JP2010181866A - Positive photosensitive resin composition, cured film, interlayer dielectric, organic electroluminescence display device, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of molding a pattern having superior transparency, to provide a pattern cured film and an interlayer dielectric having superior solvent resistance, heat resistance and insulating properties, to provide an electroluminescence (EL) display device having high reliability by including the interlayer dielectric, and to provide a liquid crystal display device. <P>SOLUTION: In the positive photosensitive resin composition including (A) a copolymer including structural units of the following (A-1), (A-2) and (A-3), (B) a photosensitive agent and (C) a cross-linking agent, the copolymer independently respectively includes 10 to 50 mol% of (A-1) and (A-2). (A-1) is a structural unit including carboxyl group. (A-2) is a structural unit formed by adding a compound including an epoxy ring and an unsaturated group to a carboxyl group. (A-3) is a structural unit other than the (A-1) and (A-2). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition, a cured film using the positive photosensitive resin composition, an interlayer insulating film using the cured film, an organic EL display device using the same, and a liquid crystal display device Is.

For interlayer insulating films such as organic EL display devices and liquid crystal display devices, polyimide resins having excellent electrical characteristics and mechanical characteristics are used. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition, and is applied to a substrate, followed by patterning with actinic light, development, thermal imidization treatment, etc., thereby forming an interlayer insulating film of a semiconductor device. The surface protective film and the like, the flattening film of the display device, the interlayer insulating film, etc. can be easily formed, and the process can be greatly shortened compared with the conventional non-photosensitive polyimide precursor composition. Have.
However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Solvent measures have been demanded.

  In response to this, recently, various proposals of heat-resistant photosensitive resin materials using photosensitive polyimide precursors and photosensitive polybenzoxazole precursors that can be developed with an alkaline aqueous solution have been made in the same manner as photoresists. (For example, refer to Patent Document 1). However, the heat-resistant resin material in which naphthoquinone diazide is added to a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor has an insufficient effect of inhibiting the dissolution of naphthoquinone diazide in an alkaline aqueous solution, resulting in insufficient pattern formation. was there.

  Other positive photosensitive resins include those using a polyphenylene oxide resin obtained by oxidative coupling polymerization using a copper catalyst (see, for example, Patent Document 2). However, it has been found that the polyphenylene oxide resin lacks heat resistance and insulation. The reason for this is not clear, but the polyphenylene oxide resin is synthesized by oxidative coupling polymerization with a copper catalyst, so the catalyst may remain in the resin. This shortage is presumed to be caused by this residual catalyst.

  Further, as an interlayer insulating film such as a liquid crystal display device having high transparency, for example, unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, radical polymerizable compound having an epoxy group, and other radical polymerizable A radiation-sensitive resin composition containing a resin soluble in an alkaline aqueous solution, which is a compound copolymer, and a radiation-sensitive acid-generating compound is known (see, for example, Patent Documents 3 and 4). However, an interlayer insulating film produced using the above-described known techniques is not satisfactory in all of the performances of transparency, heat resistance, solvent resistance, and insulation.

JP 2004-133088 A JP 2000-275842 A Japanese Patent No. 2961722 JP-A-2005-70735

  This invention makes it a subject to provide the photosensitive resin composition which is excellent in transparency and can be patterned. Another object of the present invention is to provide a pattern cured film and an interlayer insulating film that are excellent in solvent resistance, heat resistance, and insulation by using the photosensitive resin composition. Furthermore, it is an object of the present invention to provide a highly reliable organic EL display device and liquid crystal display device by providing the interlayer insulating film.

The present inventor has found that the above problem is solved by the following configuration.
<1> (A) a copolymer containing the following structural units (A-1), (A-2), and (A-3), (B) a photosensitive agent, and (C) a crosslinking agent, A positive photosensitive resin composition, wherein the copolymer is a copolymer containing 10 to 50 mol% of (A-1) and (A-2) independently.
(A-1) Structural unit containing a carboxy group
(A-2) Structural unit in which a compound containing an epoxy ring and an unsaturated group is added to a carboxy group
(A-3) Structural units other than (A-1) and (A-2)

<2> The positive photosensitive resin composition according to <1>, wherein the structural unit other than (A-3) (A-1) and (A-2) is a structural unit having a ring structure.
<3> The positive photosensitive resin as described in <1> or <2>, wherein the structural unit other than (A-3) (A-1) and (A-2) is a structural unit having an alicyclic structure. Resin composition.

<4> A copolymer containing the structural units (A), (A-1), (A-2), and (A-3) is represented by (A-3), (A-1), and (A- The positive photosensitive resin composition according to any one of <1> to <3>, which is a copolymer containing a structural unit other than 2) in a range of 10 to 60 mol%.
<5> Copolymer weight containing each structural unit of (A) (A-1), (A-2), and (A-3) in terms of mass with respect to the total solid content of the positive photosensitive resin composition <1>-containing a coalescence in a range of 40% to 70%, containing the (B) photosensitizer in a range of 5% to 40%, and containing the (C) a cross-linking agent in a range of 3% to 40%. The positive photosensitive resin composition as described in any one of <4>.

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the photosensitive agent (B) is a compound having a 1,2-naphthoquinonediazide group.
<7> (C) The crosslinking agent is at least one selected from the group consisting of an epoxy compound, an oxetane compound, a compound containing a methacryloyl group or an acryloyl group, a melamine compound, a glycoluril compound, and a phenol compound. The positive photosensitive resin composition according to any one of <1> to <6>.

<8> The positive photosensitive resin composition according to any one of <1> to <7>, further comprising (D) a thermal radical generator.
<9> The positive photosensitive resin composition according to <8>, wherein the (D) thermal radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower.

<10> A cured film obtained by coating the positive photosensitive resin composition according to any one of <1> to <9> on a substrate and curing the coating by light or heat.
<11> An interlayer insulating film using the cured film according to <10>.
<12> An organic EL display device comprising the interlayer insulating film according to <11>.
<13> A liquid crystal display device comprising the interlayer insulating film according to <11>.

  According to the present invention, it is possible to provide a pattern-forming photosensitive resin composition having excellent transparency, and by using the photosensitive resin composition, the solvent resistance, heat resistance, and insulation are excellent. In addition, a patterned cured film and an interlayer insulating film can be provided. Furthermore, by providing the interlayer insulating film, a highly reliable organic EL display device and liquid crystal display device can be provided.

