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WO2006006581A1 - Composition de résine isolante photosensible, son produit durci et son utilisation - Google Patents

Composition de résine isolante photosensible, son produit durci et son utilisation Download PDF

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Publication number
WO2006006581A1
WO2006006581A1 PCT/JP2005/012806 JP2005012806W WO2006006581A1 WO 2006006581 A1 WO2006006581 A1 WO 2006006581A1 JP 2005012806 W JP2005012806 W JP 2005012806W WO 2006006581 A1 WO2006006581 A1 WO 2006006581A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
insulating resin
compound
photosensitive insulating
photosensitive
Prior art date
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PCT/JP2005/012806
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English (en)
Japanese (ja)
Inventor
Hirofumi Gotou
Katsumi Inomata
Shin-Ichirou Iwanaga
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Jsr Corporation
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Priority to JP2006529050A priority Critical patent/JPWO2006006581A1/ja
Publication of WO2006006581A1 publication Critical patent/WO2006006581A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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

Definitions

  • Photosensitive insulating resin composition cured product thereof and use thereof
  • the present invention relates to a photosensitive insulating resin composition used for a surface protective film (overcoat film) or an interlayer insulating film (nobation film) for organic semiconductor elements, a cured product obtained by curing the same, and Regarding its use. More specifically, a cured product that can be alkali-developed, has excellent resolution as a resist, and has excellent properties such as low-temperature curability, electrical insulation, thermal shock resistance, and chemical resistance, and such a cured product.
  • the present invention relates to a photosensitive insulating resin composition that can be obtained and its use.
  • Organic materials have attracted attention as next-generation electronic device materials.
  • Organic semiconductor materials are attracting attention as a third semiconductor material following Si and GaAs, and are being actively developed.
  • Organic semiconductor materials are formed at a low temperature of 150 ° C or lower, and the degree of freedom in selecting the substrate to be used is improved. Therefore, when organic semiconductor materials are used, semiconductor devices can be easily manufactured with relatively inexpensive manufacturing equipment. There is an advantage that it can be manufactured. For example, many elements such as organic electroluminescence (EL) display elements with luminescent properties, organic memory elements that use polyvinylidene fluoride as a ferroelectric layer, and organic photoelectric conversion elements that convert light energy into electrical energy has been researched and developed.
  • EL organic electroluminescence
  • organic semiconductor materials have a problem that they have low heat resistance and cannot be applied to conventional materials and manufacturing processes when forming a passivation film, a buffer coat layer, and the like.
  • photosensitive polyimides widely used in these applications usually cannot be applied to organic semiconductor manufacturing processes because they require heating at 300 ° C. or higher for curing.
  • a copolymer obtained by copolymerizing a (meth) atalylate having an oxetanyl group and a specific hydroxy or alkoxystyrene derivative, a photo-sensitive acid A composition containing a generator, a specific cross-linking agent, and an adhesion assistant The present inventors have found that the above problems can be solved, and have completed the present invention.
  • the photosensitive resin composition includes, for example, alkali-soluble resin, cross-linking agent, intramolecular A compound having an oxetane structure, a rubber, a radiation-sensitive resin composition containing a radiation polymerization initiator (see Patent Document 1), a compound having an oxetane structure (A), a compound having a radical polymerizable unsaturated group (B ), Photoradical initiator (C), cationic polymerization initiator (D), and photosensitive resin composition containing alkali-soluble resin (E) (see Patent Document 2), alkaline-soluble resin, photopolymerizable
  • the alkali-soluble resin has a polymerizable double bond over a photocurable composition containing a monomer, a photopolymerization initiator, and a solvent, and the photocurable composition further contains an organic compound.
