阅读说明：本技术 树脂组合物及树脂膜 (Resin composition and resin film ) 是由 木下健宏 川口恭章 小林将行 林俊亮 周正伟 于 2020-03-16 设计创作，主要内容包括：本发明提供一种树脂组合物,其含有聚合物(A),该聚合物(A)至少具有源自(甲基)丙烯酸羟基苯酯的结构单元及源自亚苯基二(甲基)丙烯酸酯的结构单元。(The present invention provides a resin composition containing a polymer (A) having at least a structural unit derived from hydroxyphenyl (meth) acrylate and a structural unit derived from phenylene di (meth) acrylate.)

1. A resin composition characterized by comprising a polymer (A) having at least a structural unit derived from hydroxyphenyl (meth) acrylate and a structural unit derived from phenylene di (meth) acrylate.

2. The resin composition according to claim 1, wherein a molar ratio of the structural unit derived from hydroxyphenyl (meth) acrylate to the structural unit derived from phenylene di (meth) acrylate is 99.99: 0.01-99.00: 1.00.

3. the resin composition according to claim 1 or 2, the polymer (a) further having a structural unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group.

4. The resin composition according to claim 1 or 2, wherein the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate in the polymer (A) is 40 to 100 mol%.

5. The resin composition according to claim 3, wherein the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate in the polymer (A) is 50 to 90 mol%,

the content of the structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group is 1 to 20 mol%.

6. The resin composition according to any one of claims 1 to 5, which contains a photosensitive component (B).

7. The resin composition according to claim 6, wherein the photosensitive component (B) is a quinone diazo group-containing compound.

8. The resin composition according to claim 6 or 7, comprising 5 to 60 parts by mass of the photosensitive component (B) per 100 parts by mass of the polymer (A).

9. The resin composition according to any one of claims 1 to 8, which comprises a thermosetting resin (C).

10. A resin film produced from a cured product of the resin composition according to any one of claims 1 to 9.

Technical Field

The present invention relates to a resin composition and a resin film.

The present application claims priority based on Japanese application No. 2019-101097, 5/30/2019, the contents of which are incorporated herein by reference.

Background

Conventionally, resin films are used for protective films, interlayer insulating films, and planarization films of electronic components such as TFT (thin-film-transistor) type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state image pickup elements.

For example, in a liquid crystal display device, a transparent conductive film such as Indium Tin Oxide (ITO) is generally formed on an interlayer insulating film formed using a photosensitive resin composition, and a liquid crystal alignment film is formed thereon. Therefore, the interlayer insulating film included in the liquid crystal display element is exposed to a high temperature in the step of forming the transparent electrode film thereon. Therefore, a photosensitive resin composition capable of forming a resin film having excellent transparency and developability and excellent heat resistance is used as a material for a resin film used as an interlayer insulating film of a liquid crystal display element.

For example, patent document 1 discloses a resin film obtained by applying and drying a photosensitive resin composition containing a copolymer containing a repeating unit derived from hydroxyphenyl (meth) acrylate and a repeating unit derived from an unsaturated compound having a blocked isocyanate group on a substrate.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/091818

Disclosure of Invention

Problems to be solved by the invention

However, a resin film having excellent transparency and developability, which is formed using a conventional resin composition, is required to have further improved heat resistance.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition capable of forming a resin film excellent in transparency, developability, and heat resistance.

Another object of the present invention is to provide a resin film which is obtained from a cured product of the resin composition of the present invention and has excellent transparency, developability, and heat resistance.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems.

As a result, they have found that a resin film excellent in transparency, developability, and heat resistance can be obtained by curing a resin composition containing a polymer (a) having at least a structural unit derived from hydroxyphenyl (meth) acrylate and a structural unit derived from phenylene di (meth) acrylate, and have arrived at the present invention.

Namely, the present invention relates to the following aspects.

[1] A resin composition characterized by comprising a polymer (A) having at least a structural unit derived from hydroxyphenyl (meth) acrylate and a structural unit derived from phenylene di (meth) acrylate.

[2] The resin composition according to [1], wherein a molar ratio of the structural unit derived from hydroxyphenyl (meth) acrylate to the structural unit derived from phenylene di (meth) acrylate is 99.99: 0.01-99.00: 1.00.

[3] the resin composition according to [1] or [2], wherein the polymer (A) further has a structural unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group.

[4] The resin composition according to [1] or [2], wherein the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate in the polymer (A) is 40 to 100 mol%.

[5] The resin composition according to [3], wherein the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate in the polymer (A) is 50 to 90 mol%,

the content of the structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group is 1 to 20 mol%.

[6] The resin composition according to any one of [1] to [5], which contains a photosensitive component (B).

[7] The resin composition according to [6], wherein the photosensitive component (B) is a quinone diazide group-containing compound.

[8] The resin composition according to [6] or [7], which contains 5 to 60 parts by mass of the photosensitive component (B) per 100 parts by mass of the polymer (A).

[9] The resin composition according to any one of [1] to [8], which contains a thermosetting resin (C).

[10] A resin film which is produced from a cured product of the resin composition according to any one of [1] to [9 ].

Effects of the invention

According to the present invention, a resin composition capable of forming a resin film excellent in transparency, developability, and heat resistance can be provided.

Detailed Description

The resin composition and the resin film of the present invention will be described in detail below. The present invention is not limited to the embodiments described below.

[ resin composition ]

The resin composition of the present embodiment contains a polymer (a). The resin composition of the present embodiment may contain the polymer (a), and further contain the photosensitive component (B) and/or the thermosetting resin (C).