It is a schematic sectional drawing of the organic electroluminescence display using TFT. It is a schematic sectional drawing of the liquid crystal display device using TFT.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises (A) a copolymer containing the following structural units (A-1), (A-2), and (A-3), (B) a photosensitive agent, and ( C) A positive photosensitive resin composition comprising a crosslinking agent, wherein the copolymer is a copolymer containing (A-1) and (A-2) independently from 10 to 50 mol%. It is a thing.
(A-1) Structural unit containing a carboxy group
(A-2) Structural unit in which a compound containing an epoxy ring and an unsaturated group is added to a carboxy group
(A-3) Structural units other than (A-1) and (A-2) The constituent components of the photosensitive resin composition will be described below.

<Copolymer containing structural units (A), (A-1), (A-2), and (A-3)>
The (A) copolymer of the present invention comprises the structural units (A-1), (A-2), and (A-3), and (A-1) and (A-2) It is a copolymer (hereinafter also referred to as “specific copolymer”) containing 10 to 50 mol% each independently. Each structural unit will be described below.

<(A-1) Structural unit containing a carboxy group>
(A-1) The structural unit containing a carboxy group includes, for example, an unsaturated polycarboxylic acid having at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid. Examples thereof include structural units containing unsaturated carboxylic acid such as carboxylic acid.

  Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be its acid anhydride. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxyethyl). , Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like.

  The unsaturated polyvalent carboxylic acid may be a polymer of mono (meth) acrylate having carboxy groups at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. It is done.

  The structural unit containing a carboxy group may be a single structural unit or may be composed of two or more structural units.

  As a method for introducing the structural unit containing a carboxy group into the specific copolymer, the following carboxy group-containing monomer is preferably copolymerized. As carboxy group-containing monomers, acrylic acid, methacrylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, monoalkyl fumarate Those such as esters, 4-carboxystyrene and the like are preferred.

<(A-2) Structural unit in which compound containing epoxy ring and unsaturated group is added to carboxy group>
(A-2) As a structural unit in which a compound containing an epoxy ring and an unsaturated group is added to a carboxy group, a compound containing an epoxy ring and an unsaturated group is added to the carboxy group of the structural unit containing the carboxy group. A structural unit obtained by reacting an epoxy ring is preferred.

The compound containing an epoxy ring and an unsaturated group may be a compound having at least one epoxy ring and an unsaturated bond group between carbons, such as glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl). Mention may be made of compounds such as methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate and allyl glycidyl ether.
Among these, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate are preferable, and glycidyl methacrylate, 3,4-epoxycyclohexyl) methyl acrylate is solvent resistant. Most preferable from the viewpoint.

<(A-3) Structural units other than (A-1) and (A-2)>
The specific copolymer further includes structural units other than (A-1) and (A-2) as (A-3). The structural unit of (A-3) is not particularly limited as long as it is a structural unit other than the above-described (A-1) and (A-2). The structural unit is preferably derived from a vinyl monomer.

Examples of vinyl monomers that can be the structural unit of (A-3) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (Meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Specific examples of such vinyl monomers include the following compounds.
In this specification, when both “acrylic and methacrylic” are indicated, it may be described as “(meth) acrylic”.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

As the structural unit of (A-3), those containing a ring structure such as an aromatic ring or an alicyclic ring are preferable, and as the structural unit containing a ring structure, cyclohexyl (meth) acrylate, (meth) acrylic acid t -Butylcyclohexyl, phenyl (meth) acrylate, 3-methoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy (meth) acrylate Polyethylene glycol, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyl (meth) acrylate Oxyethyl, isobornyl (meth) acrylate, styrene, methyl Styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, groups that can be deprotected by acidic substances Examples include hydroxystyrene protected with (for example, t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene, of which cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethacrylate (meth) acrylate Preferred are cyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and styrene, cyclohexyl (meth) acrylate, dicyclo (meth) acrylate Nteniru, (meth) dicyclopentenyloxyethyl acrylate, (meth) dicyclopentanyl acrylate more preferred. When the ring structure is included, the developability is good.
Most preferably, the ring structure is a structural unit having an alicyclic structure, and examples of the alicyclic structure include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid isobornyl, etc., specifically, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclo Pentenyl, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are preferred. By including the alicyclic structure, the insulation resistance is improved.

The content of (A-1), (A-2) and (A-3) contained in the specific polymer is such that (A-1) and (A-2) are each independently 10 to 50 mol% Range. Preferably, (A-1) and (A-2) are each independently in the range of 12 to 45 mol%, and most preferably (A-1) and (A-2) are each independently 15 to It is in the range of 40 mol%. Within this range, developability is good in (A-1), and both developability and solvent resistance can be achieved in (A-2).
Further, the structural unit (A-3) contained in the specific copolymer is preferably in the range of 10 to 60 mol%, more preferably in the range of 15 to 55 mol%, most preferably 20 to 50 mol%. Range. Within this range, both developability and insulation resistance can be achieved.

  The specific copolymer used in the present invention is not particularly limited in molecular weight, but in terms of alkali dissolution rate, film physical properties and the like, the weight average molecular weight is preferably 1,000 to 500,000, and preferably 3,000 to 300,000. 000 is more preferable, and 5,000 to 200,000 is particularly preferable. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

The specific copolymer can be synthesized by copolymerizing monomers having the structural units (A-1), (A-2), and (A-3) when polymerized. Further, a monomer having a structural unit of (A-1) and (A-3) is copolymerized when polymerized, and an epoxy ring and an unsaturated group are added to the carboxy group of the obtained copolymer. It can also be synthesized by adding a compound containing it.
Examples of polymer compounds that can be suitably used in the present invention will be given below, but the present invention is not limited thereto.

When obtaining the copolymer and performing the addition reaction, it is preferably performed in a solvent. Any monomer may be used as long as the raw material monomer for copolymerization can be dissolved at a necessary concentration and does not adversely affect the properties of the film formed from the resulting copolymer. For example, water, methanol, ethanol, propanol, etc. ketones, cyclohexanone, ketone solvents such as acetophenone, ethyl acetate, acetic acid alcohol solvents, acetone, alcohol acetone, methyl ethyl ketone, methyl isobutyl, propylene glycol monomethyl ether acetate, γ-butyrolactone , Ester solvents such as methyl benzoate, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4- Diisopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-o Aromatic hydrocarbon solvents such as toxylene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone, dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2- Halogen solvents such as dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, and aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane can be used.

  Among these, more preferred solvents are tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1 Amide solvents such as 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferred Is an amide solvent such as N-methylpyrrolidinone and dimethylacetamide. These may be used alone or in admixture of two or more.

  The boiling point of the organic solvent used for the copolymerization reaction and the addition reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.

