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WO2007105649A1 - Composition durcissable, filtres colores et affichage a cristaux liquides - Google Patents

Composition durcissable, filtres colores et affichage a cristaux liquides Download PDF

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Publication number
WO2007105649A1
WO2007105649A1 PCT/JP2007/054714 JP2007054714W WO2007105649A1 WO 2007105649 A1 WO2007105649 A1 WO 2007105649A1 JP 2007054714 W JP2007054714 W JP 2007054714W WO 2007105649 A1 WO2007105649 A1 WO 2007105649A1
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WO
WIPO (PCT)
Prior art keywords
group
curable composition
meth
acid
acrylate
Prior art date
Application number
PCT/JP2007/054714
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English (en)
Japanese (ja)
Inventor
Kouji Yamauchi
Naoto Sekiguchi
Original Assignee
Mitsubishi Chemical Corporation
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 Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Priority to KR1020087011650A priority Critical patent/KR101167868B1/ko
Priority to CN2007800044421A priority patent/CN101379132B/zh
Publication of WO2007105649A1 publication Critical patent/WO2007105649A1/fr

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Classifications

    • 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
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • Pixels, black matrixes, photo spacers, rib materials, overcoats, etc. used in the manufacture of display members such as liquid crystal display devices are generally obtained by applying a curable composition to a substrate. It is formed through a step of forming a physical layer.
  • Patent Document 2 discloses an apparatus for cleaning the nozzle tip.
  • the coating operation needs to be interrupted to clean the nozzles, which hinders manufacturing tact.
  • the cleaning is not complete, the remaining liquid will be collected at the tip of the nozzle, so there was a problem that it would lead to uneven application (unevenness).
  • the adhesion (a) formed on the edge of the glass specimen is 2 g or less, and the viscosity increase when the curable composition is stored at 35 ° C for 2 weeks under normal pressure is 1. Ocps or less. It exists in the curable composition characterized by the above-mentioned.
  • the water content in the composition is 0.4% by weight or more, preferably 0.5% by weight or more, more preferably 0.6% by weight or more, and particularly preferably 0. 7% by weight or more, 2.0% by weight or less, preferably 1.5% by weight or less, more preferably 1.2% by weight or less, and particularly preferably 0.9% by weight or less. If the water content is too low, the effect of reducing foreign matter will not be exhibited, and if it is too high, there will be problems with curability and long-term storage.
  • Steps (1) and (2) are repeated a total of 250 times to form a deposit derived from the curable composition on the glass test piece.
  • the speed at which the test piece is immersed in the curable composition is 12.5 mmZ seconds. In order to make the immersion time of the test piece uniform, it is preferable that the speed at the time of immersion is the same as the take-out speed described later.
  • Step (2) “The glass specimen is taken out from the curable composition at a rate of 12.5 mmZ seconds. The glass test piece is held vertically with the tip down, and then dried for 52 seconds under conditions of an atmospheric temperature of 23 ° C., a humidity of 55%, and a wind speed of 0.5 ⁇ 0.2 mZ seconds. "
  • a curable composition having an amount (a) of 2 g or less can be obtained.
  • the curable composition is not uniformly ejected from the nozzle coat of the die coater, resulting in uneven coating and streaks, and the dripping liquid does not spread sufficiently uniformly during spin coating, causing radial coating unevenness and uncoated areas. Problems such as generation and unevenness due to insufficient leveling during drying occur.
  • the ring formed by linking R 7 and R 8 is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.
  • the curable composition of the present invention when used for a power filter or a liquid crystal display element, the heat resistance of the curable composition is improved or the cured composition is used. It is possible to increase the intensity of a pixel formed using a conductive composition.
  • mono (meth) acrylate having the structure represented by the general formula (1) is used alone. Or two or more of them may be used in combination.
  • the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butylcetosolve acetate; diethylene glycol monomethyl ether acetate, carbitol acetate.
  • solvents may be used alone or in combination of two or more.
  • the amount of these solvents used is usually 30 to: LOOO parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. If the amount of solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.
  • dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride And anhydrides of three or more bases such as benzophenone tetracarboxylic acid anhydride and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and Z or succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.
  • the carboxyl group-containing linear alkali-soluble resin may be obtained by copolymerizing the above carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group. Good.
  • polymerizable monomers are not particularly limited, but include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth).
  • styrene methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyxetyl (meth) acrylate, Hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide.
  • carboxyl group-containing linear alkali-soluble resin examples include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, Polymerizable monomers that do not contain hydroxyl groups such as isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl maleimide, and 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Copolymers of hydroxyl-containing monomers such as attalylate and 4-hydroxybutyl (meth) atelate; (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) Co-polymerization with (meth) acrylic acid esters such as acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate Copo
  • a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
  • the acid value of the carboxyl group-containing linear alkali-soluble coconut resin in the present invention is usually 30 to 500 KOHmgZg, preferably 40 to 350 KOHmgZg, and more preferably 50 to 300 KOHmgZg.
  • Epoxy group-containing unsaturated compounds include ethylenically unsaturated groups and epoxy groups in the molecule. There is no particular limitation as long as it has a silyl group.
  • the alicyclic epoxy group-containing unsaturated compound for example, 2, 3 epoxycyclopentinole group, 3, 4 epoxycyclohexenole group, 7, 8 And an epoxy [tricyclo [5. 2. 1. 0] decyl-2-yl] group.
  • the preferred alicyclic epoxy group-containing unsaturated compound preferably derived from a (meth) atalyloyl group includes the following general formulas (3a) to (3) And a compound represented by 3m).
  • R A R 0 R 4D each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group
  • L 2 represents a divalent linking group
  • L 3 represents a divalent group. Represents a linking group or a direct bond of Two or more of L 3 may be bonded to each other to form a ring.
  • a 4-1) A polymer formed by polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate.
  • the proportions of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component are not particularly limited, but (meth) acrylic acid in all monomer components is usually 10 to 90% by weight, preferably Is 15 to 80% by weight, more preferably 20 to 70% by weight. Further, benzyl (meth) acrylate is usually 5 to 90% by weight, preferably 15 to 80% by weight, and more preferably 20 to 70% by weight in all monomer components. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be rough during development, and if it is too small, development may be impossible. Also, if the amount of benzyl (meth) acrylate is too much or too little, dispersion tends to be difficult.
  • preferred examples of the general formula (6) include compounds represented by the following general formula (7).
  • Halogen atom hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, t butyl group, amyl group, tamyl group, n monohexyl
  • a linear or branched alkyl group having 1 to 18 carbon atoms such as a group, n-heptyl group, n-octyl group, t-octyl group, etc .; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc.
  • the (A-4) acrylic resin in the present invention preferably has an acid group, including the polymers described in (A-4-1) and (A-4-2).
  • an acid group including the polymers described in (A-4-1) and (A-4-2).
  • the resulting curable composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing).
  • acid-epoxy curing Alternatively, a composition in which an uncured part can be visualized with an alkali developer can be obtained.
  • the acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. These acid groups may be used alone or in combination of two or more.