  • a photocurable composition containing a peroxide (see Patent Document 3) is known, but the alkali-soluble resin used in these resin compositions contains a (meth) acrylate having an oxetal group. Containing as a monomer component of rosin is not.
  • the photosensitive resin composition is a negative resist composition containing an alkali-soluble resin as a base resin, and is used in the structure of the alkali-soluble resin or in combination with the alkali-soluble resin.
  • a negative resist composition containing an oxetane structure in the structure of the compound to be prepared (see Patent Document 4) is also known, but this composition uses a specific cadmium-containing compound as a crosslinking agent.
  • the photosensitive resin composition is a photosensitive resin composition containing an alkali-soluble resin, a crosslinking agent, and a photopolymerization initiator, and the alkali-soluble resin has an organic polymer having a phenolic hydroxyl group.
  • a photosensitive resin composition which is a polymer containing a compound represented by the following general formula (1) in which structural unit is modified with an oxsilane compound and Z or oxetane compound as a structural unit, and an alkali-soluble resin, a crosslinking agent A modified poly (p-hydroxystyrene) represented by the following general formula (2), wherein the alkali-soluble resin contains an oxsilane ring and a Z or oxetane ring:
  • This photosensitive resin composition (see Patent Document 5) is also known in the art.
  • This composition is a compound in which the phenolic hydroxyl group of the alkali-soluble resin used is modified with an oxetane compound. It has a return unit.
  • n and n represent an integer of 1 or more, and X represents a functional group containing an oxsilane ring and a Z or oxetane ring.
  • the photosensitive resin composition also includes a radiation-sensitive composition containing a polymer compound (A) having a carboxyl group and an oxetane skeleton, a quinonediazide compound (B), and a polyvalent phenolic compound (C).
  • An active rosin composition (see Patent Document 6) is also known.
  • Patent Document 1 Japanese Patent Laid-Open No. 11 65116
  • Patent Document 2 JP 2001-228610 A
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-83754
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-343748
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2002-229204
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-156843
  • An object of the present invention is to provide a cured product that can be cured at a low temperature without hindering the function of an organic semiconductor element or the like and has excellent properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. It is an object of the present invention to provide a photosensitive insulating resin composition suitable for use in a surface protective film and an interlayer insulating film, a cured product thereof, and a use thereof.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • At least the component (B) is selected from an onion salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.
  • An electronic component comprising an insulating layer formed using the photosensitive insulating resin composition according to (1).
  • the cured product of the photosensitive insulating resin composition according to the present invention is excellent in electrical insulation, heat resistance, thermal shock resistance, and chemical resistance.
  • FIG. 1 is a cross-sectional view of a thermal shock resistance evaluation substrate.
  • FIG. 2 is a schematic diagram of a thermal shock evaluation substrate.
  • the photosensitive insulating resin composition according to the present invention contains (A) a copolymer, (B) a photosensitive acid generator, (C) a crosslinking agent, and (D) an adhesion assistant.
  • the (A) copolymer used in the present invention is a copolymer obtained from a (meth) acrylic acid ester having an oxetanyl group and a monomer represented by the following general formula (3), preferably Is a copolymer obtained from a (meth) acrylic acid ester having an oxetal group, a monomer represented by the following general formula (3), and another vinyl monomer.
  • Examples of the (meth) acrylic acid ester having an oxetanyl group include (meth) acrylic acid (3-ethyl-3-oxetal) methyl.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the monomer represented by the general formula (3) examples include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, ⁇ -methyl- ⁇ -hydroxystyrene, ⁇ -methylm-hydroxystyrene, ⁇ -methyl o-hydroxystyrene, p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-etoxystyrene, m-etoxystyrene, o-etoxystyrene, p-t-butoxystyrene, m-t-butoxystyrene O-t-butoxystyrene, ⁇ -methyl p-t-butoxystyrene, ⁇ -methyl p-t-butoxystyrene, ⁇ -methyl-p-t butoxystyrene, and the like.
