誘導体、ジァリールェテン誘導体などが挙げられる。 サーモク口ミック化合物とは、温度変化に伴って物質の色が可逆的に変化する化合 物の総称であり、例えば、サリチリデンァ二リン類、ポリチォフェン誘導体、テトラハロ ゲノ錯体、エチレンジァミン誘導体錯体、ジニトロジアンミン銅錯体、 1,4—ジァザシク 口オクタン（daco)錯体、へキサメチレンテトラミン（hmta)錯体、サルチルアルデヒド（sa len)類錯体などが挙げられる。 [0113] The photochromic compound is preferably an organic compound, for example, an azobenzene derivative, a spiropyran derivative, a fulgide derivative, a diarylethene derivative, or the like. A thermochemical compound is a general term for compounds in which the color of a substance changes reversibly with changes in temperature.For example, salicylidene dilins, polythiophene derivatives, tetrahalogeno complexes, ethylene diamine derivative complexes, dinitrodiammine copper complexes. 1,4-diazasic octane (daco) complex, hexamethylenetetramine (hmta) complex, saltyl aldehyde (sa len) complex and the like.
機能性化合物の層の厚さは、 0. lnm〜100 μ m、例えば、 lnm〜l μ mであって 良い。  The thickness of the functional compound layer may be 0.1 nm to 100 μm, for example, 1 nm to 1 μm.
[0114] 機能性化合物を溶解する溶媒の例は、有機溶媒 (特に油溶性有機溶媒)、水溶性 有機溶媒、および水である。機能性化合物が水に難溶性の場合、有機溶媒 (特に、 油溶性有機溶媒)または水溶性有機溶媒に溶解させる必要がある。  [0114] Examples of the solvent that dissolves the functional compound are an organic solvent (particularly an oil-soluble organic solvent), a water-soluble organic solvent, and water. When the functional compound is sparingly soluble in water, it must be dissolved in an organic solvent (especially an oil-soluble organic solvent) or a water-soluble organic solvent.
本発明において、機能性ィ匕合物を溶解する溶媒は、表面張力 40mNZm以下、例 えば 30mN/m以下である有機溶媒であることが好まし 、。表面張力が 40mNZm以 下であることによって、溶液がパターン形状にそって容易に濡れ拡がることができる。  In the present invention, the solvent that dissolves the functional compound is preferably an organic solvent having a surface tension of 40 mNZm or less, for example, 30 mN / m or less. When the surface tension is 40 mNZm or less, the solution can easily spread along the pattern shape.
[0115] 有機溶媒としては、アルコール、エステル、ケトン、エーテル、炭化水素（例えば、脂 肪族炭化水素および芳香族炭化水素)等が挙げられ、有機溶媒はフッ素化されて ヽ てもされていなくてもどちらでも良い。有機溶媒の具体例は、パーフルォロデカリン、 ハイド口フルォロエーテル、 HCFC225、クロ口ホルム、 1,1, 2,2—テトラクロ口エタン、テ トラクロ口エチレン、クロ口ベンゼン、酢酸ブチル、へキサン、イソペンタン、トルエン、 キシレン、テトラヒドロフランなどが挙げられる。また、水溶性有機溶媒の具体例は、ァ セトン、メチルェチルケトン、メチルアミルケトン、酢酸ェチル、プロピレングリコール、 プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルァ セテート、ジプロピレングリコーノレモノメチノレエーテル、ジプロピレングリコーノレモノメ チルエーテルアセテート、ジプロピレングリコール、トリプロピレングリコール、ジメチル ホルムアミド、ジメチルスルホキシド、メチルセ口ソルブ、セロソルブアセテート、ブチル セロソルブ、ブチルカルビトール、カルビトールアセテート、乳酸ェチル、イソプロピル アルコール、メタノール、エタノールなどが挙げられる。 [0115] Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (for example, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvents are not allowed to be fluorinated. But either is fine. Specific examples of the organic solvent include perfluorodecalin, hydrated fluoroether, HCFC225, chloroformated form, 1,1,2,2-tetrachloroethane, tetrachloroethylene, cyclobenzene, butyl acetate, hexane, Examples include isopentane, toluene, xylene, and tetrahydrofuran. Specific examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl caffeosolve, cellosolve Examples thereof include acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl acetate, isopropyl alcohol, methanol, and ethanol.
水を用いる場合は、界面活性剤や上記の水溶性有機溶媒などを添加して、表面張 力を低下させても良い。  When water is used, the surface tension may be reduced by adding a surfactant or the above water-soluble organic solvent.
[0116] 機能性ィ匕合物の溶液における機能性ィ匕合物の濃度は、 0. 1〜20重量％、例えば 、 1〜10重量％であって良い。  [0116] The concentration of the functional compound in the solution of the functional compound may be 0.1 to 20% by weight, for example, 1 to 10% by weight.
溶媒の除去は、蒸発などによって行える。溶媒の除去は、基材を、加熱 (例えば、 6 0〜200°C)することによって、行える。溶媒除去は、減圧（例えば、 0. 01〜： LOOPa) 下で行っても良い。  The solvent can be removed by evaporation or the like. The solvent can be removed by heating the substrate (for example, 60 to 200 ° C.). The solvent removal may be performed under reduced pressure (for example, 0.01-: LOOPa).
[0117] 本発明の基板は、電子、光学、医療、化学分析などの幅広い用途のデバイスに用 いることが可能である。例えば、電子デバイスとしては、トランジスタ、メモリ、発光ダイ オード (EL)、レーザー、太陽電池などの集積回路に利用できる。これらのデバイス 力もフレキシブルディスプレイ、無線タグ、ウェアラブルなコンピュータなどが製造され る。また、光学デバイスとしては、ディスプレイ用画素、光メモリ、光変調素子、光シャ ッター、第二次高調波（SHG)素子、偏光素子、フォトニッククリスタル、レンズアレイ などに、医療デバイスとしては、 DNAアレイ、タンパク質アレイなどのバイオチップなど に利用できる。化学分析デバイスとしては、微小化学プラント、微小化学分析システ ムなどのマイクロ化学チップに利用できる。  [0117] The substrate of the present invention can be used in a wide range of devices such as electronic, optical, medical and chemical analyses. For example, electronic devices can be used in integrated circuits such as transistors, memories, light emitting diodes (EL), lasers, and solar cells. With these device capabilities, flexible displays, wireless tags, and wearable computers are manufactured. Optical devices include display pixels, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, and medical devices include DNA arrays. It can be used for biochips such as protein arrays. As a chemical analysis device, it can be used for micro chemical chips such as micro chemical plants and micro chemical analysis systems.
[0118] 本発明のフォトリソグラフィー用表面処理剤は、ディスプレイ用カラーフィルタをイン クジェット法で製造する際に必要となるブラックマトリクスの撥液ィ匕に極めて有用であ る。インクジェット法はカラーフィルタを低コストで製造するための技術として期待され ているが、インクジェット技術単独ではブラックマトリクス内（画素部）に赤、緑、青のィ ンクを正確に印刷するだけの着弾精度が不足している。そのため、ブラックマトリクス の上部を撥液ィ匕して、誤って外れたインク液滴を画素内に引き戻す必要がある。また 、画素の膜厚を稼ぐために赤、緑、青のインクがブラックマトリクスの高さを超える量ま で注入される場合には、ブラックマトリクスの上部の撥液ィ匕が必須である。前者の撥 液性はインク溶液の転落角が、後者の撥液性は静的接触角が指標となる。 [0118] The surface treatment agent for photolithography of the present invention is extremely useful for the liquid repellency of a black matrix, which is necessary when producing a color filter for display by the inkjet method. The inkjet method is expected as a technology for manufacturing color filters at a low cost, but the inkjet technology alone has a landing accuracy that accurately prints red, green, and blue ink in the black matrix (pixel area). Is lacking. For this reason, it is necessary to repel the upper part of the black matrix and draw back ink droplets that have been accidentally removed into the pixels. Also When red, green, and blue inks are injected in amounts exceeding the height of the black matrix in order to increase the pixel film thickness, the liquid repellent layer on the top of the black matrix is essential. The former liquid repellency is indicated by the drop angle of the ink solution, and the latter liquid repellency is indicated by the static contact angle.
従来、ブラックマトリクスの撥液ィ匕のためには、大気圧プラズマ法により CF、 SF、  Conventionally, for liquid repellency of black matrix, CF, SF,
4 6 4 6
CHFなどのフッ素ガスをブラックマトリクスに吸着させていた（特開 2000 353594)。 Fluorine gas such as CHF was adsorbed on the black matrix (JP 2000 353594).
3  Three
しかし、この方法ではプラズマに由来する欠陥のために均一な撥液領域が形成され ないことや、ブラックマトリクスの上部のみならず側面も撥液ィ匕される問題があった。こ れらの欠点を改善するために、フッ素系ポリマータイプの感光性撥液処理剤が考案 された。 However, this method has a problem that a uniform liquid repellent region cannot be formed due to defects derived from plasma, and not only the upper part of the black matrix but also the side surface is liquid repelled. In order to remedy these drawbacks, a fluoropolymer type photosensitive liquid repellent was devised.
例えば、 For example,
特開平 11 281815 JP 11 281815
特開 2004— 151618 JP 2004-151618
特開 2005— 315984 JP 2005-315984
を参照できる。 Can be referred to.
しかし、これらの文献で開示されているフッ素系ポリマーには、撥液性と、感光性組 成物を形成する他素材との相溶性を両立できるものではな力つた。これに対し、本発 明のフォトリソグラフィー用表面処理剤は極めて高い撥液性と相溶性を両立している 以下に、本発明のフォトリソグラフィー用表面処理剤を用いてブラックマトリクスを撥 液ィ匕するための二つの方法について説明する。  However, the fluoropolymers disclosed in these documents have not been able to achieve both liquid repellency and compatibility with other materials forming the photosensitive composition. On the other hand, the surface treatment agent for photolithography of the present invention has both extremely high liquid repellency and compatibility. In the following, the black matrix is made liquid repellent by using the surface treatment agent for photolithography of the present invention. Two methods for doing this will be described.