  The concentration of the solute in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

Optimum conditions for the polymerization reaction in the present invention vary depending on the type and concentration of the solvent, but the reaction temperature is preferably 0 ° C to 230 ° C, more preferably 100 ° C to 230 ° C, and particularly preferably 140 ° C to At 200 ° C., the reaction time is preferably 1 to 50 hours, more preferably 2 to 40 hours, particularly preferably 3 to 30 hours.
Moreover, it is preferable to make it react in inert gas atmosphere (for example, nitrogen, argon, etc.) in order to suppress the oxidative decomposition of a high molecular compound. It is also preferred to polymerize under light-shielding conditions to suppress unwanted photoreactions.

<(B) Photosensitive agent>
The photosensitive agent (B) used in the photosensitive resin composition of the present invention refers to a compound that imparts the function of forming an image by exposure to the photosensitive resin composition and / or gives the trigger. Specific examples include (B-1) a compound that generates an acid upon exposure (photoacid generator), (B-2) a photosensitive quinonediazide compound, and (B-3) a dihydropyridine compound. Two or more of these photosensitizers can be used in combination. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.

(B-1) Photoacid generator The photoacid generator is used for photocation polymerization photoinitiators, photoradical polymerization photoinitiators, dye photodecolorants, photochromic agents, or microresists. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Preferred photosensitizers include imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid.

  Further, a group capable of generating an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin, for example, US Pat. No. 3,849,137, German Patent No. 3914407. Description and JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 And compounds described in JP-A 63-146029, etc. can be used.

  Further, compounds capable of generating an acid by light described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In general formulas (ZI) to (ZIII), R ^{201 to} R ²⁰⁷ each independently represents an organic group. The number of carbons in the organic group R ²⁰¹ to R ²⁰⁷ are ranges of 1 to 30, preferably from 1 to 20. Two members out of R ^{201 to} R ²⁰⁷ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ^{201 to} R ²⁰³ include an alkylene group (eg, butylene group, pentylene group).
X ⁻ represents a non-nucleophilic anion, and preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ⁴⁻ , PF ⁶⁻ , SbF ^{6− and the} like. An organic anion having a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following general formula.

In the above general formula, Rc ₁ represents an organic group.
Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, preferably an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an aryl group which may be substituted, or these And a group in which a plurality of groups are linked by a linking group such as a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Examples of the organic group of Rc ₃ , Rc _4, and Rc ₅ include the same organic groups as those of Rc ₁ , preferably a C 1-4 perfluoroalkyl group.
Rc ₃ and Rc ₄ may be bonded to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, Rc ₃ and Rc ₄ are preferably bonded to form a ring, so that the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

  Among these, at least one of the aryl groups of the triarylsulfonium salt preferably has an electron withdrawing group as a substituent, and the sum of Hammett values of the substituents bonded to the aryl skeleton is greater than 0.18. It is preferable.

Here, the electron withdrawing group means a substituent having a Hammett value (Hammet substituent constant σ) larger than 0. In the present invention, from the viewpoint of increasing sensitivity, the sum of Hammett values of substituents bonded to the aryl skeleton in the photoacid generator is preferably 0.18 or more, more preferably greater than 0.46. More preferably, it is larger than 0.60.
The Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. Is preferably more than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.

The Hammett value in the present invention uses the numerical values described in Naoki Inamoto, Chemistry Seminar 10 Hammett's Rule-Structure and Reactivity- (published by Maruzen Co., Ltd. in 1983).
Examples of the electron withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxy group, and a carbonyl group. The Hammett values of these substituents are shown below. A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH ₃ , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the like. The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value. For example, (m: 0.50) means that the Hammett value when the substituent is introduced at the meta position is 0.50. Indicates that

Among these substituents, nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity. Among them, —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity. from the viewpoint, -F, -CF 3, -Cl, -Br are preferable.

  These substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46. The number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.

As described above, since the Hammett value of the substituent varies depending on the position of introduction, the sum of Hammett values in the photoacid generator according to the present invention is determined by the type of substituent, the introduction position, and the number of introductions. Become.
The Hammett value is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing property. Preferred substitution positions are preferably m-position and p-position, and most preferably p-position, from the viewpoint of synthesis.
Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. A halogen atom, most preferably a triarylsulfonium salt structure in which —Cl is introduced, is preferable, and a structure in which —Cl is substituted at the p-position is more preferable.

  Examples of the sulfonic acid anion included in the triarylsulfonium salt contained in the photosensitive resin composition of the present invention include an arylsulfonic acid anion and an alkanesulfonic acid anion, which are substituted with a fluorine atom or an organic group having a fluorine atom. The anions that are present are preferred.

  Compounds having a triarylsulfonium salt structure are disclosed in, for example, J. Org. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1 pamphlet, or European Patent (EP) No. 1113005.

  Although a specific example is given below, it is not limited to these.

Among compounds that generate an acid upon irradiation with actinic rays or radiation, preferred compounds (photoacid generators) include a sulfonic acid or an alkyl or arylcarboxylic acid substituted with an electron-withdrawing group, which has a strong pKa of 2 or less as a generated acid. An acid, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
Examples of the photoacid generator include N-hydroxyimide sulfonate compounds and oxime sulfonates.
Preferred imide sulfonate compounds as photoacid generators include compounds of the following general formula.

In the formula, C ₁ (carbon atom) and C ₂ (carbon atom) are bonded by a single bond or a double bond, and R ⁵¹ or R ⁵² may be the same or different, and the following (1) to (4) (1) each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C ₁ and C ₂ Form. (3) Represents a residue containing (4) N-sulfonyloxyimide, which forms a condensed aromatic ring containing C ₁ and C ₂ .
R ⁵³ represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.

In the general formula (PA-5), when R ⁵¹ and R ⁵² correspond to the case of (1), the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include alkyl groups having 1 to 4 carbon atoms such as tert-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the aryl group include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group. When R ⁵¹ and R ⁵² correspond to the case of (2), for example, the following partial structure can be given.

When R ⁵¹ and R ⁵² correspond to the case of (3), for example, the following partial structure can be given.

When R ⁵¹ and R ⁵² correspond to the case of (4), so-called at least two N-sulfonyloxyimide residues are a single bond at the portion of R ⁵¹ and R ⁵² having the partial structures of (1) to (3) above. Or the thing couple | bonded with the following bivalent organic groups can be mention | raise | lifted. However, the following linking groups are used alone or in combination of two or more.
[Divalent organic _{group]: -O -, - S -,} - SO -, - SO 2 -, - NH -, - CO -, - CO 2 -, - NHSO 2 -, - NHCO -, - NHCO 2 −

^Examples of the alkyl group for R ⁵³ include a linear or branched alkyl group having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable. Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom. However, the halogen atom to be substituted may be plural types per molecule. Examples of the cyclic alkyl group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group, and polycyclic substituents such as norbornyl group, adamantyl group, and tricyclodecanyl group. I can give you. Examples of the alkenyl group include linear or branched alkenyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkenyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.