  • vinyl monomers having a phenolic hydroxyl group are exemplified.
  • a vinyl monomer in which this group is protected by a protective group is copolymerized to form a copolymer. After that, the protective group is deprotected to form a copolymer having a phenolic hydroxyl group.
  • butyl monomers examples include aromatic vinyl compounds such as styrene, ⁇ -methyl styrene, ⁇ methyl styrene, ⁇ chloro styrene, m chloro styrene, ⁇ , ⁇ dimethylolene, amino styrene, and divinyl benzene;
  • Unsaturated monocarboxylic esters such as methyl crotonate, ethyl crotonate, methyl cinnamate, and ketyl cinnamate; fluoroalkyl (meth) acrylates such as ptafluorobutyl (meth) acrylate; trimethylsiloxa -Siloxal compounds such as dimethyldimethylpropyl (meth) acrylate and tris (trimethylsilyl ether);
  • Mono- or di (meth) acrylates of alkylene glycols such as ethylene glycolanol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol; 2-methoxyethyl (meth) acrylate , 2-Ethoxyethyl (meth) ate, 3-Eto
  • Polyhydric alcohols such as glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms, for example), tetramethylolalkane (alkane has 1 to 3 carbon atoms, for example 1 to 3)
  • Oligo (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate or tetra (meth) acrylate;
  • Epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxy cyclohexyl) ethyl (meth) acrylate, allyl glycidyl ester Containing monomer;
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 — hydroxypropyl (meth) acrylate; 2-hydroxyethyl crotonate, croton Hydroxyalkyl esters of unsaturated carboxylic acids, such as 2-hydroxypropyl acid and 2-hydroxypropyl quinoate;
  • Unsaturated alcohols such as (meth) aryl alcohol
  • Unsaturated (mono) carboxylic acids such as (meth) acrylic acid, crotonic acid, and cinnamate
  • Unsaturated anhydrides such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid, and their diesters;
  • Examples include vinyl chloride, vinyl acetate, cinnamate, crotonic ester, dicyclopentadiene, and ethylidene norbornene.
  • the copolymer which is the component (A) of the present invention can be produced by, for example, a known solution polymerization in the presence of a chain transfer agent, if necessary, using a radical polymerization initiator.
  • an organic solvent can be suitably used as the polymerization medium used for the solution polymerization.
  • the organic solvent include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like. Glycol monoalkyl ether acetates;
  • Propylene glycol monoalkyl ethers such as propylene glycol monomethino ethenore, propylene glycol monomethino enoate, propylene glycol monopropyl ether, propylene glycol monomono butenoate;
  • Propylene glycol dialkyl ethers such as propylene glycol dimethylol ether, propylene glycol jetino ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
  • Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethanolate acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
  • Cellosonolevs such as echinorescerosolev, butinorescerosolev;
  • Carbitols such as butyl carbitol
  • Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, n -propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate ;
  • Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
  • Aromatic hydrocarbons such as toluene and xylene
  • Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone;
  • Ratatons such as ⁇ -petit lolacun are listed.
  • organic solvents can be used alone or in admixture of two or more.
  • the copolymer ( ⁇ ) is a copolymer of a (meth) acrylic acid ester having an oxetanyl group and a hydroxy or alkoxy styrene derivative represented by the general formula (3), it has an oxetal group.
  • copolymer ( ⁇ ) (meth) acrylic acid ester having a force oxetal group and a general formula
  • the number average molecular weight (hereinafter referred to as " ⁇ ") of the copolymer ( ⁇ ) by gel permeation chromatography (GPC) is typically 1,000 to 100,000, preferably 3,00 to 50,000.
  • the photo-sensitive acid generator ( ⁇ ⁇ ) used in the present invention generates acid by irradiation with radiation.
  • the compound is not particularly limited, and examples thereof include at least one selected from onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Specific examples are shown below.
  • Examples of the onium salt compound include a ododonium salt, a sulfo-um salt, a phospho-um salt, a diazo-um salt, and a pyridi-um salt.
  • o-um salt examples include diphloe rhodonyum trifluoromethanes norephonate, diphenorehodenium p tonorenosnorehonate, diphenorehodenium.
  • Examples of the compound containing a hydrogen atom and a rogen include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like.