一番目の方法は、本発明のフォトリソグラフィー用表面処理剤中に黒色の顔料を分 散させたものを用いて、フォトリソグラフィ一法により、親液性透明基板上に撥液化さ れたブラックマトリクスを形成する方法である。このときのフォトリソグラフィー用表面処 理剤の例としては、例えば、  The first method uses a black pigment dispersed in a lyophilic transparent substrate by a photolithography method using a surface treatment agent for photolithography of the present invention in which a black pigment is dispersed. It is a method of forming. As an example of the surface treatment agent for photolithography at this time, for example,
架橋性官能基 (E)と酸性基 (F)を有するフッ素系ポリマー (B) Fluoropolymer (B) having crosslinkable functional group (E) and acidic group (F)
5— 10重量％  5-10% by weight
架橋剤 (C) 1 5重量％ Cross-linking agent (C) 15% by weight
光架橋触媒 (D) 1— 5重量％ 20重量％カーボンブラック分散液 10— 20重量％ Photocrosslinking catalyst (D) 1—5% by weight 20% carbon black dispersion 10-20% by weight
溶媒 残部 (合計 100重量％とする）  Solvent balance (100% by weight in total)
が挙げられる。  Is mentioned.
[0120] 二番目の方法は、親液性透明基板上に均一に形成された感光性榭脂ブラック層の 上に、本発明のフォトリソグラフィー用表面処理剤を均一に塗布した後、フォトリソダラ フィ一法により、親液性透明基板上に撥液化されたブラックマトリクスを形成する方法 である。このときのフォトリソグラフィー用表面処理剤の例としては、例えば、 酸性基 (F)を有するフッ素系ポリマー（B) 5— 10重量％  [0120] The second method is to apply a photolithographic surface treatment agent of the present invention uniformly on a photosensitive resin black layer uniformly formed on a lyophilic transparent substrate, One method is to form a lyophobic black matrix on a lyophilic transparent substrate. Examples of surface treatment agents for photolithography at this time include, for example, a fluorine-based polymer (B) having an acidic group (F) 5 to 10% by weight
架橋剤 (C) 1 5重量％  Cross-linking agent (C) 15% by weight
光架橋触媒 (D) 1— 5重量％  Photocrosslinking catalyst (D) 1—5% by weight
溶媒 残部 (合計 100重量％とする）  Solvent balance (100% by weight in total)
が挙げられる。  Is mentioned.
[0121] これらのいずれかで撥液化されたブラックマトリクスを有する透明基板上に、カラー フィルタ用の赤、黒、黄の顔料分散液をインクジヱット法により塗布し、溶媒を除去す ることでカラーフィルタが極めて低コストで製造できる。  [0121] On a transparent substrate having a black matrix repellent with any of these, a red, black, or yellow pigment dispersion for color filter is applied by an ink jet method, and the solvent is removed to remove the color filter. Can be manufactured at an extremely low cost.
実施例  Example
[0122] 以下に実施例により本発明を具体的に説明するが、本発明はこれらに限定されな い。  [0122] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[0123] 静的接触角と転落角は次の方法で測定した。  [0123] The static contact angle and the sliding angle were measured by the following methods.
静的接触角 ¾落角の測定  Static contact angle ¾Measurement of drop angle
静的接触角は、水平に置いた基板にマイクロシリンジ力 水、または、 n—へキサデ カンを 2 L滴下し、滴下 1秒後の静止画をビデオマイクロスコープで撮影することによ り求めた。  The static contact angle was obtained by dropping 2 L of microsyringe-powered water or n-hexadecane on a horizontally placed substrate and taking a still image 1 second after dropping with a video microscope. .
また、転落角は以下の方法で求めた。水平に置いた基板にマイクロシリンジから、 水の場合は 20 μ L、 n—へキサデカンとプロピレングリコールモノメチルエーテルァセ テート (PGMEA)の場合は 5 μ L滴下し、基板を毎秒 2° の速度で傾斜させ、液滴が 転落し始めるまでを、ビデオマイクロスコープで動画として記録した。その動画を再生 し、液滴が転落し始める角度を転落角とした。 [0124] 製造例 1 The sliding angle was determined by the following method. Drop 20 μL for water and 5 μL for n-hexadecane and propylene glycol monomethyl etherate (PGMEA) from a microsyringe onto a horizontally placed substrate, and add the substrate at a rate of 2 ° per second. It was tilted and recorded as a moving picture with a video microscope until the droplet started to fall. The video was replayed and the angle at which the droplet began to fall was defined as the falling angle. [0124] Production Example 1
還流冷却管、窒素導入管、温度計、撹拌装置を備えた四つ口フラスコ中にフッ素 系モノマー CH =C (F) COOCH CH C F (略称 α— F) 100g、 HCFC225 40  Fluorine monomer CH = C (F) COOCH CH C F (abbreviation α-F) 100g, HCFC225 40 in a four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer, and stirrer
2 2 2 4 9  2 2 2 4 9
Ogを入れ、 50°Cに加熱後、 30分間窒素気流下で撹拌した。これに 2,2'—ァゾビスィ ソブチ口-トリル 0. 5gを添カ卩し、 18時間重合した。反応液中の残存モノマーをガスク 口マトグラフィ一で分析することより、重合率が 95%以上であることを確認した。得られ た反応液をメタノールで沈殿、真空乾燥して、フッ素系ポリマーを単離した。得られた フッ素系ポリマーの分子量を GPCで測定すると、重量平均分子量は 21, 000 (ポリス チレン換算）であった。  Og was added, and the mixture was heated to 50 ° C and stirred for 30 minutes under a nitrogen stream. To this was added 0.5 g of 2,2′-azobisi soft mouth-tolyl and polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography, and it was confirmed that the polymerization rate was 95% or more. The resulting reaction solution was precipitated with methanol and vacuum dried to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 21,000 (in terms of polystyrene).
[0125] 製造例 2, 3,比較製造例 1 [0125] Production Example 2, 3, Comparative Production Example 1
製造例 1のフッ素系モノマーを、それぞれ、 CH =C (Cl) COOCH CH C F (略  The fluorinated monomers of Production Example 1 are each represented by CH = C (Cl) COOCH CH C F
2 2 2 4 9 称 a— C1)、CH =C (H) COO (CH ) SO C F (略称 S02Pr)、CH =CHCOO  2 2 2 4 9 Nominal a— C1), CH = C (H) COO (CH) SO C F (abbreviation S02Pr), CH = CHCOO
2 2 3 2 4 9 2  2 2 3 2 4 9 2
CH CH C F (略称 α—H)に置き換えたものを製造例 2, 3,比較製造例 1とした。  Products replaced with CH 2 CH 3 C F (abbreviation α—H) were designated Production Example 2 and 3, and Comparative Production Example 1.
2 2 4 9  2 2 4 9
重量平均分子量は、それぞれ、 16, 000、 9, 000、 15, 000であった。  The weight average molecular weights were 16,000, 9,000, and 15,000, respectively.
[0126] 実施例 1〜3、比較例 1 [0126] Examples 1 to 3, Comparative Example 1
基板のシリコンウェハはアセトンで洗浄後、真空紫外光を照射することにより、表面 を超親水化した。この基板に、製造例 1〜3,比較製造例 1のフッ素系ポリマーを HC FC225で希釈して調製した 1重量％溶液を、 2000rpm、 1分間の条件でスピンコー トして、膜厚 (溶媒を除いた膜厚） lOOnmの膜を作製した。この膜の静的接触角と転 落角を測定した。結果を表 1に示す。併記したガラス転移点はバルタのポリマーにつ いて測定したものである。静的接触角は実施例と比較例でほとんど差がないが、転 落角は実施例の方が比較例よりもはるかに小さぐ液体が転がりやすい。  The substrate silicon wafer was cleaned with acetone, and then the surface was made superhydrophilic by irradiation with vacuum ultraviolet light. A 1 wt% solution prepared by diluting the fluoropolymers of Production Examples 1 to 3 and Comparative Production Example 1 with HC FC225 was spin-coated on this substrate at 2000 rpm for 1 minute to obtain a film thickness (solvent Excluded film thickness) An lOOnm film was prepared. The static contact angle and rolling angle of this film were measured. The results are shown in Table 1. The glass transition point shown is measured for Balta polymer. The static contact angle is almost the same between the example and the comparative example, but the falling angle is much smaller in the example than in the comparative example, and the liquid tends to roll.
[0127]  [0127]
Figure imgf000042_0001
[0128] これらの膜にライン/スペース =10 μ m/10 μ mのフォトマスクを密着させ、 10分間、 真空紫外光を照射することにより、照射領域を親液化し、撥液領域と親液領域から成 るパターン基板を作製した。
Figure imgf000042_0001
[0128] A photomask of line / space = 10 μm / 10 μm was adhered to these films and irradiated with vacuum ultraviolet light for 10 minutes to make the irradiated region lyophilic, and the lyophobic region and lyophilic solution. A patterned substrate consisting of regions was fabricated.
これらのパターン基板にポリ（9, 9ージォクチルフルオレン） [American Dye Source 社製 ADS129BE]の 1重量0 /0トルエン溶液をインクジェット法により塗布した。インクジェ ットは、ノズル径を 50 mとし、オンデマンド法で行った。トルエン乾燥後の薄膜を光 学顕微鏡で観察したところ実施例 1〜3ではライン幅 10 μ mの親液領域に沿って明 瞭に分裂したポリマー薄膜が形成された。一方、比較例 1では不明瞭にしか分裂しな かった。 Was applied by poly These patterned substrate (9, 9-1-di O Chi le fluorene) [American Dye Source, Inc. ADS129BE] inkjet method 1wt 0/0 solution in toluene. The inkjet was performed by an on-demand method with a nozzle diameter of 50 m. When the thin film after drying with toluene was observed with an optical microscope, in Examples 1 to 3, a polymer thin film clearly divided along the lyophilic region having a line width of 10 μm was formed. On the other hand, in Comparative Example 1, it was split only indefinitely.