^Examples of the aryl group of R ⁵³ include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl group such as xylyl group, mesityl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group and other lower alkoxy groups, vinyl group, allyl group, propenyl group, butenyl group, etc. And an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Preferably, a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Two or more kinds of substituents on the aryl group and the aralkyl group may be used. Specific examples of these compounds are shown below, but are not limited thereto.

  Preferred examples of the oxime sulfonate compound as the photoacid generator include compounds of the following general formula (PA-6).

In General Formula (PA-6), R ⁶¹ and R ⁶² each independently have an alkyl group, an alkenyl group, an alkynyl group, or a substituent that may have a substituent having 1 to 16 carbon atoms. A cycloalkyl group, a cycloalkenyl group, an optionally substituted aryl group, a heteroaryl group, or a cyano group. R ⁶¹ and R ⁶² are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R ⁶¹ or R ^{62 of the} compound represented by another general formula (PA-6) via a linking chain containing —O—, —S—, —N—, and —CO—. .
R ⁶³ represents an alkyl group which may have a substituent having 1 to 16 carbon atoms, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

Examples of the alkyl group having 1 to 16 carbon atoms in R ^{61 to} R ⁶³ include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, t-amyl group, n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group and other alkyl groups, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.

Examples of the alkenyl group for R ⁶¹ and R ⁶² include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, A 2-oxo-3-pentenyl group, a decapentaenyl group, a 7-octenyl group and the like can be mentioned.

Examples of the alkynyl group in R ⁶¹ and R ⁶² include an ethynyl group, a propargyl group, a 2-butynyl group, a 4-hexynyl group, a 2-octynyl group, a phenylethynyl group, and a cyclohexylethynyl group.

Examples of the cycloalkyl group in R ^{61 to} R ⁶³ include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

Examples of the cycloalkenyl group for R ⁶¹ and R ⁶² include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group, and the like.

Examples of the aryl group in R ^{61 to} R ⁶³ include those having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group, which may have a substituent.

The above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following formula (1A).
Here, the alkyl group and the cycloalkyl group have the same meanings as described above. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.

In the formula ^{(1A), R 61} and ^{R 62} have the same meanings as ^{R 61} and ^{R 62} in formula (PA-6).

  Specific examples of the compound represented by the general formula (PA-6) are shown below, but the present invention is not limited thereto.

  Specific examples of more preferable oxime sulfonate compounds include the following (z66) to (z70).

  As a general formula of nitrobenzyl sulfonate preferable as a photoacid generator, a compound represented by the general formula (TA-9) can be given.

Z in this formula is an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkylaryl group, a halogen-substituted alkyl group having 1 to 30 carbon atoms, a halogen-substituted aryl group, a halogen-substituted alkylaryl group, Nitro-substituted aryl group having 6 to 30 carbon atoms, nitro-substituted alkylaryl group, aryl group having 6 to 30 carbon atoms and halogen substituent, alkylaryl group having nitro substituent and halogen substituent and groups having the formula _{C 6 H 4 SO 3 CHR'C 6} H 4-m Q m (NO) 2 (R ' is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms, is selected from an acyl group), R ⁹ are selected from hydrogen atoms and methyl groups, and nitro substituted aryl group having 6 to 30 carbon atoms, each Q is a hydrocarbon group having 1 to 30 carbon atoms, hydrin Karubonokishi group, NO _2, independently selected from halogen atoms and organosilicon groups, the value of m is 0, 1 or 2, provided that Q is not an acidic group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.
Specific examples of the compound represented by the general formula (TA-9) include the following compounds.

(B-2) Quinonediazide photosensitizer
(B-2) 1,2-quinonediazide photosensitizer as a quinonediazide photosensitizer is obtained by, for example, condensing a 1,2-quinonediazidesulfonyl chloride with a hydroxy compound, an amino compound, etc. in the presence of a dehydrochlorinating agent. can get.

  Examples of the 1,2-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4- Although sulfonyl chloride etc. can be used, use of naphthoquinone-1,2-diazide-4-sulfonyl chloride is preferable in terms of sensitivity.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -A] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ] -Ethylidene] bisphenol and the like can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl. Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino 4,4′-dihydroxybiphenyl, 4,4′-diamino 3,3′-dihydroxybiphenyl, bis (3-amino 4-hydroxyphenyl) propane, bis (4-amino3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino3-hydroxyphenyl) sulfone, bis (3-amino-4- Hydroxyphenyl) hexafluoropropane Bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  1,2-quinonediazide sulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of 1,2-quinonediazide sulfonyl chloride. It is preferred that A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 1/1 to 1 / 0.9. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 24 hours.

  As the reaction solvent, solvents such as dioxane, 1,3-dioxolane, acetone, methyl ethyl ketone, tetrahydrofuran, chloroform, N-methylpyrrolidone, γ-butyrolactone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine and the like.

  Examples of quinonediazide photosensitizers include compounds having the following structures.

  In the formula, D is independently H or any of the following groups.

  However, at least 1 D should just be said quinonediazide group in each compound.

In the photosensitive resin composition of the present invention, the blending amount of (B) the photosensitive agent is the difference in dissolution rate between the exposed part and the unexposed part, and the allowable range of sensitivity, and (A) the total amount of the specific copolymer. When it is 100 mass parts, 1-25 mass parts is preferable, and 5-20 mass parts is more preferable.
As a photosensitizer, it can be used individually by 1 type or in combination of 2 or more types, and (B-1) photoacid generator and (B-2) quinonediazide photosensitizer may be used in combination.

  In the present invention, the (B) photosensitizer is preferably a (B-2) quinonediazide photosensitizer, and more preferably a compound having a 1,2-naphthoquinonediazide group. (B) When a compound having a 1,2-naphthoquinonediazide group is used as a photosensitizer, high sensitivity and good developability are obtained.

  Among the above-mentioned (B) photosensitizers, the following compounds are preferred, and D is independently a hydrogen atom or a 1,2-naphthoquinonediazide group from the viewpoint of high sensitivity.