  • halogen-containing compounds include 1,10 dibromo-1-n-decane, 1,1 bis (4-cylinder) -1,2,2 trichloroethane, phenol-bis (trichloro S-triazine derivatives such as methyl) S-triazine, 4-methoxyphenyl-bis (trichloromethyl) S-triazine, styryl-bis (trichloromethyl) S-triazine, naphthyl-bis (trichloromethyl) -S-triazine .
  • Examples of the sulfone compounds include 13-ketosulfone compounds, j8-sulfonylsulfone compounds, and (X diazo compounds of these compounds. Examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.
  • sulfonic acid compounds examples include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like.
  • Preferable specific examples include benzoin tosylate, pyrogallol tristrifluormethane sulphonate, o ditrobenzino trifnore aromethanesulphonate, o ditrobenzinole p toluenesulfonate, and the like.
  • the sulfonimide compound examples include N (trifluoromethylsulfo-loxy) succinimide, N— (trifluoromethylsulfo-loxy) phthalimide, N— (trifluoromethylsulfo-loxy) diphenylmaleimide, N- (trifluoro) Fluoromethylsulfoloxy) bicyclo [2.2.1] hept-5ene-2,3 dicarboximide, N- (trifluoromethylsulfoloxy) naphthylimide, and the like.
  • diazomethane compounds include bis (trifluoromethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (phenolsulfol) diazomethane, and the like.
  • these photosensitive acid generators (B) can be used alone or in combination of two or more.
  • the blending amount of the photosensitive acid generator (B) is 100 parts by weight of the copolymer (A) from the viewpoint of securing the sensitivity, resolution, pattern shape, etc. of the resin composition of the present invention. In contrast, 0.1 to 20 parts by weight, preferably 0.5 to: L0 parts by weight. When the blending amount of the light-sensitive acid generator (B) is less than 0.1 part by weight, curing may be insufficient and heat resistance is lowered. When it exceeds 20 parts by weight, transparency to radiation is lowered. The pattern shape may be deteriorated.
  • the crosslinking agent (C) used in the present invention is a compound having a group capable of reacting with the copolymer (A). It is.
  • the crosslinking agent (c) used in the present invention is at least one selected from an epoxy compound, an isocyanate compound, a blocked product thereof, and a nitrogen-containing compound in which all or part of the active methylol group is alkyl etherified. is there.
  • epoxidized polybutadiene bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, glycidyl ester type Epoxy compounds such as epoxy resin, phenol novolac, and epoxy resin;
  • Isocyanate compounds such as tolylene diisocyanate and blocked products thereof; (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea urea and other active methylol groups Examples thereof include nitrogen-containing compounds in which all or part of them are alkyl etherified.
  • the amount of the crosslinking material (C) is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, per 100 parts by weight of the copolymer (A). If the amount of the crosslinking agent (C) is less than 1 part by weight, curing may be insufficient, and if it exceeds 50 parts by weight, the resolution may be deteriorated.
  • the adhesion assistant (D) used in the present invention is an adhesion to an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. It is a compound that improves Specific examples include silane coupling agents and thiol compounds.
  • silane coupling agent examples include ⁇ - (2-aminoethyl) aminopropyltrimethylpyrutrimethoxysilane, urea propyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and the like.
  • thiol-based compound a monothiol such as t-dodecyl mercaptan and a polyvalent thiol such as trithiocyanouric acid are used. In the present invention, it is preferable to use a silane coupling agent.
  • the amount of the adhesion assistant (D) is 0.5 to LO parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A). If the blending amount of the adhesion assistant (D) is less than 0.5 parts by weight, the adhesion may be insufficient, and if it exceeds 10 parts by weight, the thermal shock resistance of the cured film will decrease. There is a fear.
  • a solvent may be added to improve the handleability of the photosensitive insulating resin composition and to adjust the viscosity and storage stability.
  • the type of such a solvent is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethenoylethenore acetate and ethylene glycol monoethyl ether acetate;
  • Propylene glycol monoalkyl ethers such as propylene glycol monomethino ethenore, propylene glycol monomethino enoate, propylene glycol monopropyl ether, propylene glycol monomono butenoate;
  • Propylene glycol dialkyl ethers such as propylene glycol dimethylol ether, propylene glycol jetino ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
  • Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethanolate acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