[0129] 実施例 4, 5、比較例 2  [0129] Examples 4, 5 and Comparative Example 2
基板は実施例 1と同じものを使用した。実施例 4では、ビスフエノール A—ジヒロロキ シェチルエーテルジアタリレート（架橋剤） 45重量％、 a—F (フッ素系モノマー） 25重 量％、両末端をメタクリロイル基で変性した分子量 5, 000のジメチルポリシロキサン（ 架橋剤） 25重量％、 2 ヒドロキシー2—メチルー 1 フエ-ルプロパン (光重合開始剤 ) 5重量％となるように混合溶解させ、この溶液をドクターブレードを用いて基板上に 膜厚 (溶媒を除いた膜厚）が 100 mとなるように塗布した。実施例 5、比較例 2では 、それぞれ、 — Fを α Cl、 a—Hに置き換えた。  The same substrate as in Example 1 was used. In Example 4, bisphenol A-dihirochetyl ether diatalylate (crosslinking agent) 45% by weight, a-F (fluorine monomer) 25% by weight, both ends modified with methacryloyl groups and having a molecular weight of 5,000 Dimethylpolysiloxane (cross-linking agent) 25% by weight, 2-hydroxy-2-methyl-1 phenol propane (photopolymerization initiator) 5% by weight are mixed and dissolved, and this solution is deposited on the substrate using a doctor blade. The film was applied so that the film thickness (excluding the solvent) was 100 m. In Example 5 and Comparative Example 2, —F was replaced with α Cl and a—H, respectively.
[0130] 窒素雰囲気下で、ライン/スペース =10 μ m/10 μ mのフォトマスクを介して、処理基 板に波長 365nmの紫外線を積算照度 lOOOmjZcm2の条件で照射した。この操作 で照射領域は架橋し溶媒に不溶となる。次にメタノールに基板を浸漬することにより 未照射領域のフッ素系ポリマーを溶解、除去することにより、撥液領域と親液領域か ら成るパターン基板を作製した。 [0130] Under a nitrogen atmosphere, through a photomask having a line / space = 10 μ m / 10 μ m , the ultraviolet rays having a wavelength of 365nm was irradiated under the condition of integral illuminance LOOOmjZcm 2 to the processing board. This operation crosslinks the irradiated area and makes it insoluble in the solvent. Next, a patterned substrate comprising a liquid repellent region and a lyophilic region was prepared by dissolving and removing the fluoropolymer in the unirradiated region by immersing the substrate in methanol.
これらのパターン化基板にポリ（9, 9ージォクチルフルオレン）の 1重量0 /0トルエン溶 液をインクジェット法により塗布した。トルエン乾燥後の薄膜を光学顕微鏡で観察した ところ実施例 4, 5ではライン幅 10 mの親液領域に沿って明瞭に分裂したポリマー 薄膜が形成された。一方、比較例 2では不明瞭にしか分裂しな力 た。 1 weight 0/0 toluene solvent solution of poly these patterned substrate (9, 9-1-di O Chi le fluorene) was coated by an inkjet method. When the toluene-dried thin film was observed with an optical microscope, in Examples 4 and 5, a polymer thin film clearly divided along the lyophilic region having a line width of 10 m was formed. On the other hand, in Comparative Example 2, the force was split only indefinitely.
[0131] 製造例 4  [0131] Production Example 4
還流冷却管、窒素導入管、温度計、撹拌装置を備えた四つ口フラスコ中に oc -C1 50g、メタクリノレ酸 50g、イソプロピノレアノレ =f一ノレ 400gを人れ、 70oCにカロ熱後、 30 分間窒素気流下で撹拌した。これに 2, 2'—ァゾビスイソプチ口-トリル lgを添加し、 1 8時間重合した。反応液中の残存モノマーをガスクロマトグラフィーで分析することより 、重合率が 95%以上であることを確認した。得られた反応液をへキサンで沈殿、真空 乾燥して、フッ素系ポリマーを単離した。得られたフッ素系ポリマーの分子量を GPC で測定すると、重量平均分子量は 35, 000 (ポリスチレン換算)であった。 Oc -C1 in a four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer 50 g, 50 g of methacrylolic acid, and 400 g of isopropylenoleole = f monoole were collected and stirred at 70 ° C. for 30 minutes under a nitrogen stream. To this, 2,2′-azobisisopetityl-tolyl lg was added and polymerized for 18 hours. The residual monomer in the reaction solution was analyzed by gas chromatography, and it was confirmed that the polymerization rate was 95% or more. The resulting reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 35,000 (polystyrene conversion).
[0132] 比較製造例 2 [0132] Comparative Production Example 2
製造例 4のフッ素系モノマーを α—Hに置き換えたものを比較製造例 2とした。重量 平均分子量は、 32, 000であった。  Comparative Production Example 2 was obtained by replacing the fluorinated monomer of Production Example 4 with α-H. The weight average molecular weight was 32,000.
[0133] 実施例 6、比較例 3 [0133] Example 6, Comparative Example 3
製造例 4または比較製造例 2のフッ素系ポリマー 10重量％、酸発生剤 WPAG— 1 99 (和光純薬） 1重量％、酸架橋剤サイメル 303 (日本サイテックインダストリーズ） 5 重量％、プロピレングリコールモノメチルエーテル 84重量0 /0の溶液を、実施例 1と 同様の基板にスピンコートして基板上に膜厚 (溶媒を除!ヽた膜厚) 5 μ mの膜を作製 した。 110°Cで 3分間加熱後、この膜にライン/スペース =10 μ m/10 μ mのフォトマス クを介して、 365nmの紫外線を積算照度 lOOmiZcm2の条件で照射し、さらに 110 °Cで 3分間加熱した。この操作で照射領域は架橋して溶媒に不溶となる。次に、 2. 3 8重量0 /0テトラメチルアンモ-ゥムヒドロキシド水溶液に 1分間浸漬することにより現像 した後、水洗して、撥液領域と親液領域から成るパターン基板を作製した。 Fluoropolymer 10% by weight in Production Example 4 or Comparative Production Example 2, acid generator WPAG-1 99 (Wako Pure Chemicals) 1% by weight, acid crosslinking agent Cymel 303 (Nippon Cytec Industries) 5% by weight, propylene glycol monomethyl ether a solution of 84 weight 0/0 and was spin-coated to form a film having a thickness (excluding the solvent! wasヽthickness) 5 mu m on a substrate same substrate as in example 1. After heating at 110 ° C for 3 minutes, this film was irradiated with 365nm UV light via a photomask with a line / space = 10 μm / 10 μm under the condition of integrated illuminance lOOmiZcm 2 and at 110 ° C. Heated for 3 minutes. By this operation, the irradiated region is cross-linked and becomes insoluble in the solvent. Next, 2.3 8 wt 0/0 tetramethylammonium - was developed by immersion for 1 minute in Umuhidorokishido aqueous solution, washed with water, to produce a patterned substrate made of liquid-repellent region and the lyophilic region.
これらのパターン化基板にポリ（9, 9ージォクチルフルオレン）の 1重量0 /0トルエン溶 液をインクジェット法により塗布した。トルエン乾燥後の薄膜を光学顕微鏡で観察した ところ実施例 6ではライン幅 10 mの親液領域に沿って明瞭に分裂したポリマー薄膜 が形成された。一方、比較例 3では不明瞭にしか分裂しな力 た。 1 weight 0/0 toluene solvent solution of poly these patterned substrate (9, 9-1-di O Chi le fluorene) was coated by an inkjet method. When the thin film after drying with toluene was observed with an optical microscope, in Example 6, a polymer thin film clearly divided along the lyophilic region having a line width of 10 m was formed. On the other hand, in Comparative Example 3, the force was split only indefinitely.
[0134] 製造例 5 [0134] Production Example 5
還流冷却管、窒素導入管、温度計、撹拌装置を備えた四つ口フラスコ中に ex - C1 50g、 tーブチノレメタタリレート 50g、醉酸ブチノレ 400gを人れ、 70oCにカロ熱後、 30 分間窒素気流下で撹拌した。これに 2, 2'—ァゾビスイソプチ口-トリル lgを添加し、 1 8時間重合した。反応液中の残存モノマーをガスクロマトグラフィーで分析することより 、重合率が 95%以上であることを確認した。得られた反応液をへキサンで沈殿、真空 乾燥して、フッ素系ポリマーを単離した。得られたフッ素系ポリマーの分子量を GPC で測定すると、重量平均分子量は 36, 000 (ポリスチレン換算）であった。 Reflux condenser, nitrogen inlet, thermometer, in a four-necked flask equipped with a stirrer ex - C1 50 g, t chromatography butyrate Honoré meth Tari rate 50 g, which person醉酸Buchinore 400 g, Caro heat to 70 o C Thereafter, the mixture was stirred for 30 minutes under a nitrogen stream. To this, 2,2′-azobisisopetityl-tolyl lg was added and polymerized for 18 hours. By analyzing the residual monomer in the reaction solution by gas chromatography It was confirmed that the polymerization rate was 95% or more. The resulting reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 36,000 (polystyrene conversion).
[0135] 比較製造例 3  [0135] Comparative production example 3
製造例 5のフッ素系モノマーを α—Hに置き換えたものを比較製造例 3とした。重量 平均分子量は、 33, 000であった。  Comparative Production Example 3 was obtained by replacing the fluorinated monomer of Production Example 5 with α-H. The weight average molecular weight was 33,000.
[0136] 実施例 7、比較例 4  [0136] Example 7, Comparative Example 4
製造例 5または比較製造例 3のフッ素系ポリマー 10重量％、光酸発生剤 WPAG— 199 (和光純薬） 1重量％、酢酸ブチル 89重量％の溶液を、実施例 1と同様の基板 にスピンコートして基板上に膜厚 (溶媒を除 ヽた膜厚) 3 μ mの膜を作製した。 110°C で 3分間加熱後、この膜にライン/スペース =10 μ m/10 μ mのフォトマスクを介して、 3 65nmの紫外線を積算照度 1 OOmjZcm2の条件で照射し、さらに PEB処理として 11 0°Cで 3分間加熱した。この操作で、酸発生剤から発生した強酸の作用により、照射 領域の t—ブチルメタタリレートの t—ブチル基が脱離し、カルボン酸となる。次に、 2. 38重量0 /0テトラメチルアンモ-ゥムヒドロキシド溶液に 1分間浸漬することにより現像 した後、水洗、乾燥、 200°Cで 30分間熱処理して、撥液領域と親液領域から成るパ ターン基板を作製した。 Spin a solution of 10% by weight of the fluoropolymer of Production Example 5 or Comparative Production Example 3, 1% by weight of the photoacid generator WPAG-199 (Wako Pure Chemical Industries) and 89% by weight of butyl acetate onto the same substrate as in Example 1. A film having a thickness of 3 μm (film thickness excluding the solvent) was prepared on the substrate. After 3 minutes heating at 110 ° C, through a photomask having a line / space = 10 μ m / 10 μ m in this film, the 3 65 nm of ultraviolet irradiation under the condition of integral illuminance 1 OOmjZcm 2, as further PEB treatment Heated at 110 ° C. for 3 minutes. By this operation, the t-butyl group of t-butyl metatalylate in the irradiated region is eliminated by the action of a strong acid generated from the acid generator to form a carboxylic acid. Then, 2. 38 wt 0/0 tetramethylammonium - was developed by immersion for 1 minute in Umuhidorokishido solution, washed with water, dried, and heat-treated for 30 minutes at 200 ° C, consisting of liquid-repellent region and the lyophilic region A pattern substrate was fabricated.