(Polymer (A))

The polymer (a) contained in the resin composition of the present embodiment has at least a structural unit derived from hydroxyphenyl (meth) acrylate and a structural unit derived from phenylene di (meth) acrylate. The polymer (A) may contain a monomer unit having a hydroxyalkyl group and an ethylenically unsaturated group and a structural unit derived from another monomer, if necessary.

In the present invention, "(meth) acrylate" means at least one selected from methacrylate and acrylate.

In the resin composition of the present embodiment, the polymer (a) has a structural unit derived from hydroxyphenyl (meth) acrylate, and is imparted with alkali solubility.

Specific examples of the structural unit derived from hydroxyphenyl (meth) acrylate include a structural unit derived from o-hydroxyphenyl (meth) acrylate, a structural unit derived from m-hydroxyphenyl (meth) acrylate, and a structural unit derived from p-hydroxyphenyl (meth) acrylate. The polymer (a) may have only one kind of structural units derived from hydroxyphenyl (meth) acrylates having different bonding positions of these substituents, or may have two or more kinds of structural units derived from hydroxyphenyl (meth) acrylates having different bonding positions of these substituents. Among the structural units derived from hydroxyphenyl (meth) acrylate, structural units derived from p-hydroxyphenyl (meth) acrylate are preferred, particularly from the viewpoint of developability when the resin composition of the present embodiment is used as a photosensitive resin composition and reactivity when the polymer (a) is synthesized.

The content of the structural unit derived from hydroxyphenyl (meth) acrylate in the polymer (a) is preferably 39.5 to 99.95 mol%, more preferably 44.5 to 94.9 mol%, and still more preferably 49.6 to 89.8 mol%. When the content of the structural unit is 39.5 mol% or more, the resin composition has more excellent alkali solubility and can form a resin film having a good pattern shape. When the content of the structural unit is 99.95 mol% or less, the content of the structural unit derived from phenylene di (meth) acrylate can be sufficiently secured, and therefore, more excellent heat resistance can be obtained.

In the resin composition of the present embodiment, since the polymer (a) has a structural unit derived from phenylene di (meth) acrylate, the degree of polymerization of the polymer (a) becomes high, and the polymer (a) has high purity. Therefore, the resin film obtained by curing the resin composition of the present embodiment has good heat resistance.

Specific examples of the structural unit derived from phenylene di (meth) acrylate include a structural unit derived from 1, 2-phenylene di (meth) acrylate, a structural unit derived from 1, 3-phenylene di (meth) acrylate, and a structural unit derived from 1, 4-phenylene di (meth) acrylate. The polymer (a) may have only one kind of structural unit derived from phenylene di (meth) acrylate in which the bonding positions of these substituents are different, or may have two or more kinds of structural units derived from phenylene di (meth) acrylate in which the bonding positions of these substituents are different. Among the structural units derived from phenylene di (meth) acrylate, 1, 4-phenylene di (meth) acrylate is preferable, particularly from the viewpoint of reactivity when the polymer (a) is synthesized.

The content of the structural unit derived from phenylene di (meth) acrylate in the polymer (a) is preferably 0.05 to 0.5 mol%, more preferably 0.1 to 0.45 mol%, and still more preferably 0.15 to 0.4 mol%. If necessary, the content of the organic solvent may be 0.15 to 0.25 mol% or 0.25 to 0.4 mol%. When the content of the structural unit is 0.05 mol% or more, the resin composition can be obtained which is a resin film obtained by curing the resin composition and has better heat resistance. When the content of the structural unit is 0.5 mol% or less, the content of the structural unit derived from hydroxyphenyl (meth) acrylate can be sufficiently secured, and therefore, a resin composition capable of forming a resin film having a good pattern shape can be obtained.

The molar ratio of the structural unit derived from hydroxyphenyl (meth) acrylate to the structural unit derived from phenylene di (meth) acrylate in the polymer (a) (structural unit derived from hydroxyphenyl (meth) acrylate: structural unit derived from phenylene di (meth) acrylate) is preferably 99.99: 0.01-99.00: 1.00, more preferably 99.95: 0.05-99.50: 0.50. when the molar ratio of the structural unit derived from hydroxyphenyl (meth) acrylate is 99.00 or more, the resin composition has more excellent alkali solubility and can form a resin film having a good pattern shape. When the molar ratio of the structural units derived from phenylene di (meth) acrylate is 0.01 or more, the effect of improving the heat resistance of a resin film made of a cured product of the resin composition is remarkable.

In the polymer (a), the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate is preferably 40 to 100 mol%, more preferably 50 to 90 mol%, and still more preferably 60 to 85 mol%. If necessary, the amount of the surfactant may be 60 to 70 mol% or 70 to 85 mol%. When the total content of the structural units is 40 mol% or more, the resin composition has more excellent alkali solubility and can form a resin film having a good pattern shape.

The polymer (a) preferably contains a structural unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group, particularly in order to obtain a polymer having a high purity of the polymer and to obtain a resin film having excellent various characteristics such as transparency, heat resistance, and developability.

The hydroxyalkyl group in the structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group is preferably a hydroxyalkyl group having 1 to 8 carbon atoms, and more preferably a hydroxyalkyl group having 2 to 6 carbon atoms. Specific examples thereof include hydroxyethyl, hydroxypropyl and hydroxybutyl.

Specific examples of the structural units derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group include structural units derived from monomers such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, 5- (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, and 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene.