  • a monomer having an acid group and Z or "a monomer capable of imparting an acid group after polymerization" (hereinafter referred to as "a simple group for introducing an acid group”). May be referred to as a “mer”.) May be used as a monomer component.
  • a treatment for adding an acid group as described later is required after the polymerization.
  • Examples of the monomer having an acid group include a monomer having a strong carboxyl group such as (meth) acrylic acid tataconic acid; a monomer having a phenolic hydroxyl group such as N-hydroxyphenol maleimide; and maleic anhydride. Among these, (meth) acrylic acid is preferable.
  • Examples of the monomer capable of imparting an acid group after the polymerization include 2-hydroxy ester. Monomers having a hydroxyl group such as til (meth) atalylate; Monomers having an epoxy group such as glycidyl (meth) atalylate; Monomers having an isocyanate group such as 2-isocyanatoetyl (meth) atalylate It is done.
  • a radical polymerizable double bond for example, "a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as "introducing a radical polymerizable double bond”). After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.
  • Examples of monomers capable of imparting a radically polymerizable double bond after polymerization include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic anhydride groups such as maleic anhydride and itaconic anhydride Monomers having a glycidyl (meth) acrylate, 3
  • the content ratio is not particularly limited, but 95% by weight or less is preferred. The amount% or less is more preferable.
  • the polymerization temperature and polymerization concentration are the types and ratios of monomer components used. Depending on the molecular weight of the target polymer Different.
  • the polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C.
  • the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.
  • a polymerization initiator may be used as necessary.
  • polymerization initiator examples include tamenno, id-peroxide, diisopropylbenzene hydride peroxide, di-t-peroxide, lauroyl peroxide, benzoyl-peroxide, and t-butyl-peroxyisopropyl carbonate.
  • Organic peroxides such as t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy 2-ethyl hexanoate; 2, 2 '—azobis (isobutyor-tolyl), 1, 1' —azobis ( And azo compounds such as 2,2′-azobis (2,4 dimethylvalero-tolyl), dimethyl 2,2′-azobis (2-methylpropionate), and the like.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction.
  • the cyclization rate of the ether dimer is not necessarily 100 mol%.
  • the acrylic resin when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. There is.
  • the treatment is different depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyxetyl (meth) acrylate is used.
  • a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate
  • a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.
  • a monomer having a carboxyl group such as (meth) acrylic acid taconic acid
  • glycidyl (meth) If a compound having an epoxy group and a radically polymerizable double bond, such as attalylate, 3, 4 epoxycyclohexylmethyl (meth) acrylate, o (or m-, or p) benzylbenzyl glycidyl ether, is added.
  • a monomer having a carboxyl group such as (meth) acrylic acid taconic acid
  • a compound having an epoxy group and a radically polymerizable double bond such as attalylate, 3, 4 epoxycyclohexylmethyl (meth) acrylate, o (or m-, or p) benzylbenzyl glycidyl ether
  • the acid value is preferably 30 to 500 mgKOHZg, more preferably 50 to 400 mgKOHZg. If the acid value is less than 30 mg KOHZg, it may be difficult to apply to alkaline development, and if it exceeds 500 mg KOHZg, the viscosity tends to be too high to form a coating film.
  • the polymer having the compound represented by the general formula (4) as an essential monomer component is a compound known per se, such as those disclosed in JP-A-2004-30020. Examples thereof include compounds described in JP-A No. 3 and JP-A 2004-300204.
  • VAV VAV These may be used alone or in combination of two or more.
  • R 61 represents hydrogen or an ethyl group
  • R 62 represents hydrogen or an alkyl group having 1 to 6 carbon atoms
  • r is an integer of 2 to 10.
  • the compound of the general formula (8) includes, for example, polyethylene glycol mono (meta) such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate. ) Atarylate; Alkoxypolyethylene dallic (meth) acrylate, such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, etc. It is done.
  • polyethylene glycol mono (meta) such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate.
  • Atarylate Alkoxypolyethylene dallic (meth) acrylate, such as methoxydiethylene glycol mono (meth) acrylate, methoxytri
  • copolymer type epoxy resin specifically, "CP-15” manufactured by NOF Corporation. “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA”, “CP-50S”, “CP-50M”, “CP-20MA” and the like.
  • the molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000 as the weight average molecular weight in terms of polystyrene measured by GPC.
  • the weight average molecular weight is less than the above range, there are many cases where problems occur in the film-forming property.
  • the resin exceeds the above range, gelling may occur during the addition reaction of ⁇ , ⁇ unsaturated monocarboxylic acid. There is a risk that it will be difficult to manufacture.
  • Examples of the a, ⁇ -unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, and the like, preferably acrylic acid and methacrylic acid, and in particular, acrylic acid is reacted. It is preferred because of its rich nature.
  • a known method can also be used for the addition reaction of polybasic acid anhydrides, and it is carried out by continuing the reaction under the same conditions as the addition reaction of ⁇ , ⁇ -unsaturated carboxylic acid or ester thereof. be able to.
  • epoxy acrylate resins having a carboxyl group include naphthalene-containing resins described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331.
  • fluorene-containing coagulants described in JP-A No. 2001-354735; JP-A 2005-126674, JP-A 2005-55814, JP-A 2004-295084, and the like.
  • the ethylenic compound has an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the curable composition of the present invention is irradiated with actinic rays.
  • the monomer in this invention means the concept corresponding to what is called a polymeric substance, and also contains a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
  • Examples of ethylenic compounds include unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, and aliphatic polyhydroxy compounds. Esters with unsaturated carboxylic acids, esters with aromatic polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids with polyvalent carboxylic acids and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds By esterification reaction with polyhydric hydroxy compounds such as Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting the obtained ester, polyisocyanate compound and a (meth) atallyloyl group-containing hydroxy compound.
  • unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, and aliphatic polyhydroxy compounds.
  • Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) atallyloyl group-containing hydroxy compound include hexamethylene diisocyanate and trimethylhexamethyate.
  • ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allylic esters such as diaryl phthalate; vinyl such as dibi-phthalate. And group-containing compounds.
  • the preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg'KOHZg, and particularly preferably 5 to 30 mg * KOHZg. If the acid value of the polyfunctional monomer is too low, the image-dissolving property tends to be lowered. If it is too high, the production and handling may be difficult, the photopolymerization performance may be deteriorated, and the pixel surface may be smoothed. Curability such as property may be inferior. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid group as the whole polyfunctional monomer is I prefer to adjust it to fall within the range.
  • the curable composition of the present invention comprises (D) a pigment as an essential component.
  • a pigment as an essential component.
  • Various color pigments such as brown pigments can be used.
  • the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.
  • various inorganic pigments can be used. Specific examples of usable pigments are indicated by pigment numbers.
  • the following “C. I.” means the color index (C. I.).
  • red pigments CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 17 4, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194
  • CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and CI pigment yellow 83, 138, 139, 150, 180 is more preferable. is there.
  • Purple pigments include CI pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
  • C. I. pigment violet 19, 23 is preferable, and C. I. pigment violet 23 is more preferable.
  • the CI pigment range is 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48. 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 Of these, CI pigment oranges 38 and 71 are preferred.
  • examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide and the like.