これらのパターン化基板にポリ（9, 9ージォクチルフルオレン）の 1重量0 /0トルエン溶 液をインクジェット法により塗布した。トルエン乾燥後の薄膜を光学顕微鏡で観察した ところ実施例 7ではライン幅 10 mの親液領域に沿って明瞭に分裂したポリマー薄膜 が形成された。一方、比較例 4では不明瞭にしか分裂しな力 た。 1 weight 0/0 toluene solvent solution of poly these patterned substrate (9, 9-1-di O Chi le fluorene) was coated by an inkjet method. When the thin film after drying with toluene was observed with an optical microscope, in Example 7, a polymer thin film clearly divided along the lyophilic region having a line width of 10 m was formed. On the other hand, in Comparative Example 4, the force was split only indefinitely.
[0137] 製造例 6  [0137] Production Example 6
還流冷却管、窒素導入管、温度計、撹拌装置を備えた四つ口フラスコ中にフルォ ロアタリレート CH =C (Cl) COOCH CH C F (略称 α Cl) 50g、メタクリノレ酸 20g  In a four-necked flask equipped with a reflux condenser, nitrogen inlet, thermometer, and stirrer, fluoroatalylate CH = C (Cl) COOCH CH C F (abbreviation α Cl) 50 g, methacrylolic acid 20 g
2 2 2 4 9  2 2 2 4 9
、 2 ェチル 2 ァダマンチルメタタリレート（略称 AdEMA) 30g、ラウリルメルカプ タン 5g、プロピレングリコールモノメチルエーテルアセテート 300gを入れ、 70°Cにカロ 熱後、 30分間窒素気流下で撹拌した。これに 2,2' ァゾビスイソプチ口-トリル lgを 添加し、 18時間重合した。反応液中の残存モノマーをガスクロマトグラフィーで分析 することより、重合率が 95%以上であることを確認した。得られた反応液をへキサンで 沈殿、真空乾燥して、フッ素系ポリマーを単離した。得られたフッ素系ポリマーの分子 量を GPCで測定すると、重量平均分子量は 11, 000 (ポリスチレン換算）であった。 また、 DSCで測定したガラス転移点は 135°Cであった。 DSCの温度範囲と昇温速度 は、 1 st RUN： - 50 - 200°C ( 10°C/min) , 2nd RUN： - 50 - 200°C ( 10°C/min )であり、ガラス転移点をは 2nd RUNの補外ガラス転移終了温度とした。 Then, 30 g of 2-ethyl 2-adamantyl metatalylate (abbreviated as AdEMA), 5 g of lauryl mercaptan, and 300 g of propylene glycol monomethyl ether acetate were added, followed by heating at 70 ° C. and stirring for 30 minutes under a nitrogen stream. To this was added 2,2′azobisisobutyl-tolyl lg and polymerized for 18 hours. Residual monomer in reaction solution is analyzed by gas chromatography As a result, it was confirmed that the polymerization rate was 95% or more. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. When the molecular weight of the obtained fluoropolymer was measured by GPC, the weight average molecular weight was 11,000 (polystyrene conversion). The glass transition point measured by DSC was 135 ° C. DSC temperature range and heating rate are 1 st RUN:-50-200 ° C (10 ° C / min), 2nd RUN:-50-200 ° C (10 ° C / min), and glass transition point Is the extrapolated glass transition end temperature of 2nd RUN.
[0138] 製造例 7, 8,比較製造例 3 [0138] Production Examples 7, 8, Comparative Production Example 3
製造例 6のフルォロアタリレートを、それぞれ、 CH =C (H) COO (CH ) SO C F  Fluoroatalylate of Production Example 6 is CH = C (H) COO (CH) SO C F respectively
2 2 3 2 4 9 2 2 3 2 4 9
(略称 S02Pr)、 CH =C (CH ) COOCH CH C F (略称 a— CH3)、 CH =CH (Abbreviation S02Pr), CH = C (CH) COOCH CH C F (abbreviation a-CH3), CH = CH
2 3 2 2 4 9 2 2 3 2 2 4 9 2
COOCH CH C F (略称 a—H)に置き換えたものを製造例 7, 8,比較製造例 3と COOCH CH C F (abbreviation a-H) replaced with production examples 7, 8, comparative production example 3 and
2 2 4 9  2 2 4 9
した。重量平均分子量は、それぞれ、 9, 000、 12, 000、 10, 000であった。ガラス 転移点はそれぞれ 115° 、87° 、71° であった。  did. The weight average molecular weights were 9, 000, 12,000, and 10,000, respectively. The glass transition points were 115 °, 87 °, and 71 °, respectively.
[0139] 実施例 8〜： L0,比較例 5 [0139] Example 8-: L0, Comparative Example 5
製造例 6 (実施例 8に相当）、製造例 7 (実施例 9に相当）、製造例 8 (実施例 10に相 当）、製造比較例 3 (比較例 5に相当）のフッ素系ポリマー 10重量％、酸架橋剤サイメ ル 300 [へキサメトキシメチルメラミン] (日本サイテックインダストリーズ社製) 4重量％ 、酸発生剤 CGI— 1397 [(5—プロピルスルフォ-ルォキシイミノー 5H—チォフェン —2—イリデン)―（2—メチルフエ-ル)ァセトニトリル] (チノく'スぺシャリティ'ケミカル ズ社製） 0. 5重量0 /0、プロピレングリコールモノメチルエーテルアセテート 85. 5重 量％の溶液を、実施例 1と同様の方法で超親水化したガラス基板にスピンコートして 基板上に膜厚 (溶媒を除 ヽた膜厚) 3 μ mの膜を作製した。 110°Cで 3分間加熱後、 この膜にライン/スペース =10 μ m/10 μ mのフォトマスクを介して、キャノン製マスクァ ライナ PLA— 501から 365nmの紫外線を積算照度 30mjZcm2の条件で照射し、さ らに PEB処理として 110°Cで 3分間加熱した。この操作で照射領域は架橋して溶媒 に不溶となる。次に、アルカリ現像液 P3 disperse M (ヘンケルジャパン社製）の 15% 水溶液に 1分間浸漬することにより現像した後、水洗、乾燥、 200°Cで 1時間加熱し て、撥液領域と親液領域から成るパターン基板を作製した。パターンを電界効果型 走査型電子顕微鏡 (FE— SEM)で観察したところ、実施例 8〜10では線幅 10 m の明瞭なラインパターンが形成された。一方、比較例 5ではラインの形状に乱れが観 察された。 Fluoropolymers of Production Example 6 (corresponding to Example 8), Production Example 7 (corresponding to Example 9), Production Example 8 (corresponding to Example 10), Production Comparative Example 3 (corresponding to Comparative Example 5) 10 % By weight, acid crosslinking agent Cymele 300 [Hexamethoxymethylmelamine] (Nippon Cytec Industries, Ltd.) 4% by weight, acid generator CGI-1397 [(5-propylsulfoxy-oxyimino 5H-thiophene-2-Ilidene) - (2-Mechirufue - Le) Asetonitoriru] (Chinoku made 'scan Bae Shariti' Chemical Co., Ltd.) 0.5 weight 0/0, the propylene glycol monomethyl ether acetate 85.5 by weight% of the solution, as in example 1 A superhydrophilic glass substrate was spin-coated by the same method, and a film having a thickness of 3 μm (thickness excluding the solvent) was produced on the substrate. After heating at 110 ° C for 3 minutes, this film was irradiated with UV light from Canon Maskliner PLA — 501 to 365 nm through a photomask of line / space = 10 μm / 10 μm under the condition of an integrated illumination of 30 mjZcm 2 Furthermore, it was heated at 110 ° C for 3 minutes as a PEB treatment. This operation crosslinks the irradiated area and makes it insoluble in the solvent. Next, the film was developed by immersing it in a 15% aqueous solution of alkaline developer P3 disperse M (Henkel Japan) for 1 minute, washed with water, dried, and heated at 200 ° C for 1 hour. A patterned substrate consisting of regions was produced. When the pattern was observed with a field-effect scanning electron microscope (FE—SEM), in Examples 8 to 10, the line width was 10 m. A clear line pattern was formed. On the other hand, in Comparative Example 5, disorder was observed in the line shape.
[0140] これらのパターン基板に液晶ディスプレイ カラーフィルタ用着色剤をインクジェット 法により塗布した。インクジェット装置は Litrex 70(Litrex社製)を用いて、一滴当た りの容量 15pLで、ドット密度 80 mの間隔でパターン基板に吐出した。均一に親水 化した基板を用いた場合、溶媒乾燥後に約 200 mの直径の薄膜が形成されること が光学顕微鏡で観察された。一方、ノターン基板を用いた場合、実施例 8〜10では 線幅 10 μ mの親液領域に沿って明瞭に分裂したカラー薄膜が形成された。これに 対し、比較例 5では親液領域のみならず撥液領域にも薄膜が形成される箇所が存在 し、カラー薄膜の分裂は不完全であった。  [0140] A colorant for a liquid crystal display color filter was applied to these pattern substrates by an inkjet method. The ink jet device used Litrex 70 (manufactured by Litrex) was ejected onto the pattern substrate with a capacity of 15 pL per drop and a dot density of 80 m. When using a uniformly hydrophilic substrate, it was observed with an optical microscope that a thin film with a diameter of about 200 m was formed after solvent drying. On the other hand, when a noturn substrate was used, in Examples 8 to 10, a color thin film that was clearly split along the lyophilic region having a line width of 10 μm was formed. On the other hand, in Comparative Example 5, there were portions where a thin film was formed not only in the lyophilic region but also in the lyophobic region, and the color thin film was not completely split.