The polymer (a) may have only one structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group, or may have two or more structural units derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group. Among the above-mentioned structural units derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group, a structural unit derived from 2-hydroxyethyl (meth) acrylate and/or a structural unit derived from 2, 3-dihydroxypropyl (meth) acrylate is preferable because of the availability of the monomer and the good polymerizability in synthesizing the polymer (a).

When the polymer (a) has the structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group, the total content of the structural unit derived from hydroxyphenyl (meth) acrylate and the structural unit derived from phenylene di (meth) acrylate in the polymer (a) is preferably 50 to 90 mol%, more preferably 60 to 85 mol%. If necessary, the content may be 60 to 70 mol% or 70 to 85 mol%. When the total content of the structural units is 50 mol% or more, the resin composition has more excellent alkali solubility and can form a resin film having a good pattern shape.

In the polymer (a), the content of the structural unit derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group is preferably 1 to 20 mol%, and more preferably 5 to 15 mol%. If necessary, the content may be 5 to 10 mol% or 10 to 15 mol%. If the total content of the above-mentioned structural units is 1 mol% or more, the polymer purity is high and the developability is good, and therefore, it is preferable. When the total content of the structural units is 20 mol% or less, it is preferable to relatively increase the content of the structural unit derived from hydroxyphenyl (meth) acrylate and the content of the structural unit derived from phenylene di (meth) acrylate, since good heat resistance can be ensured.

The polymer (a) may contain a constitutional unit derived from an ethylenically unsaturated group-containing monomer other than the above three monomers for adjusting transparency, heat resistance, adhesiveness, chemical resistance, electrical characteristics, refractive index, coatability, developability, storage stability, mechanical strength, and the like.

Examples of the structural unit derived from another ethylenically unsaturated group-containing monomer include styrene compounds derived from styrene, methylstyrene, methoxystyrene and the like; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octadecyl (meth) acrylate; glycidyl group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate, glycidyl α -ethacrylate, 3, 4-epoxybutyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, and vinylbenzyl glycidyl ether; alicyclic epoxy group-containing ethylenically unsaturated monomers such as vinylcyclohexene monoxide and 3, 4-epoxycyclohexylmethyl (meth) acrylate; (meth) acrylic acid; carboxyl group-containing ethylenically unsaturated monomers such as crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinylbenzoic acid, carboxyphenyl (meth) acrylate, carboxyphenyl (meth) acrylamide, succinic acid mono [2- (meth) acryloyloxyethyl ] ester, ω -carboxypolycaprolactone mono (meth) acrylate, 5-carboxybicyclo [2.2.1] hept-2-ene, and the like, or anhydrides thereof; cyclic hydrocarbon group-containing (meth) acrylates such as dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; 2,2- (meth) acryloyloxyethyl glycoside; aromatic group-containing (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, methoxyphenyl (meth) acrylate, and 3-methyl-4-hydroxyphenyl (meth) acrylate; cycloolefin compounds such as bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene and 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene; polyenes such as 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene; (meth) acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, o-hydroxyphenyl (meth) acrylamide, m-hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl (meth) acrylamide, 3, 5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, trifluoromethyl (meth) acrylate, and the like.

The polymer (A) may contain only one kind of structural unit derived from other ethylenically unsaturated group-containing monomer, or may contain two or more kinds of structural units derived from other ethylenically unsaturated group-containing monomer. Among the structural units derived from other ethylenically unsaturated group-containing monomers, from the viewpoint of adjusting the alkali developability, it is preferable to include one or more structural units derived from a styrene compound, an alkyl (meth) acrylate, and glycidyl (meth) acrylate, and particularly preferable to include one or more structural units derived from styrene, methyl (meth) acrylate, and glycidyl (meth) acrylate.

The content of the structural unit derived from another ethylenically unsaturated group-containing monomer in the polymer (a) is preferably 5 to 45 mol%, more preferably 10 to 30 mol%.

The weight average molecular weight Mw of the polymer (A) is preferably 1500 to 20000, more preferably 3000 to 10000, and further preferably 5000 to 8000. The amount of the surfactant may be 5000 to 6500 or 6500 to 8000, if necessary. If the weight average molecular weight is 1500 or more, a flat coating film is obtained by coating the resin composition containing the polymer (A). Further, the resin composition has excellent developability and a good pattern shape. The resin composition can be used to obtain a resin film having excellent heat resistance. Further, if the weight average molecular weight is 20000 or less, a resin composition having good sensitivity is obtained, and the pattern shape after development becomes good.

The molecular weight distribution (Mw/Mn) of the polymer (A) is preferably 1.1 to 5.0, more preferably 1.1 to 4.0, and still more preferably 1.1 to 2.5. If necessary, the amount of the surfactant may be 1.1 to 1.8, 1.8 to 2.5, or the like. When the molecular weight distribution is in the above range, a good pattern can be formed by exposing and developing the resin composition.

The method for producing the polymer (a) is not particularly limited, and examples thereof include a method of polymerizing monomers as raw materials of the polymer (a) by a polymerization method such as radical polymerization, cationic polymerization, anionic polymerization, and coordinated anionic polymerization. Specifically, it is preferable to use a method in which a polymerization initiator is added to a solution obtained by mixing a monomer as a raw material of the polymer (A) with a solvent inert to polymerization at a concentration of 10 to 50% by mass, and the mixture is reacted at a temperature of 70 to 120 ℃ for 5 to 10 hours to carry out radical polymerization.