  • a plurality of the above-mentioned various pigments can be used in combination.
  • a green pigment and a yellow pigment may be used in combination, or a blue pigment and a purple pigment may be used in combination.
  • black pigments examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black.
  • carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.
  • carbon black coated with a resin for the production of a resin black matrix having a high optical density and a high surface resistivity.
  • the carbon black coated with resin is described in, for example, JP-A-9-26571, JP-A-971733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating the known carbon black in a method.
  • red, green and blue pigments can be mixed and used as a black pigment.
  • Color materials that can be mixed to prepare a black pigment include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170) Safranin O K70: 100 (50240), Erioglaucine X (42080), No.
  • pigments that can be used in combination are represented by CI numbers.
  • the red curable composition is preferably 15 to 50% by weight, more preferably 20 to 45% by weight in the total solid content.
  • the green curable composition include those containing 15 to 60% by weight, more preferably 20 to 50% by weight of the total solids, and blue curable compositions.
  • the composition preferably has a color of 5 to 35% by weight, more preferably 10 to 30% by weight in the total solid content. The thing containing material is mentioned.
  • the black curable composition preferably contains 20 to 80% by weight, more preferably 30 to 70% by weight of the coloring material in the total solid content.
  • the curable composition of the present invention preferably further contains (E) a dispersant.
  • the type of the dispersant (E) is not particularly limited as long as the effects of the present invention are not impaired, but (E-1): a graft copolymer containing a nitrogen atom, (E-2): containing a nitrogen atom Acrylic block copolymer (E-3): It is preferable to contain one or more dispersants selected from urethane resin dispersants.
  • the performance of the dispersant is greatly influenced by its adsorption behavior on the solid surface.
  • the adsorption behavior is excellent in the order of random copolymer, graft copolymer, and block copolymer. ing. ([Column is Jones ana Richards, 'Polymers at Surfaces and Interfaces p281].
  • an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a suitable portion can be arranged in the portion requiring solvent affinity.
  • This dispersibility is particularly good for dispersing colorants containing pigments with a small crystallite size. It is presumed to affect
  • Y is a hydrogen atom or —CO—R 52 (R 52 is ethyl,
  • W is an alkyl group having 1 to 50 carbon atoms or 1 to 5 carbon atoms having a hydroxyl group.
  • a sialkyl group is preferred.
  • the content of the repeating unit represented by the formula (I) or (II) in the graft copolymer of the present invention is usually higher, preferably 50 mol% or more, and preferably 70 mol% or more.
  • the content ratio of the repeating unit represented by formula (I) and the repeating unit represented by formula (II) is not limited. It is preferable to contain a large amount of.
  • the total number of repeating units represented by the formula (I) or the formula (II) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50 in one molecule.
  • the graft copolymer of the present invention has a terminal of —NH and —R 51 —NH (R 51 is as defined above for R 51 ).
  • the amine value of the graft copolymer of the present invention is usually 5 to: LOOmgKOHZg, preferably 10 to 70 mgKOHZg, and more preferably 15 to 40 mgKOHZg or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate.
  • the weight average molecular weight in terms of polystyrene measured by GPC of the above-mentioned dispersant is 3000-: L0 0000 force preferred ⁇ , 5000-50000 force particularly preferred! / ⁇ . If the weight average molecular weight force is less than 3000, aggregation of the coloring material cannot be prevented, and the viscosity may increase or gelation may occur. Solubility may be insufficient.
  • graft copolymer having the same structure as described above can be applied.
  • a side chain has a quaternary ammonium base and a Z or amino group A block, and does not have a quaternary ammonium base and Z or amino group.
  • A-B block copolymers and Z- or B-A-B block copolymers are also preferred because they can be used together.
  • R 31, R 32, R 33 in the N + R 31 R 32 R 33 each independently, more preferred are optionally substituted alkyl group having 1 to 3 carbon atoms, or a substituted It may have a group, a phenol group or a substituent, and may be a benzyl group.
  • examples of the divalent linking group X 1 include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R — —, one COO and one R d . 1 (provided that R d and R d are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms: L0
  • the Z- of the counter-on is Cl-, Br-, ⁇ , CIO-, BF-, CH COO-, PF-, etc.
  • the amino group is preferably one NR 41 R 42 (provided that each of R 41 and R 42 independently has a cyclic or chain alkyl group which may have a substituent or a substituent. It represents a good aryl group or an aralkyl group which may have a substituent.) More preferably, an amino group represented by the following formula may be mentioned.
  • R 44 represents a hydrogen atom or a methyl group.
  • R 41 and R 42 are preferably methyl groups.
  • R 43 is preferably a methylene group or an ethylene group.
  • R 44 is preferably a hydrogen atom.
  • Examples of such a compound include a substituent represented by the following formula.
  • the partial structure containing the specific quaternary ammonium base and Z or amino group as described above may be contained in one or more A blocks. In that case, two or more grades 4
  • the ammonia base and / or amino group-containing partial structure may be contained in the A block in any form of random copolymerization or block copolymerization.
  • Examples of the partial structure that may be contained in the partial structural force A block that does not contain the quaternary ammonium base and / or amino group include the (meth) acrylic acid ester monomer described later.
  • a partial structure derived from one is mentioned.
  • the quaternary ammonium base and the partial structure containing no Z or amino group, the content in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the quaternary ammonia base and / or amino group-free partial structure is not included in the A block.
  • the B block constituting the block copolymer of the dispersant for example, styrene monomers such as styrene and a-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (meta) ) Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylate monomers such as hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; butyl acetate monomers; allylic glycidyl Glycidyl
  • R 39 represents a hydrogen atom or a methyl group.
  • R 4 may have a cyclic or chain-like alkyl group which may have a substituent, or a substituent.
  • Aryl group or substitution An aralkyl group which may have a group is represented.
  • Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block.
  • the B block may further contain a partial structure other than these. Partial structural strength derived from two or more types of monomers Does not contain quaternary ammonia salt groups.
  • each partial structure is random or block copolymerized in the B block. It may be contained in any of the embodiments.
  • the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer
  • the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block Is preferably 0 to 99% by weight, more preferably 0 to 85% by weight.
  • the acrylic dispersant used in the present invention has such a force as A block and B block.
  • Such a block copolymer is prepared, for example, by the living polymerization method shown below.
  • the radical living polymerization method is a polymerization active species power radical, and is shown, for example, in the following scheme.
  • the Amin block value in lg of the A-B block copolymer and B-A-B block copolymer according to the present invention is usually about 1 to 300 mgKOHZg.
  • the preferred range is A block. Differs depending on whether or not it has quaternary ammonia base.
  • the A block of the A—B block copolymer and B—A—B block copolymer according to the present invention has a quaternary ammonium base
  • the quaternary ammonia in the copolymer lg is used.
  • the amount of um base is preferably 0.1 to: LOmmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility.
  • Such a block copolymer may contain an amino group produced in the production process, and its amine value is usually about 1 to about LOOmgKOHZg, preferably 1 to 50 mgKOHZg, per lg of copolymer. More preferably, it is 1-30 mgKOHZg.