(Sensitizer)
In the photosensitive resin composition of the present invention, it is preferable to add a sensitizer in order to promote the decomposition in the combination with the sulfonium salt. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with sulfonium, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums (eg, , Squarylium), coumarins (for example, 7-diethylamino 4-methylcoumarin). Among them, an anthracene derivative is particularly preferable as a sensitizer.

  Preferable specific examples include (C-1) to (C-26) shown below, but are not limited thereto.

  As the sensitizer as described above, a commercially available one may be used, or it may be synthesized by a known synthesis method.

  The addition amount of the sensitizer is preferably 20 to 200 parts by mass and more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the photosensitizer.

<(C) Crosslinking agent>
In the present invention, it is preferable to use a crosslinking agent (C) as a modifier.
Here, (C) the cross-linking agent is a compound that cross-links with a specific copolymer by acid or heat. For example, melamine substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Compound, guanamine compound, glycoluril compound, urea compound, phenol compound or phenol ether compound, epoxy compound, oxetane compound, thioepoxy compound, isocyanate compound, azide compound, or methacryloyl group Examples include acryloyl group-containing compounds, but in terms of film physical properties, heat resistance, and solvent resistance, epoxy compounds, oxetane compounds, methacryloyl or acryloyl group-containing compounds, melamine compounds, glycoluril compounds. Compounds, and Phenol-based compound is preferably used.

<Compound containing alkoxymethyl group or acyloxymethyl group>
It is known that a compound containing an alkoxymethyl group or an acyloxymethyl group prevents melting of the pattern and thermal shrinkage during curing without impairing the lithography performance. In addition, it is known that chemical resistance can be improved when applied to a low-temperature curing process.
The alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. In the case of an alkoxymethyl group, 2 carbon atoms are particularly preferred, and in the case of an acylmethyl group, 3 carbon atoms are particularly preferred.
1-10 are preferable, as for the total number of the alkoxymethyl group and acyloxymethyl group which the said compound has, More preferably, it is 2-8, Most preferably, it is 3-6.
The molecular weight of the compound is preferably 1500 or less, and more preferably 180 to 1200.

As a compound containing an alkoxymethyl group or an acylromethyl group, an alkoxymethyl group or an acyloxymethyl group is directly bonded to a (CL-1) phenol derivative, and (CL-2) bonded to a nitrogen atom. Examples thereof include a compound bonded to an aromatic carbon atom of a (CL-3) triazine derivative (melamine type).
Examples of the (CL-1) compound include compounds represented by the following general formula.

In the formula, R ⁸ represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an action of an acid. The group which decomposes | disassembles and produces an alkali-soluble group is shown.
R ⁷ represents each independently an alkyl group, a cycloalkyl group or an alkenyl group, E is representative of the m ² divalent linking group. Examples of the linking group include an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3-phenylene, 1,4- Phenylene, naphthylene, etc.), ether groups, carbonyl groups, ester groups, amide groups, and m ² valent groups obtained by removing m ² -2 of any hydrogen atom in a divalent group combining these groups. . When E is monovalent, a hydrogen atom, an alkyl group that is a monovalent group corresponding to the above divalent group, an aryl group, and the like can be given.
The p 1, 2, q is 0 to 2, as ^{m 2} 1 to 8, preferably 2 to 6.

The group capable of decomposing by an acid as R ⁶ to generate an alkali-soluble group is a group decomposing by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxy group. For example, it is eliminated by the action of an acid. group, or _{^{-C (R 4) 2 -COOR 5}} (R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 5} is. represents a group capable of leaving by the action of acid).
Decomposing by the action of an acid, as a base to produce an alkali-soluble group, when R ⁶ is a group capable of leaving by the action of an acid, by the action of an acid, by R ⁶ itself is disengaged, -OH occurs, also When R ⁶ is —C (R ⁴ ) ₂ —COOR ⁵ , R ⁵ is released by the action of an acid to produce —COOH.
Examples of the group capable of leaving by the action of an acid include an acetal group and a tertiary ester group.
Specific examples of the acetal group include alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like.

  Specific examples of the ester group include a t-butyl group, a t-amyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a 1-ethylcyclohexyl group.

Specific examples of the compound having an alkoxymethyl group of (CL-1) include the following structures.
In addition, the compound which has an acyl rosymethyl group can mention the compound which changed the alkoxymethyl group of the following compound into the acyloxymethyl group.
The compound having an alkoxymethyl group or acyloxymethyl in the molecule is not limited to the following compounds.

  Examples of the compound (CL-2) include compounds represented by the following general formula.

In the formula, R ¹⁰³ represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, R ¹⁰¹ and R ¹⁰² represent a monovalent organic group, and R ¹⁰¹ and R ¹⁰² are bonded to each other. You may form a 5-8 membered ring.

  Examples of the compound (CL-3) include melamine compounds. Specific examples of melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine , A compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

  As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound or a compound synthesized by a known method may be used.

<Compound containing methacryloyl group or acryloyl group>
The photosensitive resin composition of the present invention may use a compound containing a methacryloyl group or an acryloyl group for the purpose of improving film physical properties.
The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It has been found that the addition of this compound improves film properties. Therefore, a compound having 2 or more, more preferably 4 or more acryloyl groups and methacryloyl groups in one molecule is preferable.

  Preferred specific examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedio Such as rudi (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc. Polyfunctional alcohols obtained by addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated, in Japanese Patent Publication Nos. 48-41708, 50-6034, 51-37193, etc. Described urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; epoxy resins and (meth) Such as multifunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

<Epoxy compounds and oxetane compounds>
The photosensitive resin composition of the present invention may use an epoxy compound or an oxetane compound as the crosslinking agent (C).
The epoxy compound and the oxetane compound are compounds containing an epoxy group or an oxetanyl group, and are generally called epoxy resins or oxetane resins.
Examples of the epoxy resin include bisphenol A type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, and alicyclic epoxy compound.

  For example, as bisphenol A type epoxy resin, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. (Above manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. (above made by Nagase ChemteX Corporation), Plaxel GL-61, GL-62, G101, G102 (above Daicel Chemical Industries, Ltd. In addition to ()), these similar bisphenol F type epoxy resins and bisphenol S type epoxy resins can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel Cytec Co., Ltd.) can also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (manufactured by Nagase ChemteX Corporation),
Examples of the biphenyl type include 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl.

  Examples of the alicyclic epoxy compounds include Celoxide 2021, 2081, 2083, 2085, Eporide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), Santo Tote ST-3000, ST. -4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. In addition, Epototo YH-434 and YH-434L, which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

Among these epoxy resins, preferably novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. Examples of such a material include Epicron N-660, N-670, N-680, N-690, YDCN-704L (manufactured by DIC) and EHPE3150 (manufactured by Daicel Chemical).
As the crosslinking agent (C) of the present invention, two or more kinds of epoxy resins may be contained.