The content (molar ratio) of the structural unit derived from each monomer in the polymer (a) corresponds to the molar ratio of the monomers as the raw material of the polymer (a). Therefore, by adjusting the kind and molar ratio of the monomer as a raw material of the polymer (a), the polymer (a) containing a predetermined structural unit in a predetermined content (molar ratio) can be obtained.

Examples of the polymerization initiator used in the production of the polymer (a) include azo initiators such as 2,2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2-butyronitrile), 2 ' -azobisisobutyronitrile, dimethyl-2, 2 ' -azobisisobutyrate and 1,1 ' -azobis (cyclohexane-1-carbonitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, and t-butyl peroxybenzoate.

The amount of the polymerization initiator used in the production of the polymer (a) is preferably 1 to 15 parts by mass, more preferably 1 to 13 parts by mass, and still more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total monomers as raw materials of the polymer (a). If necessary, the amount of the surfactant may be 1 to 5 parts by mass, 5 to 8 parts by mass, 8 to 12 parts by mass, or the like.

Examples of the solvent used in the production of the polymer (A) include methanol, ethanol, 1-propanol, isopropanol, butanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and bis (di) sThe alkyl group includes, for example, toluene, xylene, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and ethyl lactate.

In the polymerization of the polymer (a), a chain transfer agent may be used for the purpose of adjusting the molecular weight. Specific examples of the chain transfer agent include alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan.

(photosensitive component (B))

The resin composition of the present embodiment may contain a photosensitive component (B) as needed. The resin composition of the present embodiment can be used as a photosensitive resin composition by containing the photosensitive component (B).

The photosensitive component (B) is not particularly limited as long as it is a component having photosensitivity, but a compound containing a quinone diazo group is preferably used. The quinone diazo group-containing compound suppresses alkali solubility in unexposed portions of a coating film formed by coating a resin composition. In addition, the quinone diazo group-containing compound generates carboxylic acid in an exposed portion of a coating film formed by applying the resin composition, thereby improving the alkali solubility of the coating film, and a positive pattern can be formed.

As the quinone diazide group-containing compound, for example, a condensate of a hydroxyl group-containing compound having a phenolic hydroxyl group or an alcoholic hydroxyl group and a 1, 2-diazonaphthoquinone sulfonic acid halide is preferably exemplified.

Specifically, there may be mentioned 1, 2-diazonaphthoquinone sulfonate ester of 2,3, 4-trihydroxybenzophenone, 1, 2-diazonaphthoquinone sulfonate ester of 2,2 ', 4,4 ' -tetrahydroxybenzophenone, 1, 2-diazonaphthoquinone sulfonate ester of 2,3,4,4 ' -tetrahydroxy-3 ' -methoxybenzophenone, 1, 2-diazonaphthoquinone sulfonate ester of 2,4,6,3 ', 4 ', 5 ' -hexahydroxybenzophenone, 1, 2-diazonaphthoquinone sulfonate ester of 2-methyl-2- (2, 4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxybenzdihydropyran, 1 of 2- [ bis { (5-isopropyl-4-hydroxy-2-methyl) phenyl } methyl ] phenol, 2-diazonaphthoquinone sulfonate, 1, 2-diazonaphthoquinone sulfonate of 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl } -4, 6-dihydroxyphenyl) -1-methylethyl ] -3- (1- (3- {1- (4-hydroxyphenyl)) -1-methylethyl } -4, 6-dihydroxyphenyl) -1-methylethyl) benzene, 1, 2-diazonaphthoquinone sulfonate of 4, 6-bis {1- (4-hydroxyphenyl) -1-methylethyl } -1, 3-dihydroxybenzenedibis (2, 4-dihydroxyphenyl) methane, 1 of bis (p-hydroxyphenyl) methane, 2-diazonaphthoquinone sulfonate, 1, 2-diazonaphthoquinone sulfonate of 1,1, 1-tris (p-hydroxyphenyl) ethane, 1, 2-diazonaphthoquinone sulfonate of 1,1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 1, 2-diazonaphthoquinone sulfonate of 4,4 ' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol, 1, 2-diazonaphthoquinone sulfonate of 3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spirobiindan-5, 6,7,5 ', 6 ', 7 ' -hexanol, 1 of 2,2, 4-trimethyl-7, 2 ', 4 ' -trihydroxyflavan, 2-diazonaphthoquinone sulfonate, and the like, and they may be used alone or in combination of two or more.

In particular, as the quinone diazo group-containing compound, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene-1, 2-diazonaphthoquinone-5-sulfonate is preferably used in order to improve photosensitivity.

The content of the photosensitive component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the polymer (A). If necessary, the amount of the organic solvent may be 10 to 15 parts by mass, 15 to 25 parts by mass, 25 to 35 parts by mass, or 35 to 50 parts by mass. When the content of the photosensitive component (B) is 5 parts by mass or more, more favorable developability is obtained. Further, if the content of the photosensitive component (B) is 60 parts by mass or less, the transparency, insulation property, flatness, and the like of the coating film made of the resin composition become more favorable.

(thermosetting resin (C))

The resin composition of the present embodiment may contain a thermosetting resin (C) as needed. The thermosetting resin (C) is used as a crosslinking component for crosslinking the resin composition.

Examples of the thermosetting resin (C) include methylated melamine resin, methylolated urea resin, methylolated benzoguanamine resin, alkoxyalkylated melamine resin, alkoxyalkylated urea resin, alkoxyalkylated benzoguanamine resin, methylolated phenol resin, alkoxyalkylated phenol resin, epoxy compound, aziridine compound, cyanate ester compound, isocyanate compound, epoxy compound, and the like,Oxazoline compoundsAcid anhydride group-containing compounds, formyl group-containing compounds, and the like.