  • the amine value of the copolymer is usually about 50 to 300 mgKOHZg, preferably 50 to 200 mgKOH / g, per lg.
  • the amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the amino group with acid.
  • the acid value of this block copolymer is usually less than lOOmgKOHZg, which is generally preferred to be lower, although it depends on the presence and type of acidic groups that form the acid value, and its molecular weight is
  • Mw weight average molecular weight in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. If the molecular weight of the block copolymer is too small, the dispersion stability decreases, and if it is too large, the developability and resolution tend to decrease.
  • urethane resin dispersant a polyisocyanate compound is reacted with a compound having one or two hydroxyl groups in the same molecule and a compound having active hydrogen and tertiary amino group in the same molecule.
  • a urethane resin obtained by the treatment is particularly preferred.
  • Examples of the above polyisocyanate compounds include para-phenylene-diisocyanate, 2,4-tolylene-diisocyanate, 2,6-tolylene-diisocyanate, 4,4'-diphenyl- Rumethane diisocyanate, naphthalene 1,5 diisocyanate, tolidine diisocyanate, etc.
  • the polyisocyanate is preferably an organic diisocyanate trimer, and most preferably a tolylene diisocyanate trimer and an isophorone diisocyanate trimer. These may be used alone or in combination. May be.
  • the polyisocyanate trimer As a process for producing the isocyanate trimer, the polyisocyanate is converted to an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carbonates and the like. Use this to perform partial trimerization of isocyanate groups, stop the trimerization by adding catalyst poison, and then remove unreacted polyisocyanate by solvent extraction and thin-film distillation. The method of obtaining the isocyanurate group containing polyisocyanate of this is mentioned.
  • trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carbonates and the like.
  • Examples of the compound having one or two hydroxyl groups in the same molecule include polyether dariconol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds has 1 to 25 carbon atoms. And an alkyl group of the alkyl group or a mixture of two or more of these.
  • polyether glycol examples include polyether diol, polyether ester diol, or a mixture of two or more of these.
  • polyether diols are those obtained by homo- or copolymerization of alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyotatam. Tylene glycol, or a mixture of two or more thereof.
  • Polyetherester diols include those obtained by reacting a mixture of an ether group-containing diol or other dallicol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide.
  • polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • polyester glycol examples include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3 butanediol, 1,4 butanediol, 2,3 butanediol, 3-methyl-1,5-pentanediol, neopentyl Glycol, 2-methyl-1,3 propanediol, 2-methyl-2-propyl 1,3 propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl- 2, 4 Pentanediol, 2, 2, 4 Trimethyl-1, 3 Alipha
  • a product obtained by condensation for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene Z-propylene adipate, or the like, or the diol or a monohydric alcohol having 1 to 25 carbon atoms as an initiator.
  • Polylatatonediol obtained by using There poly Lata tons monool For example, poly force Purorata tons glycol, poly valeronitrile rata tons, or a mixture of two or more thereof.
  • polyester glycol is a poly-prolactor It is a compound obtained by ring-opening addition polymerization of ⁇ -strength prolatatone with tonglycol or alcohol having 1 to 25 carbon atoms as an initiator, more specifically ⁇ -strength prolatatone.
  • polyether glycol and polyester glycol are particularly preferred.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
  • the active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom, a hydroxyl group
  • the active hydrogen examples thereof include hydrogen atoms in functional groups such as amino groups and thiol groups.
  • amino groups, particularly primary amino group hydrogen atoms are preferred.
  • a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, and ⁇ -butyl, or the dialkylamino group is linked to form a heterocyclic structure.
  • a dimethylamino group and an imidazole ring are preferred because of excellent dispersion stability.
  • Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule are: ⁇ , ⁇ ⁇ ⁇ ⁇ dimethyl-1,3 propanediamine, ⁇ , ⁇ ⁇ jetyl-1,3 propanediamine, ⁇ , ⁇ dipropinole 1 , 3 Propanadamine, ⁇ , ⁇ -Dibutinoleol 1, 3 Propandamine, ⁇ , ⁇ ⁇ ⁇ ⁇ Dimethylethylene diamine, ⁇ , ⁇ ⁇ Jetylethylene diamine, ⁇ , ⁇ Dipropylethylene diamine, ⁇ , ⁇ Dibutylethylene diamine Amines, ⁇ , ⁇ Dimethylolene 1, 4 Butanediamin, ⁇ , ⁇ ⁇ Jetinore 1,4 Butanediamine, ⁇ , ⁇ Dipropyl—1, 4 Butanediamin, ⁇ , ⁇ Dibutyl—1, 4 Butanediamin, etc.
  • tertiary amino group is a nitrogen-containing heterocycle
  • a pyrazole ring an imidazole Ring, triazole ring, tetrazole ring, indole ring, force rubazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazol ring, benzothiadiazole ring, etc.
  • the preferred use ratio of these urethane resin dispersant raw materials is that the compound having one or two hydroxyl groups in the same molecule is usually 10 to 200 per 100 parts by weight of the polyisocyanate compound. Parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0. 3 to 24 parts by weight.
  • Esters such as butyl acetate and cellosolve; hydrocarbons such as benzene, toluene, xylene and hexane; some alcohols such as diacetone alcohol, isopropanol, sec-butanol and tert-butanol; methylene chloride, Halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and jetyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide Is used.
  • a catalyst for production a usual urethanization reaction catalyst is used.
  • tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin ditatoate, stanasoctoate; iron systems such as iron acetyl cetate and ferric chloride; 3 such as triethylamine, triethylenediamine, etc. Class amin type and the like.
  • the dispersing ability tends to decrease, and if it exceeds the above range, the developability tends to decrease.
  • the dispersant used in the curable composition of the present invention may contain other dispersants in addition to the various dispersants described above.
  • dispersants examples include polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. You can.
  • the content ratio of the (E) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less based on the (D) pigment. Further, it is usually 5% by weight or more, preferably 7% by weight or more, particularly preferably 10% by weight or more. If the content of the dispersant is too small, adsorption to the coloring material is insufficient and aggregation cannot be prevented, and viscosity may increase or gelation may occur, resulting in poor dispersion stability and reaggregation. And problems such as thickening may occur.
  • the (E) dispersant of the present invention is one in which the nitrogen atom in the adsorption part to the pigment does not have ion properties. That is, it is preferably a nitrogen atom that is not quaternized, such as tertiary amine, secondary amine, primary amine, cyclic amine, or imino group. This is probably the same for any of the dispersants (E-1), (E-2), and (E-3), regardless of the type of dispersant.
  • each dispersant described above generally has an anchor portion (pigment adsorbing portion) and a tail portion (a portion that controls dispersibility). Do not have ionicity in the adsorption section! In the case of a dispersant containing a nitrogen atom, a solvent molecule or a water molecule in the solvent forms a hydrogen bond with an electron pair of the nitrogen atom and enters between a plurality of tails of the dispersant molecule. For this reason, it is thought that the structure between the tails is greatly expanded compared to dispersants with other groups such as quaternary ammine groups in the adsorption part.