[0141] 上記の電磁波硬化組成物をスピンコートした膜に、フォトマスクを介さずに全面に紫 外線を照射して調製した均一撥液領域の転落角を測定した。実施例 8〜10,比較例 5の n—へキサデカンに対する転落角はそれぞれ 15° 、 17° 、 20° 、 55° 、 PGM EAに対する転落角はそれぞれ 17° 、 20° 、 21° 、 62° であり、実施例の撥液領 域は極めて液体が転落しやす力つた。転落角においては、液滴に対して斜面方向に mg ' sin a [ここで、 m :液滴の質量、 g :重力加速度、 α：転落角]の力が加わる。すな わち、転落角は撥液領域で液滴を移動させるための最小の力を示す。実施例 8〜1 0でカラーフィルタ用着色剤の分裂性が良好であった原因は撥液領域で液滴が移動 しゃす 、ことであると推定される。  [0141] The falling angle of a uniform liquid-repellent region prepared by irradiating the entire surface of the film coated with the above-mentioned electromagnetic wave curable composition with ultraviolet rays without using a photomask was measured. In Examples 8 to 10 and Comparative Example 5, the falling angles for n-hexadecane are 15 °, 17 °, 20 °, 55 °, and the falling angles for PGM EA are 17 °, 20 °, 21 °, and 62 °, respectively. In addition, the liquid repellent area of the example was extremely strong in liquid falling. At the tumbling angle, a force of mg 'sin a [where m is the mass of the droplet, g is the acceleration of gravity, and α is the tumbling angle] is applied to the droplet. In other words, the falling angle indicates the minimum force for moving the droplet in the liquid repellent region. In Examples 8 to 10, it is estimated that the reason why the color filter colorant had good splitting properties was that the liquid droplets moved in the liquid repellent region.
[0142] 製造例 9〜20,比較製造例 4  [0142] Production Examples 9 to 20, Comparative Production Example 4
製造例 6のフルォロアタリレートと高軟ィ匕点モノマーを表 2に示すものに置き換えた 場合を製造例 9〜20,比較製造例 4とした。化合物名と略称の関係は以下の通りで ある。 CH = CHCOOCH CH C F (略称 C8 a— H)、 2—メチル—2—ァダマン  Production examples 9 to 20 and comparative production example 4 were obtained by replacing the fluoroatalylate and the high soft spot monomer of Production Example 6 with those shown in Table 2. The relationship between compound names and abbreviations is as follows. CH = CHCOOCH CH C F (abbreviation C8 a— H), 2-methyl-2-adaman
2 2 2 8 17  2 2 2 8 17
チルメタタリレート（略称 AdMMA)、メチルメタタリレート（略称 MMA)、イソボル-ル メタタリレート（略称 iBMA)、フエ-ルメタタリレート（略称 PhMA)、ノルボル-ルメチ ルメタタリレート（略称 NBMA)、シクロへキシルメタタリレート（略称 CHMA)。重量平 均分子量は、いずれも、 5, 000- 12, 000の範囲であった。ガラス転移点を表 2に 示す。 実施例 11〜22,比較例 6 Tylmetatalylate (abbreviation AdMMA), Methylmetatalylate (abbreviation MMA), Isovol Metatalylate (abbreviation iBMA), Phenol Metatalylate (abbreviation PhMA), Norbornyl Methyl Metatalylate (abbreviation NBMA), Cyclohe Xylmethalate (abbreviation CHMA). The weight average molecular weights were all in the range of 5,000 to 12,000. Table 2 shows the glass transition point. Examples 11-22, Comparative Example 6
実施例 8のフッ素系ポリマー (製造例 6)を製造例 7〜20,比較製造例 4に置き換え た場合を実施例 11〜22,比較例 6とした。ノターンを FE— SEMで観察したところ、 実施例 11〜22では線幅 10 mの明瞭なラインパターンが形成された。一方、比較 例 6ではラインの形状に乱れが観察された。これらのパターンィ匕基板にカラーフィル タ用着色剤をインクジェット法により塗布した。溶媒乾燥後の薄膜を光学顕微鏡で観 察したところ実施例 11〜22では線幅 10 /z mの親液領域に沿って明瞭に分裂した力 ラー薄膜が形成された。一方、比較例 6では親液領域のみならず撥液領域にも薄膜 が形成される箇所が存在した。  Examples 11 to 22 and Comparative Example 6 were obtained by replacing the fluoropolymer of Production Example 8 (Production Example 6) with Production Examples 7 to 20 and Comparative Production Example 4. When Noturn was observed with FE-SEM, in Examples 11 to 22, a clear line pattern having a line width of 10 m was formed. On the other hand, in Comparative Example 6, disorder was observed in the line shape. A color filter colorant was applied to these patterned substrates by an inkjet method. When the thin film after drying the solvent was observed with an optical microscope, in Examples 11 to 22, a force-strength film that was clearly split along the lyophilic region having a line width of 10 / z m was formed. On the other hand, in Comparative Example 6, there was a portion where a thin film was formed not only in the lyophilic region but also in the lyophobic region.
一方、上記の電磁波硬化組成物をスピンコートした膜に、フォトマスクを介さずに全 面に紫外線を照射して調製した均一撥液領域の静的接触角と転落角を測定した結 果を表 2に示す。  On the other hand, the results of measuring the static contact angle and the falling angle of a uniform liquid-repellent region prepared by irradiating the entire surface with ultraviolet rays on a film coated with the above-mentioned electromagnetic wave curable composition without using a photomask are shown. Shown in 2.
Figure imgf000048_0001
Figure imgf000048_0001
共重合体組成：フルォロアクリ レート（B- 1) /メタクリル酸 (B - 2) /高軟化点モノ · '一 (B— 3) Copolymer composition: Fluoroacrylate (B-1) / Methacrylic acid (B-2) / High softening point mono · One (B-3)
=50/20/30重量; 4  = 50/20/30 weight; 4
架撟剤：へキサメ トキシメチルメラミン Skull agent: hexamethoxymethylmelamine
実施例 23 Example 23
製造例 7のフッ素系ポリマー 8重量0 /0、ペンタエリスリトールテトラアタリレート 4重量 %、 2 メチル 1— [4 (メチルチオ)フエ-ル] -2 -モンフォリノプロパノン 1 (チバ 'スぺシャリティ一'ケミカルズ (株)製ィルガキュア 907) 1重量0 /0、プロピレングリコー ルモノメチルエーテルアセテート 82重量％の溶液を、実施例 1と同様の方法で超親 水化したガラス基板にスピンコートして基板上に膜厚 (溶媒を除 ヽた膜厚) 2 μ mの膜 を作製した。以下は実施例 8と同様の方法で撥液領域と親液領域から成るパターン 基板を作製した。ノターンを FE— SEMで観察したところ、線幅 10 mの明瞭なライ ンパターンが形成された。 Fluoropolymer 8 wt 0/0 of Preparation 7, pentaerythritol tetra Atari rate 4 wt%, 2-methyl-1- [4 (methylthio) Hue - le] -2 - Mont morpholinopropane propanone 1 (Ciba 'scan Bae Shariti one 'Chemicals Co. Irugakyua 907) 1 wt 0/0, propylene glycol A solution of 82% by weight of rumonomethyl ether acetate was spin-coated on a superhydrophilic glass substrate in the same manner as in Example 1, and a film thickness (film thickness excluding the solvent) of 2 μm was formed on the substrate. Was made. A patterned substrate composed of a liquid repellent region and a lyophilic region was prepared in the same manner as in Example 8 below. When Noturn was observed with FE-SEM, a clear line pattern with a line width of 10 m was formed.
[0146] これらのパターン基板に実施例 8と同様の方法でカラーフィルタ用着色剤をインク ジェット法により塗布した結果、線幅 10 mの親液領域に沿って明瞭に分裂したカラ 一薄膜が形成された。  [0146] As a result of applying the color filter colorant to these patterned substrates by the ink jet method in the same manner as in Example 8, a color thin film that was clearly split along the lyophilic region with a line width of 10 m was formed. It was done.
[0147] 製造例 21  [0147] Production Example 21
製造例 14のフルォロアタリレートを  Fluoro acrylate for Production Example 14
CH3  CH3
CH2=C  CH2 = C
COOCH2CH2NHCOOCH2CH2S _ (CH2-CH)7 - H COOCH2CH2NHCOOCH2CH2S _ (CH2-CH) 7-H
COO(CH2)3S02C4.F9 に置き換えたグラフト共重合体を製造例 21とした。重量平均分子量は 13, 000、ガラ ス転移点 125°Cであった。  The graft copolymer replaced with COO (CH2) 3S02C4.F9 was used as Production Example 21. The weight average molecular weight was 13,000 and the glass transition point was 125 ° C.
[0148] 実施例 24 [0148] Example 24
実施例 16のフッ素系ポリマー（ランダム共重合体)を製造例 21のグラフト共重合体 に置き換えた場合を実施例 24とする。パターンを FE— SEMで観察したところ、線幅 10 μ mの明瞭なラインパターンが形成された。これらのパターン基板に実施例 8と同 様の方法でカラーフィルタ用着色剤をインクジェット法により塗布した結果、線幅 10 mの親液領域に沿って明瞭に分裂したカラー薄膜が形成された。  A case where the fluoropolymer (random copolymer) of Example 16 is replaced with the graft copolymer of Production Example 21 is referred to as Example 24. When the pattern was observed with FE-SEM, a clear line pattern with a line width of 10 μm was formed. As a result of applying the color filter colorant to these pattern substrates by the ink jet method in the same manner as in Example 8, a color thin film clearly divided along the lyophilic region having a line width of 10 m was formed.