Among these thermosetting resins (C), nitrogen-containing compounds such as an oxyalkylated urea resin and an oxyalkylated melamine resin, and/or epoxy compounds are preferable in terms of providing a resin composition having excellent stability. These thermosetting resins (C) may be used alone or in combination of two or more.

The content of the thermosetting resin (C) is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, per 100 parts by mass of the polymer (A). If necessary, the amount of the surfactant may be 5 to 10 parts by mass or 10 to 15 parts by mass. When the content of the thermosetting resin (C) is 1 part by mass or more, the resin film formed by applying the resin composition is more excellent in heat resistance, chemical resistance, insulation properties, and the like. In addition, if the content of the thermosetting resin (C) is 20 parts by mass or less, the developability of the resin composition becomes further excellent.

(other Components)

The resin composition of the present invention may contain, in addition to the polymer (a), the photosensitive component (B) as an optional component, and the thermosetting resin (C) as an optional component, other components such as a solvent, an ultraviolet absorber, a sensitizer, a sensitizing aid, a plasticizer, a thickener, a dispersant, a defoaming agent, a surfactant, an adhesion aid, a heat-sensitive acid-generating compound, and a colorant, as necessary.

As the solvent, a solvent is used which dissolves each component uniformly and does not react with each component contained in the resin composition. Specifically, the solvent may be the same as the solvent exemplified as the solvent used in the production of the polymer (a).

Among the above solvents, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl methoxypropionate, ethyl ethoxypropionate can be preferably used from the viewpoints of solubility of each component contained in the resin composition, non-reactivity with each component, easiness of forming a coating film made of the resin composition, and the like. In addition, in order to improve the in-plane uniformity of the film thickness of the coating film formed by coating the resin composition with these solvents, high boiling point solvents such as N-methylpyrrolidone, γ -butyrolactone, and N, N-dimethylacetamide may be used in combination.

When the resin composition contains a solvent, the solvent is preferably used in a range of 100 to 4000 parts by mass, more preferably 200 to 1000 parts by mass, based on 100 parts by mass of the total of the components other than the solvent in the resin composition.

[ resin film ]

The resin film of the present embodiment is made of a cured product of the resin composition of the present embodiment.

The resin film of the present embodiment is formed by applying at least one of light and heat to the resin composition of the present embodiment and curing the resin composition.

The resin composition of the present embodiment can be formed by, for example, a method in which the following steps (1) to (7) are sequentially performed when a resin film having a predetermined pattern shape such as an interlayer insulating film is formed using a composition containing the polymer (a), the photosensitive component (B), and the thermosetting resin (C). In the following steps (1) to (7), the step (4) and the step (6) are optional steps, and may be performed as needed.

Step (1): the resin composition is applied to the substrate so that the thickness after curing (thickness of the resin film) becomes a desired thickness.

Step (2): the substrate coated with the resin composition is baked (prebaked) to form a coating film.

Step (3): a part of a coating film made of the resin composition is exposed to active light or radiation.

Step (4): the substrate having the exposed coating film is post-heated.

Step (5): the exposed coating film is developed using a developer.

Step (6): the developed coating film is subjected to blanket exposure.

Step (7): the substrate having the developed coating film is heated to thermally cure the coating film (post-baking).

The substrate used in the step (1) can be selected according to the use of the resin film. Examples of the substrate include a semiconductor substrate such as a silicon wafer, a ceramic substrate, a glass substrate, a metal substrate, and a resin substrate.

As a method for applying the resin composition, a known method can be used. Examples of the method for applying the resin composition include a spray method, a roll coating method, a spin coating method, and a bar coating method.

The thickness of the coating resin composition can be, for example, 0.1 to 30 μm after curing (thickness of the resin film).

The step (2) is performed to evaporate the solvent in the resin composition applied to the substrate. The temperature and time of the prebaking can be appropriately determined depending on the kind and content ratio of each component in the resin composition, the thickness of the resin composition to be coated, and the like. The prebaking is suitably performed by heating at a temperature of 60 to 130 ℃ for 30 seconds to 15 minutes, for example. In the case of forming an interlayer insulating film made of the resin film of the present embodiment, the film thickness at the time of completion of the prebaking is preferably in the range of, for example, 1 to 6 μm.

In step (3), the coating film made of the resin composition formed in steps (1) and (2) is exposed to active light or radiation through a mask having a predetermined pattern.

Examples of the active light or radiation include g-rays (wavelength: 436nm), i-rays (wavelength: 365nm), KrF excimer laser, ArF excimer laser, X-rays, and electron beams.

Examples of the light source of the active light or the radiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, and an excimer laser generator.

The exposure energy is usually 10mJ/cm²～1000mJ/cm²Preferably 20mJ/cm²～500mJ/cm²Energy.

By performing exposure in step (3), a region developed with the developer and a region not developed with the developer are formed on the coating film on the substrate. When a coating film made of a positive-type resin composition using a quinone diazo group-containing compound as the photosensitive component (B) is exposed, the exposed portion becomes a region developed with an aqueous developer.

In the step (4), for example, post-heating at a temperature of 70 to 130 ℃ for several seconds to several minutes is performed as necessary.

In the step (5), the exposed coating film is developed using a developer. In this way, the areas of the coating film developed by the developer are dissolved, and the areas not developed by the developer remain on the substrate. As a result, a coating film having a desired pattern shape is formed.