  • “Good re-solubility” means that the curable composition solidifies once, and immediately adjusts to the solvent when immersed in the solvent. However, the distance between the tails of the dispersant adsorbed on the pigment is small. If it is open, solvent molecules can easily enter it. For example, when water forms hydrogen bonds, some of the solvent molecules form bonds with water molecules or electron pairs of nitrogen atoms, making it easier to penetrate between the tails of the dispersant, making it easier to finer. Can be distributed It is disregarded.
  • the curable composition of the present invention contains a part of the above-mentioned (A) binder resin together with the (E) dispersant in the dispersion treatment step when preparing the curable composition described later. Thus, both may serve as a dispersant.
  • the curable composition of the present invention may further contain a photopolymerization initiation system.
  • the photopolymerization initiation system is usually used as a mixture of a photopolymerization initiator and an additive such as a sensitizing dye and a polymerization accelerator that are added as necessary, and directly absorbs light or is photosensitized. It is a component having a function of generating a polymerization active radical by causing a decomposition reaction or a hydrogen abstraction reaction.
  • titanocene derivatives dicyclopentagel titanium dichloride, dicyclopentagel titanium bisphenol, dicyclopentagel titanium bis (2, 3, 4, 5, 6 pentafluorophenyl-1 yl), dicyclopentadium titanium bis (2, 3, 5, 6-tetrafluorophene 1 yl), dicyclopentagel titanium bis ( 2, 4, 6 trifluorophenyl 1-yl), dicyclopentagel titanium di (2, 6 difluoropheny 1 yl), dicyclopentagel titanium di (2, 4 difluoropheny 1 yl), di ( Methylcyclopentagel) Titanium bis (2, 3, 4, 5, 6 Pentafluorophenol-1 yl), Di (methylcyclopentagel) Titanium bis (2, 6 difluorophenyl), Dicyclo Printer And gel titanium [2, 6 di-fluoro 3 (pyro-1-yl) -fer-1-yl].
  • biimidazole derivatives include 2- (2, -black mouth file) -4, 5 diphenyl loumidazole dimer, 2- (2, one-way mouth ring) 4, 5 bis (3 , Monomethoxyphenyl) imidazole dimer, 2- (2, monofluorophenol) —4,5 diphenylimidazole dimer, 2- (2, methoxyphenyl) —4,5 diphenyl Examples include imidazole dimer, (4, -methoxyphenyl) -4,5 diphenol imidazole dimer, and the like.
  • halomethyl oxoxadiazole derivatives include 2-trichloromethyl-1,5- (2,1-benzofuryl) -1,3,4-oxadiazol, 2-trichloromethyl-1,5- [j8- (2, -benzofuryl) bulu]- 1, 3, 4-Oxadiazole, 2 Trichloromethyl-5- [ ⁇ - (2,-(6 "Benzofuryl) butyl)]-1 1, 3, 4 Oxadiazole, 2 Trichloromethyl-5-furyl 1, 3, 4 And oxaziazole.
  • ex-aminoalkylphenone derivatives include 2-methyl-1 [4 (methylthio) phenol] 2-morpholinopropane-1-one, 2-benzyl-1-2-dimethylamino-1- (4- Morpholinophenol) 1-butanone 1, 2-benzyl-1-2-dimethylamino 1- (4 morpholinophenol) butane 1-one, 4 dimethylaminoethylbenzoate, 4-dimethylaminoiso Amylbenzoate, 4-Jetylaminoacetophenone, 4-Dimethylaminopropiophenone, 2 Ethylhexyl, 1,4-Dimethylaminobenzoate, 2, 5 Bis (4-Jetylaminobenzal) Examples include cyclohexanone, 7-jetylamino 3- (4-jetylaminobenzoyl) coumarin, and 4 (jetylamino) chalcone.
  • the oxime ester derivatives include 1,2-octanedione, 1- [4- (phen-thio) phenol], 2- ( ⁇ -benzoyloxime), ethanone, 1- [9 ethyl. 6 1 (2 methylbenzoyl) 1 9H-force rubazol-3-yl], 1 (o-acetyloxy) and the like.
  • Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t-butylanthraquinone, 1-chloro Anthraquinone derivatives such as oral anthraquinone; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-power Benzophenone derivatives such as levoxybenzophenone; 2,2-dimethoxy-2-phenyl-phenphenone, 2,2-jetoxenphenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy-2-methylphenol pro Panone, 1-hydroxy mono 1-methyl ethyl ketone ( ⁇
  • Examples of the polymerization accelerator used as necessary include ⁇ , ⁇ ⁇ ⁇ ⁇ alkyl esters of ⁇ ⁇ ⁇ ⁇ , ⁇ dialkylaminobenzoate such as ⁇ ⁇ ⁇ ⁇ dimethylaminobenzoate; 2 mercaptobenzozoazole, 2-mercaptobenzoxazole, 2 —Mercapto compounds having a heterocyclic ring such as mercaptobenzoimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.
  • the content ratio of these photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less in the total solid content. Preferably it is 30 wt% or less. If the content is extremely low, the sensitivity to exposure light may be reduced. Conversely, if the content is extremely high, the solubility of the unexposed area in the developer will be reduced, leading to poor development. There is.
  • a sensitizing dye is used for the purpose of increasing the sensitivity as necessary.
  • Sensitizing dyes can be used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239,703, JP-A-5-289335, etc.
  • amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenol group in the same molecule. Particularly preferred are, for example, 4,4, -dimethylaminobenzophenone, 4,4, -jetylaminobenzophenone, 2 aminobenzofenone, 4-aminominobenzofoenone, 4,4'-diaminobenzophenone, 3 , 3'-Diaminobenzophenone, 3,4-Diaminobenzophenone and other benzophenone compounds; 2- (p-dimethylaminophenol) benzoxazole, 2- (p-demethylaminophenol) benzoxa Sol, 2- (p dimethylaminophenol) benzo [4,5] benzoxazole, 2- (p dimethylaminophenol) benzo [6,7] benzoxazole, 2,5 bis (p Jetylaminophenol) 1, 3, 4-oxazole, 2- (p-dimethylaminophenol) be
  • the content of these sensitizing dyes is generally 0 wt% or more, preferably 0.2 wt% or more, more preferably 0.5 wt%, based on the total solid content.
  • the range is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.
  • the curable composition of the present invention may further contain a surfactant.
  • a surfactant various types such as ionic, cationic, nonionic, and amphoteric surfactants can be used, but they adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant because it is less likely to affect it.
  • Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and quaternary ammonia such as “Cotamine 24P” and “Cotamin 86W” manufactured by Kao Corporation. -Um salt type surfactants and the like. Of these, stearyltrimethylammonium salt surfactants are preferred, with quaternary ammonium salt surfactants being preferred.
  • V a so-called polyether-modified or aralkyl-modified silicone surfactant, having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane preferred by a silicone-based surfactant. Further preferred.
  • Two or more kinds of surfactants may be used in combination, for example, silicone surfactant Z fluorine surfactant, silicone surfactant Z special polymer surfactant, fluorine surfactant Z Examples include combinations of special polymer surfactants. Of these, a combination of a silicone-based surfactant Z-fluorine-based surfactant is preferable.