上記の電磁波硬化組成物をスピンコートした膜に、フォトマスクを介さずに全面に紫 外線を照射して調製した均一撥液領域の転落角を測定した結果、 n—へキサデカン に対する転落角は 10° 、PGMEAに対する転落角は 14° であり、ランダム共重合 体を用いた実施例 16よりもさらに性能が向上した。  As a result of measuring the falling angle of a uniform liquid repellent region prepared by irradiating the entire surface with ultraviolet rays on a film coated with the above-mentioned electromagnetic wave curable composition without passing through a photomask, the falling angle for n-hexadecane was 10 The sliding angle with respect to PGMEA was 14 °, and the performance was further improved as compared with Example 16 using a random copolymer.
[0149] 撥液領域における接触角の測定方法 [0149] Method for measuring contact angle in liquid repellent region
本発明の撥液領域は微小な面積であるので、そのままでは接触角を測定すること ができない。そこで、接触角を測定するために次の方法で大面積の撥液領域を作製 した。本発明の電磁波硬化組成物を 3cm X 3cmの基材にスピンコート法（2000rpm 、 30秒）により均一に塗布し、窒素雰囲気下で積算照度 lOOOmjZcm2の紫外線を 照射することにより塗膜を硬化させた。接触角は、水平に置いた基板にマイクロシリン ジから水、または、 n—へキサデカンを 2 L滴下して、全自動接触角計で測定した。 実施例 25 Since the liquid repellent area of the present invention is a small area, the contact angle should be measured as it is. I can't. Therefore, in order to measure the contact angle, a large area liquid repellent region was prepared by the following method. The electromagnetic wave curable composition of the present invention is uniformly applied to a 3 cm × 3 cm substrate by a spin coating method (2000 rpm, 30 seconds), and the coating film is cured by irradiating with an ultraviolet ray having an integrated illuminance lOOOmjZcm 2 in a nitrogen atmosphere. It was. The contact angle was measured with a fully automatic contact angle meter after dropping 2 L of water or n-hexadecane from a microsyringe onto a horizontally placed substrate. Example 25
CH =C(Cl)COO - CH CH C F [R1(C4) a—CIアタリレートと省略する] 90重量0 /0、 1CH = C (Cl) COO - CH CH CF [R1 (C4) is omitted and a-CI Atari Rate 90 weight 0/0, 1
2 2 2 4 9 2 2 2 4 9
,6 へキサンジオールジアタリレート（HX— 2Aと省略する） 10重量％を混合溶解し、 この混合物に対し、 2 メチル 1— [4 (メチルチオ)フエ-ル] - 2 -モンフォリノプロ ノ Vン一 1 (チバ 'スぺシャリティー'ケミカルズ (株)から巿販されているィルガキュア 90 7)を 5重量％添加して溶解した。この電磁波硬化組成物の接触角を表 1に示す。水 、 n—へキサデカンの 、ずれの液滴でも高!、撥液性を示した。  , 6 Hexanediol ditalylate (abbreviated as HX—2A) 10% by weight is mixed and dissolved, and this mixture is mixed with 2 methyl 1— [4 (methylthio) phenol] -2 -monfolinoprono V 1% (Irgacure 90 7 sold by Ciba 'Specialty' Chemicals) was added and dissolved. Table 1 shows the contact angles of this electromagnetic wave curable composition. Even water and n-hexadecane showed high liquid repellency even in the case of liquid droplets.
実施例 25の電磁波硬化組成物をノズル径 50 μ mのインクジェット装置から吐出し、 ライン/スペース =100 m/ 100 mの撥液領域を基板のシリコンウェハ上に描画した 。シリコンウェハはアセトンで洗浄後、真空紫外光を照射することにより、表面を超親 水化したものを用いた。この基板に、窒素雰囲気下で、積算照度 lOOOmjZcm2の 紫外線を照射することにより、電磁波硬化組成物の膜を硬化させた。 The electromagnetic wave curable composition of Example 25 was ejected from an inkjet apparatus having a nozzle diameter of 50 μm, and a liquid / repellent region of line / space = 100 m / 100 m was drawn on a silicon wafer of the substrate. The silicon wafer was cleaned with acetone and then irradiated with vacuum ultraviolet light to make the surface superhydrophilic. The film of the electromagnetic wave curable composition was cured by irradiating the substrate with ultraviolet rays having an integrated illuminance of lOOOOmjZcm 2 in a nitrogen atmosphere.
このパターン基板にポリ（9,9ージォクチルフルオレン） [F8と省略する]の 1重量0 /0ト ルェン溶液をスピンコート法（2000rpm、 30秒）により塗布した。トルエン乾燥後の薄 膜を光学顕微鏡で観察したところ、ライン幅 100 mの親液領域に沿って明瞭に分 裂したポリマー薄膜が形成された。 1wt 0/0 DOO Ruen solution of the patterned substrate to a poly (9,9 over di O Chi le fluorene) [abbreviated to F8] was coated by spin coating (2000 rpm, 30 seconds). When the thin film after drying with toluene was observed with an optical microscope, a polymer film that was clearly split along the lyophilic region with a line width of 100 m was formed.
表 3 . 均一塗膜の接触角 Table 3. Contact angle of uniform coating
Figure imgf000051_0001
Figure imgf000051_0001
モノマー組成：単官能ァクリレート /多官能ァクリレート =90/10重量比  Monomer composition: monofunctional acrylate / multifunctional acrylate = 90/10 weight ratio
[0151] 実施例 26、 27 [0151] Examples 26 and 27
実施例 25の HX— 2Aの代わりにトリメチロールプロパントリアタリレート（TMP— 3Aと 省略する）を用いた場合を実施例 26,ペンタエリスリトールテトラアタリレート (PEN— 4 Aと省略する）を用いた場合を実施例 27とした。いずれの場合も、高い撥液性を示し 、さらにパターン基板に対する F8薄膜の分裂性も良好であった。  In the case of using trimethylolpropane tritalylate (abbreviated as TMP-3A) instead of HX-2A in Example 25, Example 26, pentaerythritol tetratalate (abbreviated as PEN-4A) was used. The case was designated as Example 27. In either case, the liquid repellency was high, and the F8 thin film had good splitting ability with respect to the pattern substrate.
[0152] 実施例 28  [0152] Example 28
実施例 25の R C4) a C1アタリレートの代わりに、 CH =C(H)COO— CH CH C F  R C4 of Example 25) a C1 instead of atarylate CH = C (H) COO— CH CH C F
2 2 2 6 13 2 2 2 6 13
[R C6)アタリレートと省略する]を用い、ィルガキュア 907を 1重量％とした場合を実 施例 28とした。この系ではィルガキュア 907を 2重量％以上配合すると、電磁波硬化 組成物が均一に溶解しなカゝつた。この電磁波硬化組成物は高い撥液性を示し、さら にパターン基板に対する F8薄膜の分裂性も良好であった。 [R C6) Abbreviated as talate] was used as Example 28 when Irgacure 907 was 1% by weight. In this system, when 2% by weight or more of Irgacure 907 was added, the electromagnetic wave curable composition was not dissolved uniformly. This electromagnetic wave curable composition showed high liquid repellency, and the F8 thin film had good splitting properties with respect to the pattern substrate.
[0153] 比較例 7、 8 [0153] Comparative Examples 7 and 8
実施例 28の HX— 2Aの代わりに TMP— 3Aを用 V、た場合を比較例 7, PEN 4Aを用 いた場合を比較例 8とした。この系では TMP—3A、 PEN— 4Aを配合すると、電磁波硬 化組成物が均一に溶解しな力つた。  The case where TMP-3A was used instead of HX-2A in Example 28 was used as Comparative Example 7, and the case where PEN 4A was used was used as Comparative Example 8. In this system, when TMP-3A and PEN-4A were blended, the electromagnetic wave hardening composition did not dissolve evenly.
[0154] 比較例 9〜1 1 [0154] Comparative Examples 9 to 1 1
実施例 25の R C4) Q;—C1アタリレートの代わりにラウリルアタリレートを、多官能ァク リレートとして、 HX— 2A、 TMP— 3A、 PEN— 4Aを用いた場合を、それぞれ比較例 9, 10, 11とした。この電磁波硬化組成物は n キサデカンに対する撥液性がほとん どなぐさらにパターン基板に対する F8薄膜の分裂性も不良であった。 R C4) of Example 25 Q; —Laylyl atylate was used instead of C1 atylate, and HX—2A, TMP—3A, and PEN—4A were used as multifunctional acrylates. 10 and 11. This electromagnetic wave curable composition had almost no liquid repellency to n-xadecane, and the F8 thin film had poor splitting ability to the pattern substrate.

Claims

請求の範囲 [1] 以下のフッ素系モノマー (A)およびフッ素系ポリマー（B)からなる群から選択された 少なくとも 1種の含フッ素化合物を含有してなるフォトリソグラフィー用表面処理剤： (A) Claims [1] Surface treatment agent for photolithography comprising at least one fluorine-containing compound selected from the group consisting of the following fluorine-based monomer (A) and fluorine-based polymer (B): (A)
(A— 1)炭素数 1〜6のフルォロアルキル基を有する α位置換アタリレートモノマー [ α位の置換基:フッ素原子、塩素原子、臭素原子、ヨウ素原子、 CFX^2基 (但し、 X 1および X2は、水素原子、フッ素原子または塩素原子）、シァノ基、炭素数 1〜20の直 鎖状または分岐状のフルォロアルキル基、置換または非置換のベンジル基、置換ま たは非置換のフエ二ル基、ある 、は炭素数 1〜20の直鎖状または分岐状アルキル基(A-1) α-substituted acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms [Substituent at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ^ 2 group (provided that X 1 and X 2 represents a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl. Is a linear or branched alkyl group having 1 to 20 carbon atoms
L L
(A— 2)炭素数 1〜6のフルォロアルキル基および重合性基を含有する含フッ素シ ノレセスキォキサンモノマー  (A-2) Fluorinated cinresesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group
(A- 3)パーフルォロポリエーテル基を有する重合性モノマー  (A-3) A polymerizable monomer having a perfluoropolyether group
(A— 4)炭素数 1〜6のフルォロアルキル基と重合性基が- SO (CH ) - (nは 1〜10)  (A—4) a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are —SO (CH 2) — (n is 1 to 10)
2 2 n  2 2 n
により連結された重合性モノマー  Polymerizable monomers linked by
(A- 5)モノマー（A— 1)〜（A—4)の少なくとも 1種を繰り返し単位とするポリマ 一の末端に (メタ)アタリロイル基を有するマクロモノマー  (A-5) Macromonomer having a (meth) atallyloyl group at the end of a polymer having at least one monomer (A-1) to (A-4) as a repeating unit
力 なる群力も選択された少なくとも 1種のフッ素系モノマー、ならびに  At least one fluorinated monomer with a strong group power selected, and
(B) フッ素系モノマー (A)と同様であるフッ素系モノマー（B— 1)から誘導された 繰り返し単位を有するフッ素系ポリマー。  (B) A fluorinated polymer having a repeating unit derived from a fluorinated monomer (B-1) which is the same as the fluorinated monomer (A).