As the oxetane resin, Aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
The oxetane resin can be used alone or mixed with an epoxy resin. In particular, when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.

<Glycoluril compounds and urea compounds>
Examples of the glycoluril-based compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, tetramethylol glycol Examples thereof include compounds in which 1 to 4 methylol groups of uril are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea, and the like.

These crosslinking agents can be used in combination of two or more.
(C) As for the addition amount to the photosensitive resin composition of a crosslinking agent, 1-70 mass parts is preferable when the total amount of (A) specific copolymer is 100 mass parts, and 3-50 mass parts is more preferable.

(D) Thermal radical generator The photosensitive resin composition of the present invention may contain (D) a thermal radical generator. As the thermal radical generator in the present invention, those which are different from the photosensitive agent (B) and generally known as radical generators can be used. The thermal radical generator is a compound that generates radicals by heat energy and initiates and accelerates a polymerization reaction with a polymerizable compound such as a specific copolymer. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance are improved.

Hereinafter, although a thermal radical generator is explained in full detail, this invention is not restrict | limited by these description.
In the present invention, preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include an ester compound, a compound having a carbon halogen bond, and an azo compound.
In the present invention, from the viewpoint of heat resistance and solvent resistance of the obtained cured film, organic peroxides, azo compounds, and bibenzyl compounds are more preferable, and bibenzyl compounds are particularly preferable. Specific examples of the above-described thermal radical generator are given below, but the present invention is not limited to these.

  Specific examples of these organic peroxides include Parroyl L, Perocta O, Parroyl SA, Perhexa 25O, Perhexyl O, Nipper BMT, Nipper BW, Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Pertetra C, Perhexyl I. Perbutyl MA, perbutyl 355, perbutyl L, perbutyl I, perbutyl E, perhexyl Z, perhexa 25Z, perbutyl A, perhexa 22, perbutyl Z, perhexa V, perbutyl P, park mill D, perhexyl D, perhexyl 25B, perbutyl C (above , Manufactured by NOF Corporation).

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′. -Azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4 '-Azobis (4-cyanovaleric acid), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis (2-methylpropionamidooxime), 2,2'-azobis [2- (2-imidazoline-2 -Yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2 Methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (2,4,4-trimethylpentane) and the like can be mentioned.

  Further, a bibenzyl compound represented by the following formula (1) can be used as a radical generator.

R ³ in Formula (1) independently represents any of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, or a halogen atom. )
Specifically, the bibenzyl compound represented by the formula (1) is 2,3-dimethyl-2,3-diphenylbutane, α, α′-dimethoxy-α, α′-diphenylbibenzyl, α, α′-diphenyl-α. -Methoxybibenzyl, α, α'-dimethoxy-α, α'dimethylbibenzyl, α, α'-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane, 2, 2, 3 , 3-tetraphenylsuccinic acid nitrile, dibenzyl and the like.

A compound preferable as the above-mentioned (D) thermal radical generator is a compound having a 10-hour half-life temperature of 100 ° C. or higher and 230 ° C. or lower, more preferably 120 ° C. or higher and 220 ° C. or lower. When the 10-hour half-life temperature is in this temperature range, a cured film having excellent characteristics can be obtained.
The 10-hour half-life temperature of the thermal radical generator refers to a temperature at which half of the specific compound decomposes and generates a radical when left at a specific temperature for 10 hours.

As compounds having a 10-hour half-life temperature in the range of 100 ° C. to 230 ° C., among the above-mentioned compounds, perbutyl A, perhexa 22, perbutyl Z, perhexa V, perbutyl P, park mill D, perhexyl D, perhexa 25B, perbutyl C, 2,3-dimethyl-2,3-diphenylbutane (manufactured by NOF Corporation), and the like, are preferable as the thermal radical generator used in the present invention.
The reason is not clear, but a thermal radical generator that decomposes at a higher temperature to generate radicals is preferred, and the resulting cured film has good heat resistance and solvent resistance. Examples of such a thermal radical generator include 2,3-dimethyl-2,3-diphenylbutane (Nofmer BC-90, manufactured by NOF Corporation, 10 hour half-life temperature 210 ° C.).

The (D) thermal radical generator in the present invention may be used alone or in combination of two or more.
(D) The addition amount of the thermal radical generator to the photosensitive resin composition is preferably 0.1 to 200 parts by mass, more preferably 1 to 50, when (A) the specific copolymer is 100 parts by mass. It is most preferable from a viewpoint of a film physical property improvement that it is 5-30 mass parts.

<Adhesion promoter>
If necessary, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added to the photosensitive resin composition in the present invention.
Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. When using an adhesion promoter in the photosensitive resin composition, 0.1 to 20 parts by mass is preferable and 100 to 10 parts by mass is more preferable with respect to 100 parts by mass of the polymer compound (a).

<Solvent>
The solvent is not particularly limited as long as it can dissolve the photosensitive resin composition of the present invention, but in order to prevent the solvent from evaporating more than necessary at the time of coating, so that the solid content of the photosensitive resin composition does not precipitate at the time of coating, A solvent having a boiling point of 100 ° C. or higher is preferred.
Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol and cyclohexanone.
Further, a solvent having a high boiling point such as N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate and the like may be used supplementarily.
However, if the solvent remains in the film after curing, sufficient film physical properties cannot be obtained. Therefore, it is not preferable that the solvent having a boiling point not lower than the curing temperature (high boiling point solvent) is 30% by mass or more in the solvent. The addition amount of the high boiling point solvent is 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.

  The pattern obtained by the photosensitive resin composition of the present invention is excellent in transparency, solvent resistance, heat resistance, and insulation, and is particularly effective for electronic devices. The electronic device referred to in the present invention means an organic EL display device and an electronic device for a liquid crystal display device, and the photosensitive resin composition of the present invention is particularly effective for a planarizing film and an interlayer insulating film for a display device. Is demonstrated.

(Pattern formation method)
As a method of forming a pattern using the photosensitive resin composition of the present invention, (1) the photosensitive resin composition of the present invention is coated on a suitable substrate, and (2) the coated substrate is baked. (Pre-bake), (3) exposure with actinic rays or radiation, (4) post-heat if necessary, (5) development with aqueous developer, (6) full exposure if necessary, and (7) A cured pattern can be formed by heat curing (post-baking).