Examples of the developer used in the step (5) include aqueous developers such as aqueous solutions of bases (basic compounds) including sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4,3,0] -non-5-ene, and the like.

As the aqueous developer, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant to the above-mentioned aqueous alkali solution may be used.

In the step (5), as a developing method, a liquid-filling method, a dipping method, a shaking dipping method, a shower method, or the like can be suitably used. The developing time may be determined appropriately according to the composition of the resin composition, the kind of the developer, and the like. The developing time may be set to 30 to 120 seconds, for example. In the present embodiment, the coating film patterned into a desired pattern shape is preferably subjected to a rinsing treatment by, for example, running water washing.

The step (6) is performed as required. By exposing the entire surface of the developed coating film to light, the photosensitive component (B) remaining in the patterned coating film can be decomposed. By performing the step (6), the light transmittance of the coating film is improved.

The exposure energy in the case of performing blanket exposure is preferably100～1000mJ/cm²。

In the step (7), the developed coating film is heated by a hot plate, an oven or the like to thermally cure (post-baking) the developed coating film. In order to thermally cure the developed coating film, the post-baking temperature is preferably 120 to 250 ℃. The time of the post-baking is appropriately determined depending on the kind of the heating apparatus and the like. For example, when the substrate having the developed coating film is heated on a hot plate, it is preferable to perform the treatment for 5 to 30 minutes. For example, when the substrate having the developed coating film is heat-treated in an oven, it is preferably performed for 30 to 90 minutes.

As described above, the resin film formed on the substrate is a resin film made of a cured product of the resin composition of the present embodiment, and therefore, is excellent in insulation properties, transparency, and heat resistance.

Therefore, the resin film of the present embodiment can be used for various applications such as a planarization film, an interlayer insulating film, a protective film, and a microlens in electronic components such as an organic Electroluminescence (EL) display device, a liquid crystal display device, a magnetic head element, an integrated circuit element, and a solid-state imaging element. In particular, the resin film of the present embodiment is suitable for a planarization film and an interlayer insulating film included in an organic EL display device and a liquid crystal display device.

In addition, when the resin composition of the present embodiment contains a colorant, the resin film of the present embodiment made of a cured product thereof is excellent in insulation and heat resistance, and is excellent in color reproducibility. Therefore, the resin film of the present embodiment can be used for materials such as a black PDL (Pixel Defining Layer), a black matrix, a color filter, and a black columnar spacer in electronic components such as an organic Electroluminescence (EL) display device, a liquid crystal display device, a magnetic head element, an integrated circuit element, and a solid-state imaging element.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to the following examples.

(Synthesis of Polymer [ A-1]

In a flask equipped with a reflux condenser and a stirrer, 177 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 366 parts by mass of methyl 3-methoxypropionate as a solvent, and 19 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator were charged. Then, the flask was purged with nitrogen, and the liquid temperature was raised to 85 ℃ with stirring to react for 7 hours. A polymer solution containing the polymer [ A-1] was obtained.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-1] were measured by the methods shown below. As a result, the polymer [ A-1] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7 to 100 and a molecular weight distribution (Mw/Mn) of 1.9.

Further, the polymer purity of the polymer [ A-1] was calculated from the area percentage of the polymer component excluding the residual monomer by Gel Permeation Chromatography (GPC). As a result, the polymer purity was 90%.

[ measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) ]

The measurement was performed under the following conditions using Gel Permeation Chromatography (GPC), and the calculation was performed in terms of polystyrene.

Column: TSK gel Super HM-N3 manufactured by Tosoh corporation

Column temperature: 40 deg.C

Sample preparation: 0.2% tetrahydrofuran solution of Polymer (A)

Eluting solvent: tetrahydrofuran (THF)

A detector: ultraviolet detector (UV-8320 made by Tosoh corporation)

Flow rate: 0.6mL/min

(Synthesis of Polymer [ A-2]

Into a flask equipped with a reflux condenser and a stirrer were charged 124 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 31 parts by mass of styrene, 313 parts by mass of methyl 3-methoxypropionate as a solvent, and 13 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-2 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-2] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-2] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6,800 and a molecular weight distribution (Mw/Mn) of 1.9.

The polymer purity of the polymer [ A-2] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 91%.

(Synthesis of Polymer [ A-3]

Into a flask equipped with a reflux condenser and a stirrer were charged 124 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 30 parts by mass of methyl methacrylate, 313 parts by mass of methyl 3-methoxypropionate as a solvent, and 14 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-3 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-3] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-3] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6,900 and a molecular weight distribution (Mw/Mn) of 2.0.

The polymer purity of the polymer [ A-3] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 90%.

(Synthesis of Polymer [ A-4]

Into a flask equipped with a reflux condenser and a stirrer were charged 142 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 10 parts by mass of styrene, 13 parts by mass of 2-hydroxyethyl methacrylate, 332 parts by mass of methyl 3-methoxypropionate as a solvent, and 13 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-4 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-4] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-4] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6 to 700 and a molecular weight distribution (Mw/Mn) of 1.9.

The polymer purity of the polymer [ A-4] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 92%.

(Synthesis of Polymer [ A-5]

Into a flask equipped with a reflux condenser and a stirrer were charged 142 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 10 parts by mass of styrene, 12 parts by mass of 2-hydroxyethyl acrylate, 332 parts by mass of methyl 3-methoxypropionate as a solvent, and 13 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-5 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-5] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-5] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7 to 100 and a molecular weight distribution (Mw/Mn) of 2.0.

The polymer purity of the polymer [ A-5] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 95%.