[2] 表面処理剤が、フッ素系モノマー (A)、架橋剤 (C)および光架橋触媒 (D)を含有し てなる請求項 1に記載のフォトリソグラフィー用表面処理剤。 [2] The surface treatment agent for photolithography according to claim 1, wherein the surface treatment agent contains a fluorine-based monomer (A), a crosslinking agent (C), and a photocrosslinking catalyst (D).
[3] 表面処理剤が、フッ素系ポリマー (B)および光架橋触媒 (D)を含有してなり、フッ素 系ポリマー (B)が架橋性官能基 (E)を有する請求項 1に記載のフォトリソグラフィー用 表面処理剤。 [3] The photo treatment according to claim 1, wherein the surface treatment agent comprises a fluoropolymer (B) and a photocrosslinking catalyst (D), and the fluoropolymer (B) has a crosslinkable functional group (E). Surface treatment agent for lithography.
[4] 表面処理剤が、フッ素系ポリマー (B)、架橋剤 (C)、および光架橋触媒 (D)を含有 してなり、フッ素系ポリマー（B)が架橋性官能基 (E)を有する請求項 1に記載のフォト リソグラフィー用表面処理剤。 [5] 表面処理剤が、フッ素系ポリマー (B)、架橋剤 (C)、および光架橋触媒 (D)を含有 してなり、フッ素系ポリマー (B)が架橋性官能基 (E)と酸性基 (F)を有する請求項 1に 記載のフォトリソグラフィー用表面処理剤。 [4] The surface treatment agent contains a fluoropolymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluoropolymer (B) has a crosslinkable functional group (E). The surface treatment agent for photolithography according to claim 1. [5] The surface treatment agent contains a fluoropolymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluoropolymer (B) is acidic with the crosslinkable functional group (E). The surface treatment agent for photolithography according to claim 1, which has a group (F).
[6] 表面処理剤が、フッ素系ポリマー (B)、架橋剤 (C)、および光架橋触媒 (D)を含有 してなり、フッ素系ポリマー (B)が架橋性官能基 (E)と酸性基 (F)とシリコーン鎖 (G) を有する請求項 1に記載のフォトリソグラフィー用表面処理剤。 [6] The surface treatment agent contains a fluoropolymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluoropolymer (B) is acidic with the crosslinkable functional group (E). The surface treatment agent for photolithography according to claim 1, which has a group (F) and a silicone chain (G).
[7] 表面処理剤が、フッ素系ポリマー (B)、架橋剤 (C)、および光架橋触媒 (D)を含有 してなり、フッ素系ポリマー（B)が酸性基 (F)を有する請求項 1に記載のフォトリソダラ フィー用表面処理剤。 [7] The surface treatment agent comprises a fluoropolymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluoropolymer (B) has an acidic group (F). The surface treatment agent for photolithospheres according to 1.
[8] 表面処理剤が、フッ素系ポリマー (B)、架橋剤 (C)、および光架橋触媒 (D)を含有 してなり、フッ素系ポリマー (B)が酸性基 (F)とシリコーン鎖 (G)を有する請求項 1に 記載のフォトリソグラフィー用表面処理剤。  [8] The surface treatment agent contains a fluoropolymer (B), a crosslinking agent (C), and a photocrosslinking catalyst (D), and the fluoropolymer (B) contains an acidic group (F) and a silicone chain ( The surface treatment agent for photolithography according to claim 1, comprising G).
[9] 表面処理剤が、フッ素系ポリマー (B)、および光架橋触媒 (D)を含有してなり、フッ 素系ポリマー (B)が架橋性官能基 (E)と酸性基 (F)を有する請求項 1に記載のフォト リソグラフィー用表面処理剤。 [9] The surface treatment agent contains a fluorine polymer (B) and a photocrosslinking catalyst (D), and the fluorine polymer (B) contains a crosslinkable functional group (E) and an acid group (F). The surface treatment agent for photolithography according to claim 1, comprising:
[10] 表面処理剤が、フッ素系ポリマー (B)、および光架橋触媒 (D)を含有してなり、フッ 素系ポリマー (B)が架橋性官能基 (E)と酸性基 (F)とシリコーン鎖 (G)を有する請求 項 1に記載のフォトリソグラフィー用表面処理剤。 [10] The surface treatment agent contains a fluorine polymer (B) and a photocrosslinking catalyst (D), and the fluorine polymer (B) comprises a crosslinkable functional group (E) and an acid group (F). The surface treatment agent for photolithography according to claim 1, having a silicone chain (G).
[11] 架橋剤 (C)がラジカル重合性官能基、カチオン重合性官能基、酸と架橋可能な官 能基の 、ずれかを有する請求項 2、 4〜8の 、ずれかに記載のフォトリソグラフィー用 表面処理剤。 [11] The photo of any one of claims 2, 4 to 8, wherein the crosslinking agent (C) has any one of a radical polymerizable functional group, a cationic polymerizable functional group, and an functional group capable of crosslinking with an acid. Surface treatment agent for lithography.
[12] 架橋剤 (C)がシリコーン (メタ)アタリレートである請求項 2、 4〜8の 、ずれかに記載 のフォトリソグラフィー用表面処理剤。  [12] The surface treatment agent for photolithography according to any one of [2] and [4] to [8], wherein the crosslinking agent (C) is silicone (meth) acrylate.
[13] 架橋性官能基 (E)がラジカル重合性基、カチオン重合性基、酸と架橋可能な官能 基のいずれかである請求項 3〜6、 9、 10のいずれかに記載のフォトリソグラフィー用 表面処理剤。 [13] The photolithography according to any one of [3] to [6], [9], and [10], wherein the crosslinkable functional group (E) is any one of a radical polymerizable group, a cationic polymerizable group, and a functional group capable of crosslinking with an acid. For surface treatment agent.
[14] 表面処理剤が、フッ素系ポリマー（B)、および光酸発生剤 (I)を含有してなり、フッ 素系ポリマー (B)が、酸の作用によって酸性基に変換する酸解離性官能基 (H)を有 する請求項 1に記載のフォトリソグラフィー用表面処理剤。 [14] The surface-treating agent contains a fluorine-based polymer (B) and a photoacid generator (I), and the fluorine-based polymer (B) is converted to an acid group by the action of an acid. Has functional group (H) The surface treatment agent for photolithography according to claim 1.
[15] 表面処理剤が、フッ素系ポリマー（B)、および光酸発生剤 (I)を含有してなり、フッ 素系ポリマー (B)が、酸の作用によって酸性基に変換する酸解離性官能基 (H)とシ リコーン鎖 (G)を有する請求項 1に記載のフォトリソグラフィー用表面処理剤。 [15] The surface treating agent contains a fluorine-based polymer (B) and a photoacid generator (I), and the fluorine-based polymer (B) is acid-dissociable that is converted into an acid group by the action of an acid. The surface treatment agent for photolithography according to claim 1, which has a functional group (H) and a silicone chain (G).
[16] フッ素系ポリマー（B)が、フッ素系モノマー（B—1)力も誘導された繰り返し単位お よび不飽和有機酸 (B— 2)力 誘導された繰り返し単位を有するコポリマーである請 求項 3〜15のいずれかに記載のフォトリソグラフィー用表面処理剤。 [16] Claims in which the fluorinated polymer (B) is a copolymer having a repeating unit in which the fluorinated monomer (B-1) force is also induced and an unsaturated organic acid (B-2) force inducing the repeating unit. The surface treating agent for photolithography according to any one of 3 to 15.
[17] フッ素系ポリマー（B)において、フッ素系モノマー（B— 1)と不飽和有機酸（B— 2) の重量比が 60 :40〜98： 2である請求項 16に記載のフォトリソグラフィー用表面処理 剤。 17. The photolithography according to claim 16, wherein in the fluorine-based polymer (B), the weight ratio of the fluorine-based monomer (B-1) to the unsaturated organic acid (B-2) is 60:40 to 98: 2. Surface treatment agent.
[18] フッ素系ポリマー（B)が、さらに高軟ィ匕点モノマー（B— 3)力も誘導された繰り返し 単位を有する請求項 16に記載のフォトリソグラフィー用表面処理剤。  18. The surface treatment agent for photolithography according to claim 16, wherein the fluoropolymer (B) further has a repeating unit in which a high soft spot monomer (B-3) force is also induced.
[19] フッ素系ポリマー（B)が、 [19] Fluoropolymer (B)
フッ素系モノマー（B— 1) 20〜80重量0 /0、 Fluorine monomer (B- 1) 20 to 80 weight 0/0,
不飽和有機酸 (B— 2) 5〜30重量％、  Unsaturated organic acid (B-2) 5-30% by weight,
高軟化点モノマー（B— 3) 10〜70重量％  High softening point monomer (B-3) 10-70% by weight
力も構成される請求項 18に記載のフォトリソグラフィー用表面処理剤。  19. The surface treatment agent for photolithography according to claim 18, wherein force is also configured.