  The coated and exposed substrate can be baked at an elevated temperature as needed prior to development. Further, the developed substrate may be rinsed before curing. After development, prior to thermosetting (post-baking), post-exposure can be performed as necessary.

  As described above, the photosensitive resin composition of the present invention is applied on a semiconductor element or a glass substrate so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 to 30 μm), prebaking, exposure, A pattern for an organic EL display device or a liquid crystal display device can be formed by development and heat curing.

Hereinafter, a method for forming a pattern will be described in more detail.
The photosensitive resin composition of the present invention is coated on a suitable substrate. The substrate is a semiconductor or ceramic substrate such as a silicon wafer, glass, metal or plastic. In general, a silicon wafer is used for a semiconductor device, and a glass substrate is used for a display device. Coating methods include, but are not limited to, spray coating, spin coating, slit coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

  After coating, it is baked for several minutes to half an hour at an elevated temperature of about 70-130 ° C., depending on the method, to evaporate the remaining solvent. The resulting dried photosensitive resin composition layer is then exposed to actinic rays or radiation in a preferred pattern through a mask. As actinic rays or radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. The most preferred radiation is one having a wavelength of 436 nm (g-line), 405 nm (h-line) and 365 nm (i-line).

  It is advantageous to heat the substrate exposed to actinic rays or radiation to a temperature of about 70-130 ° C. The exposed substrate is heated in this temperature range for a short time, generally a few seconds to a few minutes. This stage of the method is commonly referred to in the art as post-exposure baking.

  The coating film is then developed with an aqueous developer and a pattern is formed. Aqueous developers include inorganic alkalis (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (eg, ethylamine, n-propylamine), secondary amines (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.

  In some cases, the pattern is then rinsed using deionized water.

The pattern is exposed as a whole after development if necessary. The exposure energy for the entire surface exposure is preferably 100 to 1000 mJ / cm ² . Full exposure is preferable from the viewpoint of improving transparency when used as a photosensitive resin composition for a display device.

  The pattern is then heat cured to obtain a final pattern. Thermosetting is performed to form a film having high heat resistance, chemical resistance, and film strength. Common photosensitive polyimide precursor compositions have been heat cured at a temperature of about 300-400 ° C. On the other hand, the photosensitive resin composition of the present invention provides a film having a film property equal to or higher than that of a conventional photosensitive polyimide precursor composition at less than 300 ° C., more specifically, 200 ° C. to 250 ° C.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(Synthesis example)
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate CHMA: cyclohexyl methacrylate St: styrene GMA: glycidyl methacrylate DCM: dicyclopentanyl methacrylate BzMA: benzyl methacrylate BTEAC: benzyltriethylammonium AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl ether acetate

<Synthesis of Binder A>
MAA (14.65 g), MMA (0.54 g), CHMA (17.55 g) are used as monomer components constituting the copolymer, and AIBN (0.5 g) is used as a radical polymerization initiator. Was subjected to a polymerization reaction in a solvent PGMEA (40.01 g) to obtain a binder A ′ solution which is a precursor of binder A. The polymerization temperature was adjusted to a temperature of 60 ° C to 100 ° C.
GMA (12.26 g), BTEAC (0.5 g), and PGMEA (14.99 g) were added to the above-mentioned binder A ′ solution and reacted to cause a PGMEA solution of binder A (Mw. 31300, solid content concentration: 45 mass%). )Obtained. The reaction temperature was adjusted to 90 ° C to 120 ° C.

<Synthesis of Binder B>
MAA (12.47 g), St (4.66 g), DCM (16.25 g) are used as monomer components constituting the copolymer, and AIBN (0.5 g) is used as a radical polymerization initiator. Was subjected to a polymerization reaction in a solvent PGMEA (40.81 g) to obtain a binder B ′ solution which is a precursor of the binder B. The polymerization temperature was adjusted to a temperature of 60 ° C to 100 ° C.
GMA (11.61 g), BTEAC (0.5 g), and PGMEA (14.19 g) were added to the above-mentioned binder B ′ solution and reacted to cause a PGMEA solution of binder B (Mw.30000, solid content concentration: 45 mass%). )Obtained. The reaction temperature was adjusted to 90 to 120 ° C.

<Synthesis of binder C>
MAA (7.79 g) and BzMA (37.21 g) are used as monomer components constituting the copolymer, AIBN (0.5 g) is used as a radical polymerization initiator, and these are used as a solvent PGMEA (55.00 g). ) To obtain a PGMEA solution of binder C (Mw. 30000, solid content concentration: 45% by mass). The polymerization temperature was adjusted to a temperature of 60 ° C to 100 ° C.

<Synthesis of binder D>
Binder D was synthesized by the method described in Synthesis Example 4 of JP-A-2005-70735.
A flask equipped with a condenser and a stirrer was charged with 8.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts of diethylene glycol ethyl methyl ether. Subsequently, 20 parts of methacrylic acid, 45 parts of glycidyl methacrylate, 15 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts of polyethylene glycol (n = 3) monomethacrylate and α-methylstyrene After 3 parts of dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing binder D having a structure having an epoxy ring.
The weight average molecular weight (Mw) in terms of polystyrene of the binder D was 8,000, and the molecular weight distribution (Mw / Mn) was 1.9. Moreover, the solid content concentration of the polymer solution obtained here was 31.5 mass%.

Binder D

Example 1
<Preparation of photosensitive resin composition>
The following composition was dissolved and mixed, and filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition of Example 1.
-Binder A solution (amount equivalent to 12.73 parts in solid content)
Photosensitizer (TAS-200 manufactured by Toyo Gosei Co., Ltd.) 4.78 parts Cross-linking agent (EHPE-3150 manufactured by Daicel Chemical Industries) 4.78 parts Adhesive (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.40 parts・ Thermal radical generator (NOFMER BC-90 manufactured by NOF Corporation) 0.32 parts ・ Solvent (PGMEA) 77 parts

(Examples 2 to 16 and Comparative Examples 1 to 4)
The types and amounts of the binder (copolymer, expressed in solid amount in Table 1), the photosensitizer, and the crosslinking agent in the composition of Example 1 were changed as shown in Table 1, and the others were carried out. In the same manner as in Example 1, photosensitive resin compositions of Examples 2 to 16 and Comparative Examples 1 to 4 were prepared.

  The structures of the photosensitive agent, the crosslinking agent, the adhesion agent, and the thermal radical generator used in Table 1 are shown below.

  Comparative photosensitizer: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate of sulfonic acid chloride (2.0 mol)

<Characteristic evaluation>
Using each photosensitive resin composition thus obtained, the solvent resistance, transparency, heat resistance, and relative dielectric constant were evaluated as follows. The results are shown in Table 2.