  • Cellosonolevs such as echinorescerosolev, butinorescerosolev;
  • Carbitols such as butyl carbitol
  • Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
  • Aliphatic carboxylic acid esters such as ethyl acetate, n -propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate ;
  • esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
  • Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, methylamylketone;
  • Amides such as N-dimethylformamide, N-methylacetamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone;
  • Ratatons such as ⁇ -petit lolacun are listed.
  • solvents may be used alone or in combination of two or more.
  • the amount of the solvent used can be appropriately determined according to the application, coating method, and the like.
  • additives can be blended in the photosensitive insulating resin composition according to the present invention as necessary.
  • polyimide acrylic polymer, polyolefin elastomer, styrene butadiene elastomer, silicon elastomer, compound having phenolic hydroxyl group and resin, resin having oxetal group;
  • High density polyethylene Medium density polyethylene, Polypropylene, Polycarbonate, Polyarylate, Aliphatic polyamide, Polyamideimide, Polysulfone, Polyethersulfone, Polyetherketone, Polyphenylenesulfide, (Modified) Polycarbodiimide, Polyetherimide, Polyesterimide, Modified polyphenylene -Thermoplastic or thermosetting resin such as lenoxide.
  • organic fillers such as sensitizers, leveling agents, silicone rubber particles or crosslinked rubber particles, silica or inorganic fillers such as alumina may be contained. .
  • Such additives can be used alone or in combination of two or more.
  • the photosensitive insulating resin composition of the present invention includes, for example, each component of the copolymer ( ⁇ ), a photosensitive acid generator ( ⁇ ), a crosslinking agent (C), and an adhesion assistant (D), and the necessary components. Depending on the condition, it is produced by mixing with other ingredients.
  • a method for producing the photosensitive insulating resin composition according to the present invention conventionally known methods can be used as appropriate, and each component may be added at once or in an arbitrary order and stirred, mixed and dispersed. Oh ,.
  • the photosensitive insulating resin composition according to the present invention is excellent in resolution, and the cured product is excellent in electrical insulation, thermal shock, adhesion, solvent resistance and the like. Accordingly, the photosensitive insulating resin composition of the present invention can be suitably used particularly as a material for an interlayer insulating film or a surface protective film of a semiconductor element.
  • the photosensitive insulating resin composition is applied to a substrate such as a silicon wafer to which a wiring pattern is applied. It is applied and dried to evaporate the solvent and form a coating film. Thereafter, the film is exposed through a desired mask pattern, and then developed with an alkaline developer to dissolve and remove the non-exposed portion to obtain a coating film on which the desired pattern is formed. Furthermore, a cured film is obtained by performing heat treatment after development in order to develop the insulating film characteristics.
  • the coating thickness can be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the photosensitive insulating resin composition.
  • radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, i-line steppers, and other ultraviolet rays, electron beams, and laser beams.
  • the film thickness is 5 to 50; ⁇ ⁇ is about 1,000 to 20 , OOOjZm 2 .
  • development is performed with an alkaline developer to dissolve and remove unnecessary non-exposed portions, thereby forming a desired pattern.
  • Examples of the development method in this case include a shower development method, a spray development method, an immersion development method, and a paddle development method, and the development conditions are usually about 1 to 10 minutes at 20 to 40 ° C. .
  • an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. may be adjusted to a concentration of about 10 to 10% by weight.
  • An alkaline aqueous solution dissolved in water can be mentioned.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
  • the film is cured by heat treatment.
  • the photosensitive acid generator (B) is decomposed to generate an acid. This acid catalysis promotes the curing reaction between the crosslinking agent (C) and the copolymer (A).
  • the photosensitive insulating resin composition according to the present invention can be heat-treated at a lower temperature than conventional photosensitive insulating resin compositions.