  • the content of these surfactants is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably in the total solid content. It is 0.01% by weight or more, particularly preferably 0.02% by weight or more. Further, it is usually used in the range of 10% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0.05% by weight or less.
  • the curable composition of the present invention includes a dispersion aid, an organic carboxylic acid or Z and an organic carboxylic anhydride, a plasticizer, a dye, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, It may contain an adhesion improver, a development improver, and the like.
  • the dispersing aid is used to improve the dispersibility and dispersion stability of the (D) pigment.
  • the (D) pigment For example, azo, phthalocyanine, quinacridone, benzimidazolone, quino Derivatives such as phthalone-based, isoindolinone-based, ditalented xazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based pigments.
  • substituents for these pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, aryl group, heterocyclic group or the like. Of the above substituents, sulfonic acid groups, quaternary salts thereof, and sulfonic acid groups that are preferred are sulfonic acid groups.
  • a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.
  • pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrole.
  • examples include sulfonic acid derivatives of oral pyrrole pigments and sulfonic acid derivatives of dioxazine pigments.
  • sulfonic acid derivatives of Pigment Yellow 138 sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, Pigment Red 272 Sulfonic acid derivatives of Pigment Red 209, sulfonic acid derivatives of Pigment Orange 71, sulfonic acid derivatives of Pigment Violet 23, more preferably sulfonic acid derivatives of Pigment Yellow 138, Pigment Red 254 It is a sulfonic acid derivative.
  • the content of these dispersion aids is usually 0.1% by weight or more, and usually 30% by weight, based on the color material component. % Or less, preferably 200% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. This is because if the added amount is small, the effect is not exerted, and conversely if the added amount is too large, the dispersibility and dispersion stability are rather deteriorated.
  • the curable resin composition of the present invention does not contain a phosphate acrylate content or Or, it is preferably 5% by weight or less based on the total solid content. Atallate phosphate is often used mainly as an adhesion improver, but tends to inhibit adsorption of highly polar pigments and dispersants, and reaggregation of the pigments is likely to occur. For this reason, the viscosity of the curable resin composition may increase and stability may decrease. This reagglomeration is accelerated by moisture contained in the composition.
  • organic carboxylic acid examples include aliphatic carboxylic acids and aromatic carboxylic acids.
  • Aromatic rubonic acids include carboxylic acids in which a carboxyl group is directly bonded to a fur group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond. Can be mentioned.
  • organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, anhydrous trichloroacetic acid, trifluoroacetic anhydride, tetrahydrophthalic anhydride, and succinic anhydride.
  • examples thereof include aliphatic carboxylic acid anhydrides such as decyl succinic acid and anhydrous 5-norbornene-2,3-dicarboxylic acid.
  • aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
  • the content ratio of these organic carboxylic acid or Z and organic carboxylic acid anhydride is usually 0.01 wt% or more, preferably 0.03 wt% in the total solid content. % Or more, more preferably 0.05% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less.
  • the curable composition of the present invention may contain a dye, such as an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinonimine dye, a quinoline dye, a nitro dye, or a carbonyl dye. And dyes and methine dyes.
  • a dye such as an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinonimine dye, a quinoline dye, a nitro dye, or a carbonyl dye.
  • dyes and methine dyes such as an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinonimine dye, a quinoline dye, a nitro dye, or a carbonyl dye.
  • anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56 CI Days Purse Blue 60 etc.
  • the curable composition of the present invention may contain a plasticizer, and examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl dallicol phthalate. Tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol and the like.
  • the content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content.
  • the pigment, (C) the solvent, and ( ⁇ ) the dispersant, which are optional components, are weighed in predetermined amounts, and in the dispersion treatment step, (D) the pigment is dispersed to obtain an ink-like liquid.
  • a paint conditioner, a sand grinder, a Bono reminole, a Rono reminole, a stone mill, a jet mill, a homogenizer, or the like can be used.
  • the pigment is made into fine particles, so that the coating characteristics of the curable composition are improved and the transmittance of the product color filter substrate and the like is improved.
  • a part of the binder resin and a dispersion aid are preferably used as appropriate.
  • the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several millimeters or zircoyu beads.
  • the temperature during the dispersion treatment is usually set to 0 ° C or higher, preferably room temperature or higher, and usually 100 ° C or lower, preferably 80 ° C or lower.
  • the dispersion time needs to be adjusted as appropriate because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.
  • the ink-like liquid obtained by the dispersion treatment is further subjected to photopolymerization, which is an essential component (A) Noinda resin, (B) monomer, and (C) solvent, and in some cases, an optional component.
  • the curable composition is obtained by mixing the starting system, the surfactant, and other components to obtain a uniform dispersion solution.
  • the obtained ink-like liquid is preferably filtered with a filter or the like.
  • the curable composition of the present invention is usually in a state where all of the constituent components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form a color filter and a liquid crystal display component.
  • the transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength.
  • the material include polyester-based resin such as polyethylene terephthalate; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylic resin such as polymethyl methacrylate; Examples thereof include a plastic resin sheet; a thermosetting resin sheet such as an epoxy resin and an unsaturated polyester resin; or various glasses.
  • glass and heat resistant resin are preferable from the viewpoint of heat resistance.
  • these transparent substrates are subjected to surface treatments such as corona discharge treatment and ozone treatment, as well as various types of resin such as silane coupling agent urethane resin.
  • a thin film forming process or the like may be performed.
  • the thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less.
  • the film thickness is usually 0. Ol / zm or more, preferably 0. 05 / zm or more, and usually 10 m or less, preferably 5 ⁇ m. m or less.
  • a black matrix is provided on the transparent substrate described above, and usually red, green, and blue images are displayed.
  • a color filter can be produced by forming an elementary image.
  • the black matrix is formed on a transparent substrate using a light shielding metal thin film or the curable composition of the present invention.
  • a chromium compound such as metal chromium, chromium oxide, chromium nitride, nickel and tungsten alloy, etc. may be used, and these may be laminated in a plurality of layers.
  • These light-shielding metal thin films are generally formed by a sputtering method, and a desired pattern is formed in a film shape by a photoresist.
  • Etching solution mixed with ceric nitrate ammonium and perchloric acid and Z or nitric acid is used for chromium, and other materials are etched using an etching solution according to the material.
  • the black matrix can be formed by stripping the positive photoresist with a special stripper.
  • a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering.
  • a coating film of the resin composition for positive photoresist is formed on the thin film.
  • the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form an image. Thereafter, this coating film can be etched to form a black matrix.
  • a black matrix is formed using a curable composition containing a black (D) pigment.
  • a black (D) pigment obtained by mixing black pigments such as carbon black, graphite, iron black, titanium black or the like, or a mixture of pigments such as red, green, and blue appropriately selected from inorganic or organic pigments
  • a curable composition containing a pigment a black matrix can be formed in a manner similar to the method of forming red, green, and blue pixel images described below.
  • the curable composition is used as at least one image forming coating liquid among black, red, green, and blue.
  • black curable compositions on the transparent substrate, for red, green, and blue curable compositions, on the black matrix forming surface formed on the transparent substrate, or for chromium compounds and other light shielding
  • a pixel image of each color is formed on a metal black matrix forming surface formed using a metal material through each process of coating, heat drying, image exposure, development, and heat curing.