[20] 不飽和有機酸（B— 2) 1S (メタ)アクリル酸、ビュル酢酸、クロトン酸、ィタコン酸、無 水ィタコン酸、マレイン酸、無水マレイン酸、フマル酸、およびケィ皮酸からなる群か ら選択された少なくとも 1種である請求項 16に記載のフォトリソグラフィー用表面処理 剤。 [20] Unsaturated organic acid (B-2) 1S (meth) acrylic acid, bulacetic acid, crotonic acid, itaconic acid, hydrous itaconic acid, maleic acid, maleic anhydride, fumaric acid, and kaycin acid 17. The surface treatment agent for photolithography according to claim 16, wherein the surface treatment agent is at least one selected from the group consisting of:
[21] 高軟化点モノマー（B— 3)力 メチルメタタリレート、フエ-ルメタタリレート、シクロへ キシルメタタリレート、イソボル-ル (メタ)アタリレート、ノルボル-ル (メタ)アタリレート、 およびァダマンチル (メタ)アタリレートからなる群力 選択された少なくとも 1種である 請求項 18に記載のフォトリソグラフィー用表面処理剤。  [21] High softening point monomer (B-3) force Methyl methacrylate, phenol methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and 19. The surface treatment agent for photolithography according to claim 18, which is at least one selected from the group force consisting of adamantyl (meth) acrylate.
[22] 炭素数 1〜6のフルォロアルキル基を有する α位置換アタリレート (A— 1)において 、 α位の置換基が、フッ素原子、塩素原子、臭素原子、ヨウ素原子、 CFXY基 (但し 、 X1および X2は、水素原子、フッ素原子または塩素原子）、シァノ基、炭素数 1〜20 の直鎖状または分岐状のフルォロアルキル基、置換または非置換のベンジル基、置 換または非置換のフ -ル基カもなる群力も選択されたものである請求項 1〜21の いずれかに記載のフォトリソグラフィー用表面処理剤。 [22] In the α-substituted attalate (A-1) having a fluoroalkyl group having 1 to 6 carbon atoms, the α-position substituent is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFXY group (provided that X 1 and X 2 are a hydrogen atom, a fluorine atom or a chlorine atom), a cyan group, or a carbon number of 1 to 20 The group force comprising a linear or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted full group is selected. Surface treatment agent for photolithography.
[23] フッ素系モノマー（A—4)にお!/、て- SO (CH ) -における nが 3〜6である請求項 1〜 [23] In the fluorine-based monomer (A-4), n in the! /,-SO (CH)-is 3-6.
2 2 n  2 2 n
22のいずれかに記載のフォトリソグラフィー用表面処理剤。  The surface treating agent for photolithography according to any one of 22 above.
[24] フッ素系モノマー（A—l)、（A— 2)、（A—4)および (A— 5)において、フルォロア ルキル基の炭素数が 4である請求項 1〜22のいずれかに記載のフォトリソグラフィー 用表面処理剤。 [24] The fluorinated monomer (A-1), (A-2), (A-4) and (A-5), wherein the fluoroalkyl group has 4 carbon atoms. The surface treatment agent for photolithography as described.
[25] 請求項 1〜24のいずれかに記載のフォトリソグラフィー用表面処理剤を用いて、フ オトリソグラフィ一法により、表面自由エネルギーが異なる複数の領域力 構成される パターンを基板上に形成することを特徴とするパターン基板の製造方法。  [25] Using the surface treatment agent for photolithography according to any one of claims 1 to 24, a pattern composed of a plurality of region forces having different surface free energies is formed on a substrate by a photolithography method. A method for producing a patterned substrate.
[26] フォトリソグラフィ一に用いられる電磁波が、 [26] The electromagnetic wave used in photolithography is
波長 10〜400nmの光、  Light with a wavelength of 10-400 nm,
波長 0.1〜10nmの X線、  X-rays with a wavelength of 0.1-10 nm,
波長 0.001〜0.01nmの電子線、または  An electron beam with a wavelength of 0.001 to 0.01 nm, or
波長 10〜300nmのレーザー光線  Laser beam with a wavelength of 10 to 300 nm
の!、ずれかである請求項 25に記載の方法。  26. The method of claim 25, wherein the!
[27] 請求項 25または 26の方法で製造されたパターン基板。 [27] A patterned substrate manufactured by the method of claim 25 or 26.
[28] 請求項 27に記載のパターン基板上に機能性ィ匕合物の溶液または分散液を塗布し [28] A functional compound solution or dispersion is coated on the patterned substrate according to claim 27.
、溶媒を除去することを特徴とするデバイスの製造方法。 A method for producing a device, comprising removing the solvent.
[29] 請求項 28に記載の製法によって製造された電子、光学、医療または分析化学用 途のデバイス。 [29] A device for electronic, optical, medical, or analytical chemistry manufactured by the manufacturing method according to claim 28.
[30] デバイス力 集積回路、ディスプレイ用画素、レンズアレイ、ノィォチップまたはマイ クロ化学チップである請求項 29に記載のデバイス。  30. The device according to claim 29, which is an integrated circuit, a display pixel, a lens array, a nanochip or a microchemical chip.
[31] 請求項 1〜24のいずれかに記載のフォトリソグラフィー用表面処理剤中に黒色の顔 料を分散させたものを用いて、フォトリソグラフィ一法により、親液性透明基板上に撥 液ィ匕されたブラックマトリクスを形成することを特徴とするディスプレイ用カラーフィルタ の製造方法。 [31] A liquid repellent material on a lyophilic transparent substrate by a photolithography method using the surface treatment agent for photolithography according to any one of claims 1 to 24 dispersed therein. A method of manufacturing a color filter for display, comprising forming a black matrix.
[32] 親液性透明基板上に均一に形成された感光性榭脂ブラック層の上に、さらに請求 項 1〜24のいずれかに記載のフォトリソグラフィー用表面処理剤を均一に塗布した後 、フォトリソグラフィ一法により、親液性透明基板上に撥液化されたブラックマトリクスを 形成することを特徴とするディスプレイ用カラーフィルタの製造方法。 [32] After the surface treatment agent for photolithography according to any one of claims 1 to 24 is further uniformly coated on the photosensitive resin black layer uniformly formed on the lyophilic transparent substrate, A method for producing a color filter for a display, comprising forming a lyophobic black matrix on a lyophilic transparent substrate by a photolithography method.
[33] 撥液化されたブラックマトリクスを有する透明基板上に、赤、黒、黄の顔料を分散し た分散液を塗布し、溶媒を除去することを特徴とする請求項 31または 32に記載のデ イスプレイ用カラーフィルタの製造方法。  [33] The method according to claim 31 or 32, wherein a dispersion liquid in which red, black, and yellow pigments are dispersed is applied onto a transparent substrate having a liquid repellent black matrix, and the solvent is removed. A method for manufacturing a color filter for display.
[34] 請求項 33の製造方法で製造されたディスプレイ用カラーフィルタ。  [34] A color filter for display manufactured by the manufacturing method according to claim 33.
[35] (A)フルォロアルキル基を含有するフッ素系モノマー、  [35] (A) a fluoromonomer containing a fluoroalkyl group,
(B)架橋剤、および  (B) a crosslinking agent, and
(C)光架橋触媒  (C) Photocrosslinking catalyst
を含んでなる電磁波硬化組成物を、非接触な微量液滴吐出法で基材に吐出して、 基材上に電磁波硬化組成物の塗膜を形成し、塗膜に電磁波を照射して硬化させる ことにより、表面自由エネルギーが異なる少なくとも 2つの領域力も構成されるパター ンを基材上に形成することを特徴とするパターン基板の製造方法。  The electromagnetic wave curable composition comprising is discharged onto a substrate by a non-contact microdroplet discharge method, a coating film of the electromagnetic wave curable composition is formed on the substrate, and the coating film is irradiated with electromagnetic waves and cured. A pattern substrate manufacturing method, comprising: forming a pattern on the base material, which also includes at least two region forces having different surface free energies.
[36] 電磁波硬化糸且成物のフッ素系モノマー (A)が [36] Fluorine monomer (A)
(A— 1)炭素数 1〜6のフルォロアルキル基を有する α位置換アタリレートモノマー [ α位の置換基:フッ素原子、塩素原子、臭素原子、ヨウ素原子、 CFX^2基 (但し、 X 1および X2は、水素原子、フッ素原子または塩素原子）、シァノ基、炭素数 1〜20の直 鎖状または分岐状のフルォロアルキル基、置換または非置換のベンジル基、置換ま たは非置換のフエ二ル基、ある 、は炭素数 1〜20の直鎖状または分岐状アルキル基(A-1) α-substituted acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms [Substituent at α-position: fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ^ 2 group (provided that X 1 and X 2 represents a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl. Is a linear or branched alkyl group having 1 to 20 carbon atoms
L L
(A— 2)炭素数 1〜6のフルォロアルキル基および重合性基を含有する含フッ素シ ノレセスキォキサンモノマー  (A-2) Fluorinated cinresesquioxane monomer containing a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group
(A- 3)パーフルォロポリエーテル基を有する重合性モノマー  (A-3) A polymerizable monomer having a perfluoropolyether group
(A— 4)炭素数 1〜6のフルォロアルキル基と重合性基が- SO (CH ) - (nは 1〜10)  (A—4) a fluoroalkyl group having 1 to 6 carbon atoms and a polymerizable group are —SO (CH 2) — (n is 1 to 10)
2 2 n  2 2 n
により連結された重合性モノマー  Polymerizable monomers linked by
(A- 5)モノマー（A— 1)〜（A—4)の少なくとも 1種を繰り返し単位とするポリマ 一の末端に (メタ)アタリロイル基を有するマクロモノマー (A-5) Polymers having at least one monomer (A-1) to (A-4) as a repeating unit A macromonomer having a (meth) attalyloyl group at one end
力もなる群力も選択された少なくとも 1種のフッ素系モノマーである請求項 35に記載 の方法。  36. The method according to claim 35, wherein at least one fluorine-based monomer is selected for both force and group power.
[37] 架橋剤 (B)がラジカル重合性官能基またはカチオン重合性官能基を有する請求項 [37] The crosslinking agent (B) has a radical polymerizable functional group or a cationic polymerizable functional group.
36または 36に記載の方法。 36. The method according to 36 or 36.
[38] 非接触な微量液滴吐出法力 Sインクジェット法またはマイクロディスペンサー法である 請求項 35に記載の方法。 [38] The method according to claim 35, wherein the method is a non-contact method for ejecting a small amount of a droplet.
[39] 基材上に撥液性の膜が形成され、パターン化された少なくとも 1つの撥液領域と少 なくとも 1つの親液領域が得られる請求項 35に記載の方法。 [39] The method according to claim 35, wherein a liquid-repellent film is formed on the substrate to obtain a patterned at least one liquid-repellent region and at least one lyophilic region.
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