  • the above curing conditions are not particularly limited, but the coating film is cured by heating at a temperature of 50 to 300 ° C for about 30 minutes to 10 hours depending on the use of the cured product. Also, it can be heated in two stages in order to sufficiently advance the curing and prevent deformation of the obtained pattern shape. For example, in the first stage, the temperature is 50 to 150 ° C. for 10 minutes to 2 It can be heated for about an hour, and further cured by heating at a temperature of 100 to 300 ° C for about 20 minutes to 8 hours. Under such curing conditions, a general oven or an infrared furnace can be used as a heating facility.
  • a 6-inch silicon wafer was spin-coated with a photosensitive insulating resin composition and heated on a hot plate at 110 ° C for 3 minutes to produce a uniform coating film having a thickness of 10 / zm. Then, using the Araina one (Karl Suss Co. MA- 100), the exposure amount at wavelength 350nm ultraviolet rays from a high-pressure mercury lamp through a patterned mask 3,000 ⁇ 5 was exposed so that OOOjZm 2. Next, the plate was heated (110 ° C) for 3 minutes at 110 ° C on a hot plate, and developed by immersing in a 38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C for 60 seconds. The minimum dimension of the obtained pattern was taken as the resolution.
  • TMAH wt% tetramethylammonium hydroxide
  • a 6-inch silicon wafer is spin-coated with a photosensitive insulating resin composition and hot-played. Heated at 110 ° C for 3 minutes to produce a 10 m thick uniform coating. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm 2. Next, after heating (PEB) at 110 ° C for 3 minutes on a hot plate, the ultraviolet ray from the high-pressure mercury lamp was exposed again so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 j / m 2 . Thereafter, the film was heated in a convection oven at 120 ° C for 2 hours to obtain a cured film.
  • PEB heating
  • the obtained substrate was subjected to a resistance test by treating with a pressure tacker tester (manufactured by Tabai Espec Co., Ltd.) for 168 hours under conditions of a temperature of 121 ° C. and a humidity of 100%.
  • the adhesion after the test was judged by performing a cross-cut test (cross cut tape method) in accordance with JIS K5400.
  • the photosensitive insulating resin composition was applied to a SUS substrate and heated on a hot plate at 110 ° C for 3 minutes to produce a uniform resin film having a thickness of 10 m.
  • UV light from a high-pressure mercury lamp was exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 jZm 2 .
  • the exposure amount in the wavelength 350nm ultraviolet high-pressure mercury lamp power even again 3, 000-5 was exposed so that OOOjZm 2.
  • the obtained cured film was treated with a pressure tacker test device (manufactured by Tabai Espec) for 168 hours under the conditions of a temperature of 121 ° C, a humidity of 100% and a pressure of 2.1 atm.
  • the volume resistivity between the layers before and after the test was measured to confirm the resistance.
  • the photosensitive insulating resin composition was applied to the substrate shown in FIGS. 1 and 2, and heated on a hot plate at 110 ° C. for 3 minutes to produce a 10 m thick resin coating on the conductor. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm 2. Next, after heating (PEB) at 110 ° C for 3 minutes on a hot plate, the ultraviolet rays from the high-pressure mercury lamp were again exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5, OOOOjZm 2 . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film.
  • PEB heating
  • a 6-inch silicon wafer was spin-coated with a photosensitive insulating resin composition and heated at 110 ° C for 3 minutes on a hot plate to produce a 10 m thick uniform coating film. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm 2. Next, after heating (PEB) at 110 ° C for 3 minutes on a hot plate, the ultraviolet ray from the high-pressure mercury lamp was exposed again so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 j / m 2 . Thereafter, the film was heated in a convection oven at 120 ° C for 2 hours to obtain a cured film. The obtained substrate was immersed in isopropyl alcohol at 60 ° C for 10 minutes, and the surface of the cured film was observed with an optical microscope. The result was determined as follows.
  • a photosensitive insulating resin composition having the composition shown in Table 1 was prepared in the same manner as in Example 1, and these characteristics were measured in the same manner as in Example 1. The results obtained are shown in Table 1. [Comparative Examples 1-2]
  • Methylamyl ketone 100 100 Resolution m) 10 20 Adhesion 100/100 0/100 Volume resistivity ( ⁇ ⁇ cm)