  • a curable composition containing a pigment of one color of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and this photomask is applied.
  • a pixel image is formed by image exposure, development, and heat curing or photocuring as necessary to create a colored layer.
  • a color filter image can be formed.
  • the curable composition of the present invention can provide a coating film having a smooth and beautiful surface without lowering the yield because aggregated foreign matters are less likely to be generated at the tip of the dispensing nozzle.
  • there is no coating unevenness during the coating or drying unevenness in the subsequent drying process and a layer having an extremely smooth surface can be formed through an exposure process, a development process, a heat treatment process, and the like. .
  • the coating conditions by the slit and spin method and the die coating method may be appropriately selected depending on the composition of the curable composition, the type of color filter to be produced, and the like.
  • the lip width at the nozzle tip is preferably 50 to 500 m, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 ⁇ m.
  • the lip running speed and the discharge amount of the liquid resin composition with lip force can be adjusted.
  • it may be adjusted mainly by the spin rotation speed and rotation time after slit coating.
  • the thickness of the coating film is usually not less than 0, preferably not less than 0.5 / zm, more preferably not less than 0.8 m, and usually not more than 20 ⁇ m, preferably 10 ⁇ m as the thickness after drying. Below, more preferably in the range of 5 ⁇ m or less. The effectiveness of the curable composition of the present invention is remarkable when used in a die coating method.
  • the coating film after the curable composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a competition oven. Usually, after preliminary drying, it is dried by heating again.
  • the conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like.
  • the drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is a force depending on the heating temperature, usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes or less.
  • a vacuum drying method in which drying is performed in a vacuum chamber without increasing the temperature may be used.
  • Image exposure is carried out by superposing a negative matrix pattern on the coating film of the colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen.
  • the light source used for said image exposure is not specifically limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, etc.
  • Light sources Argon ion lasers, YAG lasers And laser light sources such as excimer laser, nitrogen laser, helium force dominium laser, and semiconductor laser.
  • An optical filter can also be used when irradiating light of a specific wavelength.
  • the color filter is used to expose the image of the coating film of the curable composition with the above light source. After performing light, an image can be formed on the substrate by developing with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.
  • This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
  • the alkaline compound includes sodium hydroxide, potassium hydroxide, lithium hydroxide.
  • alkaline compounds such as potassium hydrogen and ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di- or tri-methylamine, mono-'di- 'or tri -Ethylamine, mono- 'or di-isopropylamine, n-butylamine, mono-di' or triisopropanolamine, ethylene
  • Organic alkaline compounds such as ethylene, ethylenedimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more.
  • the surfactant examples include non-ionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.
  • Anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters; amphoteric surfactants such as alkyl betaines and amino acids Can be mentioned.
  • the organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phenylcelesolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent can be used alone or in combination with an aqueous solution.
  • the development temperature is usually 10 ° C or higher, especially 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, especially 45 ° C or lower, and more A range of 40 ° C or lower is preferred.
  • the development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.
  • the color filter according to the present invention has, in addition to the above-described production method, (1) a curable composition containing a solvent, a phthalocyanine pigment as a pigment, and a polyimide resin as a binder resin on a substrate. It can also be produced by a method of applying and forming a pixel image by etching. Also, (2) a method of directly forming a pixel image on a transparent substrate using a printing machine using a curable composition containing a phthalocyanine pigment as a colored ink, and (3) a curable composition containing a phthalocyanine pigment.
  • the color filter after development is subjected to heat curing.
  • the thermosetting treatment conditions at this time are usually selected in the range of 100 ° C or higher, preferably 150 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower, and the time is 5 minutes or longer. Selected within 60 minutes or less.
  • the patterning image formation for one color is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter.
  • the order of patterning the four colors is not limited to the order described above.
  • ribs may be formed. Also, instead of a bead-spreading type spacer, a column structure (photo spacer) is sometimes formed by photolithography.
  • the liquid crystal display device includes, for example, the [3-1] color filter (hereinafter referred to as “power”).
  • a thin film transistor (TFT) driving substrate may be opposed to each other with a liquid crystal layer therebetween.
  • a color filter substrate coated with alignment film material and subjected to alignment treatment and a TFT drive substrate are bonded together via a peripheral sealing material, and a liquid crystal material is injected into the gap.
  • a liquid crystal display device can be obtained.
  • the liquid crystal display device usually has an alignment film formed on the color filter according to the present invention, and after a spacer is dispersed on the alignment film, the liquid crystal display device is bonded to a counter substrate and bonded to a liquid crystal. It is manufactured by forming a crystal cell, injecting liquid crystal into the formed liquid crystal cell, and connecting to a counter electrode.
  • the alignment film is preferably a resin film such as polyimide.
  • a gravure printing method and a Z or flexographic printing method are usually employed, and the thickness of the alignment film is set to several lOnm.
  • the alignment film is cured by thermal baking, it is surface-treated by treatment with a rubbing cloth after being irradiated with ultraviolet rays, and processed into a surface state capable of adjusting the tilt of the liquid crystal.
  • a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 ⁇ m is preferable.
  • a transparent resin film photospacer (PS) is formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
  • the counter substrate an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
  • the gap for bonding to the counter substrate varies depending on the application of the liquid crystal panel, but is usually selected in the range of 8 to z / m.
  • the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin.
  • the seal material is cured by UV irradiation and Z or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell.
  • Decompression degree in the liquid crystal cell is usually 1 X 10- 2 Pa or more, preferably 1 X 10- 3 or more, and usually 1 X 10- 7 Pa or less, preferably in the following range 1 X 10- 6 Pa is there.
  • the heating temperature is usually 30 ° C or higher. Above, preferably in the range of 50 ° C or higher, usually 100 ° C or lower, preferably 90 ° C or lower. Heating during decompression is usually in the range of 10 minutes to 60 minutes, and then immersed in the liquid crystal.
  • a colored curable composition filled with a test piece is attached to the arm of the actuator.
  • the glass test piece was also taken out at a speed of 12.5 mmZ seconds, and the strength of the curable composition was taken out and held vertically with the tip of the glass test piece down, and then the ambient temperature was 23 ° C, the humidity was 55%, The film was dried for 52 seconds under the condition of a wind speed of 0.5 ⁇ 0.2 mZ seconds.
  • Steps (1) and (2) were repeated a total of 250 times to form a deposit (a) derived from the curable composition on the glass test piece.
  • the ridge line with the largest amount of the deposit was selected, and the weight of the deposit (“deposit (a)”) on the ridge was measured.
  • the weight of the deposit (a) is measured in advance by the ratio of the film formed using the curable composition.
  • the volume of the deposit (a) was measured with a three-dimensional laser microscope and calculated from the product of these.
  • the moisture content was measured on condition of the following by Karl Fischer method.
  • Propylene glycol monomethyl ether acetate 220.73 parts, V-59 (Wako Pure Chemical Industries azo-based polymerization initiator) 8.5 parts by weight were charged in a reaction vessel and heated to 80 ° C under a nitrogen atmosphere.