(Synthesis of Polymer [ A-6]

Into a flask equipped with a reflux condenser and a stirrer were charged 142 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 28 parts by mass of glycidyl methacrylate, 341 parts by mass of methyl 3-methoxypropionate as a solvent, and 13 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-6 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-6] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-6] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7,000 and a molecular weight distribution (Mw/Mn) of 1.8.

Further, the polymer purity of the polymer [ A-6] was calculated by the same method as that for the polymer [ A-1 ]. As a result, the polymer purity was 91%.

(Synthesis of Polymer [ A-7]

Into a flask equipped with a reflux condenser and a stirrer were charged 142 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 7 parts by mass of 2-hydroxyethyl acrylate, 34 parts by mass of glycidyl methacrylate, 331 parts by mass of methyl 3-methoxypropionate as a solvent, and 12 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-7 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-7] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-7] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6,900 and a molecular weight distribution (Mw/Mn) of 1.9.

The polymer purity of the polymer [ A-7] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 92%.

(Synthesis of Polymer [ A-8]

Into a flask equipped with a reflux condenser and a stirrer were charged 142 parts by mass of p-hydroxyphenyl methacrylate, 1 part by mass of 1, 4-phenylene dimethacrylate, 6 parts by mass of styrene, 16 parts by mass of 2, 3-dihydroxypropyl methacrylate, 329 parts by mass of methyl 3-methoxypropionate as a solvent, and 12 parts by mass of 2, 2' -azobisisobutyronitrile as a polymerization initiator. Then, the reaction was carried out in the same manner as for the polymer [ A-1] to obtain a polymer solution containing the polymer [ A-8 ].

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-8] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-8] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6,900 and a molecular weight distribution (Mw/Mn) of 1.8.

Further, the polymer purity of the polymer [ A-8] was calculated by the same method as that for the polymer [ A-1 ]. As a result, the polymer purity was 92%.

(Synthesis of Polymer [ A-9]

A polymer [ A-9] was obtained in the same manner as in example 1, except that the amount of 1, 4-phenylene dimethacrylate used was changed.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-9] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-9] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7 to 200 and a molecular weight distribution (Mw/Mn) of 2.0.

The polymer purity of the polymer [ A-9] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 92%.

(Synthesis of Polymer [ A-10]

Polymer [ A-10] was obtained in the same manner as in example 1, except that o-hydroxyphenyl methacrylate was used instead of p-hydroxyphenyl methacrylate, and 1, 2-phenylene dimethacrylate was used instead of 1, 4-phenylene dimethacrylate.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-10] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-10] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7,000 and a molecular weight distribution (Mw/Mn) of 1.9.

Further, the polymer purity of the polymer [ A-10] was calculated by the same method as that for the polymer [ A-1 ]. As a result, the polymer purity was 88%.

(Synthesis of Polymer [ A-11]

Polymer [ A-11] was obtained in the same manner as in example 1, except that m-hydroxyphenyl methacrylate was used in place of p-hydroxyphenyl methacrylate and 1, 3-phenylene dimethacrylate was used in place of 1, 4-phenylene dimethacrylate.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-11] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-11] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7 to 100 and a molecular weight distribution (Mw/Mn) of 2.0.

The polymer purity of the polymer [ A-11] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 89%.

(Polymer [ A-12])

As the polymer [ A-12], a hydroxystyrene polymer (trade name: Maruka Lyncur S-2P (produced by Maruka petrochemical Co., Ltd.) was used.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the polymer [ A-12] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-12] had a polystyrene-equivalent weight-average molecular weight (Mw) of 6 to 700 and a molecular weight distribution (Mw/Mn) of 2.0.

The polymer purity of the polymer [ A-12] was calculated in the same manner as for the polymer [ A-1 ]. As a result, the polymer purity was 90%.

(Polymer [ A-13])

A polymer [ A-13] was obtained in the same manner as in example 1, except that 1, 4-phenylene dimethacrylate was not used.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the obtained polymer [ A-13] were measured by the same methods as for the polymer [ A-1 ]. As a result, the polymer [ A-13] had a polystyrene-equivalent weight-average molecular weight (Mw) of 7,000 and a molecular weight distribution (Mw/Mn) of 1.8.

Further, the polymer purity of the polymer [ A-13] was calculated by the same method as that for the polymer [ A-1 ]. As a result, the polymer purity was 87%.

The molar ratio of the monomers used as the raw materials, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the purity of the polymer are shown in Table 1 and Table 2 for the polymers [ A-1] to [ A-13 ].

The polymer purity of the polymers [ A-1] to [ A-13] was evaluated based on the following criteria.

Very good: over 92 percent

○：88～91％

X: less than 87%

[ Table 1]

[ Table 2]

[ preparation of photosensitive resin composition ]

(example 1)

100 parts by mass of a polymer solution (35% by mass concentration) containing the polymer [ A-1] obtained by the above-mentioned synthesis method, 6.25 parts by mass of 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene-1, 2-diazonaphthoquinone-5-sulfonate as a photosensitive component, and 2.10 parts by mass of an alkoxymethylated melamine resin (manufactured by Sanko chemical Co., Ltd., trade name: ニカラック MW-30) as a thermosetting resin were mixed with 80 parts by mass of methyl 3-methoxypropionate as a solvent and dissolved. The obtained solution was filtered using a 0.2 μm membrane filter to prepare the photosensitive resin composition of example 1.