<Evaluation of solvent resistance>
Each photosensitive resin composition was applied on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes. A 3.0 μm coating film was formed. The obtained coating film was exposed to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. A cured film was obtained by heating at 220 ° C. for 1 hour in an oven. The film thickness (T ¹ ) of the obtained cured film was measured. Then, after immersing the silicon substrate in which the cured film is formed on the 70 ° C. in a temperature controlled dimethylsulfoxide 20 minutes, the film thickness was measured (t ¹⁾ of the cured film, the film thickness change ratio by immersion {| T ¹ −T ¹ | / T ¹ } × 100 [%] was calculated. The results are shown in Table 2. When this value is 2% or less, the solvent resistance is good.
The solvent resistance was evaluated by performing only the coating film forming step, the pre-bake step, the entire surface exposure (300 mJ / cm ² (illuminance: 20 mW / cm ² )) step, and the post-bake step (220 ° C./1 h).

<Evaluation of transparency>
A cured film was formed on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) in the same manner as in the evaluation of the solvent resistance. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Table 2 shows the values of the minimum light transmittance at that time. When this value is 95% or more, it can be said that the transparency is good.

<Evaluation of heat resistance>
A cured film was formed on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) in the same manner as the evaluation of the solvent resistance, and the film thickness (T ² ) of the obtained cured film was measured. . Next, after this cured film substrate was additionally baked in an oven at 240 ° C. for 1 hour, the film thickness (t ² ) of the cured film was measured, and the film thickness change rate {| t ² −T ² | / T ² } × 100 [%] was calculated. The results are shown in Table 2. When this value is 2% or less, the heat resistance is good.

<Evaluation of relative dielectric constant>
After coating the photosensitive resin composition of the present invention on a bare wafer (N-type low resistance) (manufactured by SUMCO) using a spinner, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes. A 0 μm coating film was formed. The obtained coating film was exposed to a cumulative exposure of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The cured film was obtained by baking at 220 ° C. for 1 hour.
For this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in Table 2. When this value is 3.2 or less, it can be said that the dielectric constant is good.
The relative dielectric constant was measured and evaluated only in the coating film forming process, the pre-baking process, the entire surface exposure (300 mJ / cm ² (illuminance: 20 mW / cm ² )) process, and the post-baking process (220 ° C./1 h).

  Table 2 shows the following. Examples 1-16 by the photosensitive resin composition prepared using any of the binders A and B, which are specific copolymers of the present invention, a photosensitive agent, and a crosslinking agent, all have good transparency. The film thickness change rate in the evaluation of heat resistance and solvent resistance was small, the relative dielectric constant was small, and the insulation was good. On the other hand, Comparative Examples 1 and 2 that do not use a crosslinking agent and Comparative Examples 3 and 4 that do not use a specific copolymer are both poor in transparency and have a film thickness in heat resistance and solvent resistance evaluation. It can be seen that the rate of change is large, the relative dielectric constant is large, and the insulation is poor.

  Next, a manufacturing method of the display device of the present invention will be described by taking an example of a manufacturing method of an organic EL display device as an example. The present invention is applied to a planarizing film or an interlayer insulation formed using the photosensitive resin composition. Other than having a film, there is no particular limitation, and various structures can be adopted in application to a liquid crystal display device.

(Example 17)
An organic EL display device using TFT was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 was formed on the insulating film 3 as follows. The photosensitive resin composition prepared in Example 1 was spin-coated on a substrate, pre-baked on a hot plate (120 ° C. × 2 minutes), and then i-line (365 nm) was applied from the mask using a high-pressure mercury lamp to 100 mJ / After irradiation with cm ² (illuminance 20 mW / cm ² ), development was performed with an alkaline aqueous solution to form a pattern, and a heat treatment was performed at 220 ° C. for 30 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarization film was 2000 nm.

Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating layer 8 having a shape covering the periphery of the first electrode was formed. For the insulating layer, the photosensitive resin composition prepared in Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, an organic EL display device having good display characteristics and high reliability could be produced.

(Example 18)
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 18 was obtained.
That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 17.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT (thin Layer film transistor)
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (13)

(A) a copolymer containing the following structural units (A-1), (A-2), and (A-3), (B) a photosensitizing agent, and (C) a crosslinking agent, A positive photosensitive resin composition, wherein the coalescence is a copolymer containing 10 to 50 mol% of (A-1) and (A-2) independently.
(A-1) Structural unit containing a carboxy group
(A-2) Structural unit in which a compound containing an epoxy ring and an unsaturated group is added to a carboxy group
(A-3) Structural units other than (A-1) and (A-2)   The positive photosensitive resin composition according to claim 1, wherein the structural unit other than (A-3) (A-1) and (A-2) is a structural unit having a ring structure.   The positive photosensitive resin composition according to claim 1 or 2, wherein the structural unit other than (A-3) (A-1) and (A-2) is a structural unit having an alicyclic structure. .   The copolymer containing the structural units (A), (A-1), (A-2), and (A-3) is other than (A-3), (A-1), and (A-2) The positive photosensitive resin composition according to any one of claims 1 to 3, which is a copolymer containing 10 to 60 mol% of the structural unit.   A copolymer containing the structural units (A), (A-1), (A-2), and (A-3) in terms of mass with respect to the total solid content of the positive photosensitive resin composition is 40 5 to 70%, the photosensitive agent (B) is contained in a range of 5% to 40%, and the crosslinking agent (C) is contained in a range of 3% to 40%. The positive photosensitive resin composition as described in any one of these.   The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) photosensitive agent is a compound having a 1,2-naphthoquinonediazide group.   The (C) crosslinking agent is at least one selected from the group consisting of an epoxy compound, an oxetane compound, a compound containing a methacryloyl group or an acryloyl group, a melamine compound, a glycoluril compound, and a phenol compound. The positive photosensitive resin composition as described in any one of Claims 1-6.   Furthermore, (D) The positive photosensitive resin composition as described in any one of Claims 1-7 containing a thermal radical generator.   The positive photosensitive resin composition according to claim 8, wherein the (D) thermal radical generator has a 10-hour half-life temperature of 100 ° C or higher and 230 ° C or lower.   The cured film which apply | coated the positive photosensitive resin composition as described in any one of Claims 1-9 on a board | substrate, and was hardened | cured by light or a heat | fever.   An interlayer insulating film using the cured film according to claim 10.   An organic EL display device comprising the interlayer insulating film according to claim 11.   A liquid crystal display device comprising the interlayer insulating film according to claim 11.