  • 127.5 parts by weight of propylene glycol monomethyl ether acetate, 55 parts by weight of benzyl methacrylate and 45 parts by weight of methacrylic acid were added dropwise over 2 hours, followed by stirring for 6 hours to obtain a polymerization reaction solution.
  • a polymer solution was prepared in the same manner as in Synthesis Example 1 except that V-59 was changed to 6 parts by weight.
  • the weight average molecular weight of the obtained polymer was 20000, and the acid value was 72 mgKOHZg.
  • the synthesized polymer had a weight average molecular weight of 8000 and an acid value of 176 mgKOH / g.
  • reaction vessel was replaced with air, 27 parts by weight of acrylic acid, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours.
  • THPA tetrahydrophthalic anhydride
  • XD1000 polyglycidyl ether of dicyclopentaphene phenol polymer, weight average molecular weight 700, epoxy equivalent 252 300 parts, methacrylic acid 101 parts, p-methoxyphenol 0.2 part, triphenylphosphine 5 parts, 255 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel, and the acid value is 3. OmgKOH at 100 ° C. Stir until Zg. It took 9 hours for the acid value to reach the target (acid value 2.5).
  • the weight average molecular weight Mw measured by GPC of the dispersant thus synthesized was about 9000.
  • Example 1 of JP-A-1-229014 an acrylic BAB block copolymer having a quaternary ammonium base (dimethylbenzyl ammonium base) was synthesized.
  • the resulting copolymer had a weight average molecular weight Mw of 9000, an amine value of 10 mgKOHZg, and an acid value of OmgKOHZg.
  • CI Pigment Green 36 as coloring material, 7.3 parts by weight, CI Pigment Yellow 150, 3.1 parts by weight, propylene glycol monomethyl ether acetate as solvent, 60.0 parts by weight, as dispersant, listed in Table 1.
  • the stainless steel container is filled with 1.3 parts by weight of the total amount of the dispersant, 3.4 parts by weight of the resin described in (Table), and 225 parts by weight of zirca beads having an average particle size of 0.5 mm. After 6 hours of dispersion with a paint shaker, filter 1 The bead and the dispersion were separated to prepare a green pigment dispersion.
  • Carbon black for color (Mitsubishi Chemical “MA-8”, average particle size 24 ⁇ m, DBP oil absorption 58ml / 100g) lOOg is kneaded for 20 minutes with 500ml of ultrapure water in a twin screw machine. Ultrapure water was removed by filtration. Ultrapure water was added again to the filtered carbon black and kneaded, and filtration was repeated 4 times. Finally, the filtered carbon black was dried and washed to obtain carbon black. Add 50 parts by weight of cleaned carbon black to 10 parts by weight of bykl61 (uric rosin dispersant made by Bic 'Chemi Co., amine value 39 mgKOH / g) and PGME A, so that the solids concentration is 30% by weight. It was adjusted. The total weight of the pigment dispersion was 50 g. This was stirred with a stirrer and premixed.
  • bykl61 uric rosin dispersant made by Bic 'Chemi Co., amine value
  • dispersion treatment was performed for 6 hours in the range of 25 to 45 ° C. using a paint shaker.
  • the beads used 0.5 mm diameter Zirco Your beads and had the same weight as the dispersion.
  • the dispersion was finished (20-degree specular gloss 170 in JIS Z8741), the beads and the dispersion were separated by a filter to prepare a pigment dispersion.
  • each component was added so as to have the following blending ratio, and stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.
  • Surfactant (Sumitomo 3M “FC-430”, fluorosurfactant): An amount that gives a concentration of lOOppm in the resist solution.
  • Example 4 where the viscosity increase after storage for 2 weeks was 0.5 cps or more and 1. Ocps or less, slight force was generated during application. The number of defects in the obtained application area was small.
  • production of an aggregate foreign material can be provided.
  • a peeling piece foreign material thus, it is possible to provide a high-quality color filter and a liquid crystal display device in which the occurrence of defects due to the liquid crystal display is reduced. Accordingly, industrial applicability is extremely high in the fields of various curable compositions, color filters, and liquid crystal display devices that are used as materials for pixels, black matrices, and the like. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2006-066107, filed on March 10, 2006, are incorporated herein by reference. It is included as an indication.

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Abstract

L'invention concerne une composition durcissable générant peu de contaminants agrégés et présentant une excellente stabilité au stockage ; et des filtres colorés de grande qualité et des affichages à cristaux liquides fabriqués en utilisant la composition et souffrant de peu de défauts dus à des contaminants fragmentaires exfoliés. L'invention concerne donc une composition durcissable comprenant (A) un liant, (B) un monomère, (C) un solvant et (D) un pigment, caractérisée en ce qu'elle présente une teneur en eau comprise entre 0,4 et 2,0 % en poids, une quantité (a) de matière adhérant à une arête d'un morceau de verre pour essai inférieure ou égale à 2 μg, déterminée par un test d'applicabilité (I) comprenant quatre étapes spécifiques, et une augmentation de viscosité inférieure ou égale à 1,0 cps après stockage à 35 °C pendant 2 semaines sous pression normale ; ainsi que des filtres colorés et des affichages à cristaux liquides fabriqués en utilisant cette composition.
PCT/JP2007/054714 2006-03-10 2007-03-09 Composition durcissable, filtres colores et affichage a cristaux liquides WO2007105649A1 (fr)

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CN2007800044421A CN101379132B (zh) 2006-03-10 2007-03-09 固化性组合物、滤色器以及液晶显示装置

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KR101638354B1 (ko) * 2013-05-28 2016-07-11 동우 화인켐 주식회사 스페이서 형성용 감광성 수지 조성물 및 이로부터 제조되는 스페이서
KR101391224B1 (ko) * 2013-05-28 2014-05-02 동우 화인켐 주식회사 스페이서 형성용 감광성 수지 조성물 및 이로부터 제조되는 스페이서
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JPH10104412A (ja) * 1996-09-26 1998-04-24 Sekisui Finechem Co Ltd 着色感光性樹脂組成物及びカラーフィルター
JPH10293397A (ja) * 1997-04-22 1998-11-04 Jsr Corp カラーフィルター用感放射線性組成物
JP2002080547A (ja) * 2000-07-04 2002-03-19 Daikin Ind Ltd 活性エネルギー線硬化性水性フッ素樹脂組成物および含フッ素被覆物の形成方法
JP2002287353A (ja) * 2001-03-28 2002-10-03 Nippon Paint Co Ltd フォトソルダーレジスト組成物

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JP2009052031A (ja) * 2007-07-27 2009-03-12 Mitsubishi Chemicals Corp 着色硬化性樹脂組成物、カラーフィルタ、液晶表示装置および有機ｅｌディスプレイ
JP2009244408A (ja) * 2008-03-28 2009-10-22 Fujifilm Corp 感光性樹脂組成物、遮光性カラーフィルター及びその製造方法、並びに、固体撮像素子
KR101925820B1 (ko) 2014-09-01 2018-12-06 후지필름 가부시키가이샤 적외광 차폐 조성물, 적외광 차단 필터, 고체 촬상 소자

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KR101167868B1 (ko) 2012-07-23
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