(examples 2 to 11)

Photosensitive resin compositions of examples 2 to 11 were prepared in the same manner as in example 1 except that 100 parts by mass of the polymer solution (35% by mass concentration) containing the polymer [ A-1] was replaced with polymer solutions (35% by mass concentration) containing the polymers [ A-2] to [ A-11] obtained by the above-mentioned synthesis methods.

Comparative example 1

A photosensitive resin composition of comparative example 1 was prepared in the same manner as in example 1, except that a polymer solution containing 35 mass% of the polymer [ A-12] using methyl 3-methoxypropionate as a solvent was used in place of 100 parts by mass of the polymer solution (35 mass% concentration) containing the polymer [ A-1 ].

Comparative example 2

A photosensitive resin composition of comparative example 2 was prepared in the same manner as in example 1, except that the polymer solution (35% by mass concentration) containing the polymer [ A-13] obtained by the above-mentioned synthesis method was used in place of 100 parts by mass of the polymer solution (35% by mass concentration) containing the polymer [ A-1 ].

[ evaluation of characteristics ]

The photosensitive resin compositions of examples 1 to 11 and comparative examples 1 and 2 were evaluated for transparency, heat-resistant transparency, thermal decomposition resistance, and alkali dissolution rate by the following methods. The results are shown in tables 1 and 2.

Transparency

The photosensitive resin composition was coated on a glass substrate so that the thickness after curing became 2.6 μm. Subsequently, the glass substrate coated with the photosensitive resin composition was dried (prebaked) at a temperature of 110 ℃ for 90 seconds on a hot plate to form a coating film. Then, the dried coating film was subjected to exposure energy of 200mJ/cm using an ultra-high pressure mercury lamp as a light source²The entire surface is exposed to g rays (436nm) as active rays or radiation rays. Next, the glass substrate having the exposed coating film was placed in an oven, heated at 200 ℃ for 30 minutes, and thermally cured (post-baked) to obtain a resin film.

The thus obtained glass substrate having a resin film was evaluated by measuring the minimum transmittance at a wavelength of 400 to 800nm using a spectrophotometer (UV-1650PC (manufactured by shimadzu corporation)) with the glass substrate as a blank group, and by the following criteria.

Excellent (good): more than 95 percent

O (pass): 90 to 94 percent

X (fail): less than 89%

Heat-resistant transparency

The glass substrate having the resin film used for the evaluation of the above < transparency > was again subjected to a heat treatment at 230 ℃ for 2 hours and further at 250 ℃ for 1 hour in air. Then, the minimum transmittance at a wavelength of 400 to 800nm was measured using a spectrophotometer (UV-1650PC, Shimadzu corporation)) with a glass substrate as a blank group, and evaluated by the following criteria.

Excellent (good): over 93 percent

O (pass): 90 to 92 percent

X (fail): less than 89%

Resistance to thermal decomposition

The film thickness of the glass substrate having the resin film used for the evaluation of the above "heat-resistant transparency" was measured. Then, the glass substrate having the resin film used for the evaluation of the above "heat-resistant transparency" was reheated by heating at 200 ℃ for 30 minutes. Then, the film thickness of the glass substrate having the resin film after reheating was measured, and the rate of decrease in the film thickness of the resin film due to reheating was calculated using the film thickness, and evaluated by the following criteria.

Excellent (good): less than 10%

O (pass): 11 to 15 percent

X (fail): more than 16 percent

Alkaline dissolution velocity

The photosensitive resin composition was coated on a silicon wafer substrate so that the thickness after curing became 2.6. mu.m. Subsequently, the silicon wafer substrate coated with the photosensitive resin composition was dried (prebaked) at a temperature of 110 ℃ for 90 seconds on a hot plate to form a coating film. Then, the dried coating film was subjected to exposure energy of 200mJ/cm using an ultra-high pressure mercury lamp as a light source²G rays (435nm) as active rays or radioactive rays are irradiated, and blanket exposure is performed through an erecting mask.

Next, the substrate having the exposed coating film was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution as a developer, developed, and the dissolution rate (nm/s) of the coating film per unit time was calculated from the development time of the coating film of 2.6 μm, and evaluated by the following criteria.

Excellent (good): 151 to 500nm/s

O (pass): 101 to 150nm/s

X (fail): 100nm/s or less

As shown in tables 1 and 2, the photosensitive resin compositions of examples 1 to 11 were excellent in transparency, heat-resistant transparency, thermal decomposition resistance and alkali dissolution rate, or good in quality.

In particular, the transparency, heat-resistant transparency, thermal decomposition resistance and alkali dissolution rate of example 4, 5, 7 and 8 containing the polymer [ A-4] [ A-5] [ A-7] [ A-8] further having a structural unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group, and example 9 containing [ A-9] in which a structural unit derived from a phenylene di (meth) acrylate is contained in a large amount were all evaluated as excellent (good).

On the other hand, the photosensitive resin composition of comparative example 1, which contained the polymer [ A-12] containing no structural unit derived from hydroxyphenyl (meth) acrylate and no structural unit derived from phenylene di (meth) acrylate, was evaluated as X (failed) in terms of heat-resistant transparency, and was insufficient in heat resistance.

The photosensitive resin composition of comparative example 2, which contained the polymer [ A-13] containing no structural unit derived from phenylene di (meth) acrylate, was evaluated as having X (nonconforming) thermal decomposition resistance and insufficient heat resistance.

Industrial applicability

The present invention provides a resin composition capable of forming a resin film having excellent developability and excellent transparency and heat resistance. The resin film obtained by the present invention can be used for various applications such as a planarization film, an interlayer insulating film, a protective film, and a microlens, which are used in an organic EL display device and a liquid crystal display device.