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)

Abstract

On décrit une composition de résine isolante photosensible qui peut être durcie à basse température et permet d’obtenir un produit durci présentant d’excellentes caractéristiques diverses telles que la résolution, l’isolation électrique, la résistance à l’impact et la résistance aux produits chimiques. Une telle composition de résine isolante photosensible est adaptée pour l’utilisation en tant que films protecteurs de surface et films isolants d’intercouches. On décrit également un produit durci d’une telle composition de résine isolante photosensible et son utilisation. La composition de résine isolante photosensible contient un copolymère (A) obtenu en copolymérisant un (méth)acrylate comportant un groupe oxétanyle et un dérivé spécifique hydroxy- ou alkoxy-styrène, de préférence un copolymère (A) obtenu en copolymérisant un (méth)acrylate comportant un groupe oxétanyle, un dérivé spécifique hydroxy- ou alkoxy-styrène et un autre monomère vinylique supplémentaire, un générateur d’acide photosensible (B), un agent de réticulation (C) et un auxiliaire d’adhérence (D).
PCT/JP2005/012806 2004-07-14 2005-07-12 Composition de résine isolante photosensible, son produit durci et son utilisation WO2006006581A1 (fr)

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WO2008117619A1 (fr) * 2007-03-26 2008-10-02 Jsr Corporation Composition de résine isolante photosensible
JP2008286877A (ja) * 2007-05-15 2008-11-27 Sumitomo Bakelite Co Ltd 感光性樹脂組成物
CN101974201A (zh) * 2010-09-30 2011-02-16 昆山西迪光电材料有限公司 紫外厚膜光刻胶及其成膜树脂
JP2011059531A (ja) * 2009-09-11 2011-03-24 Jsr Corp 感放射線性樹脂組成物及びパターン形成方法
US20130129988A1 (en) * 2011-11-17 2013-05-23 Shin-Etsu Chemical Co., Ltd. Chemically amplified positive resist composition and pattern forming process
JP2013190507A (ja) * 2012-03-13 2013-09-26 Fujifilm Corp ポジ型感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
WO2014061062A1 (fr) * 2012-10-18 2014-04-24 サンアプロ株式会社 Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible
JP2014122972A (ja) * 2012-12-20 2014-07-03 Fujifilm Corp 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置
KR20140103839A (ko) * 2013-02-19 2014-08-27 제이에스알 가부시끼가이샤 네거티브형 감방사선성 수지 조성물, 경화막, 경화막의 형성 방법 및 표시 소자
JP2014186309A (ja) * 2013-02-19 2014-10-02 Jsr Corp ネガ型感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子
KR20150016087A (ko) * 2013-08-02 2015-02-11 제이에스알 가부시끼가이샤 감방사선성 수지 조성물, 경화막, 그의 형성 방법 및 표시 소자
JP5773160B2 (ja) * 2009-06-30 2015-09-02 Jsr株式会社 水分または酸素捕捉用組成物、硬化体、および電子デバイス

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KR101376319B1 (ko) * 2007-07-27 2014-03-20 주식회사 동진쎄미켐 디스플레이 소자의 실링방법

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JP2002229204A (ja) * 2001-02-02 2002-08-14 Toppan Printing Co Ltd 感光性樹脂組成物
JP2004126159A (ja) * 2002-10-01 2004-04-22 Ngk Spark Plug Co Ltd 感光性樹脂組成物及びそれを用いたプリント配線板

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JPH11106606A (ja) * 1997-09-30 1999-04-20 Jsr Corp 感放射線性樹脂組成物
JP2002229204A (ja) * 2001-02-02 2002-08-14 Toppan Printing Co Ltd 感光性樹脂組成物
JP2004126159A (ja) * 2002-10-01 2004-04-22 Ngk Spark Plug Co Ltd 感光性樹脂組成物及びそれを用いたプリント配線板

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008117619A1 (fr) * 2007-03-26 2008-10-02 Jsr Corporation Composition de résine isolante photosensible
JP2008286877A (ja) * 2007-05-15 2008-11-27 Sumitomo Bakelite Co Ltd 感光性樹脂組成物
JP5773160B2 (ja) * 2009-06-30 2015-09-02 Jsr株式会社 水分または酸素捕捉用組成物、硬化体、および電子デバイス
JP2011059531A (ja) * 2009-09-11 2011-03-24 Jsr Corp 感放射線性樹脂組成物及びパターン形成方法
CN101974201A (zh) * 2010-09-30 2011-02-16 昆山西迪光电材料有限公司 紫外厚膜光刻胶及其成膜树脂
CN101974201B (zh) * 2010-09-30 2012-10-31 昆山西迪光电材料有限公司 紫外厚膜光刻胶及其成膜树脂
US20130129988A1 (en) * 2011-11-17 2013-05-23 Shin-Etsu Chemical Co., Ltd. Chemically amplified positive resist composition and pattern forming process
JP2013190507A (ja) * 2012-03-13 2013-09-26 Fujifilm Corp ポジ型感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
WO2014061062A1 (fr) * 2012-10-18 2014-04-24 サンアプロ株式会社 Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible
JP2014122972A (ja) * 2012-12-20 2014-07-03 Fujifilm Corp 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置
KR20140103839A (ko) * 2013-02-19 2014-08-27 제이에스알 가부시끼가이샤 네거티브형 감방사선성 수지 조성물, 경화막, 경화막의 형성 방법 및 표시 소자
JP2014186309A (ja) * 2013-02-19 2014-10-02 Jsr Corp ネガ型感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子
KR102138141B1 (ko) * 2013-02-19 2020-07-27 제이에스알 가부시끼가이샤 네거티브형 감방사선성 수지 조성물, 경화막, 경화막의 형성 방법 및 표시 소자
KR20150016087A (ko) * 2013-08-02 2015-02-11 제이에스알 가부시끼가이샤 감방사선성 수지 조성물, 경화막, 그의 형성 방법 및 표시 소자
KR102164932B1 (ko) * 2013-08-02 2020-10-13 제이에스알 가부시끼가이샤 감방사선성 수지 조성물, 경화막, 그의 형성 방법 및 표시 소자

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TW200615693A (en) 2006-05-16

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