TWI844646B - Resin composition and resin film - Google Patents

Abstract

A resin composition comprises a polymer (A) having at least a constituent unit derived from hydroxyphenyl (meth)acrylate and a constituent unit derived from phenylene di(meth)acrylate.

Description

Resin composition and resin film

The present invention relates to a resin composition and a resin film. This case claims priority based on the Japanese patent application No. 2019-101097 filed on May 30, 2019, and the contents thereof are hereby incorporated by reference.

In the past, resin films were used as protective films, interlayer insulating films, and planarizing films of electronic parts such as TFT (thin-film-transistor) type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements. For example, in liquid crystal display elements, a transparent conductive film such as indium tin oxide (ITO) is usually 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 of the liquid crystal display element is exposed to high temperature conditions during the step of forming a transparent electrode film thereon. Therefore, as a material for a resin film used as an interlayer insulating film of a liquid crystal display element, a photosensitive resin composition is used that can form a resin film having good transparency and developing properties and excellent heat resistance.

For example, Patent Document 1 discloses a resin film obtained by coating a photosensitive resin composition containing a copolymer on a substrate and drying the copolymer, wherein the copolymer contains repeating units derived from hydroxyphenyl (meth)acrylate and repeating units derived from an unsaturated compound containing a blocked isocyanate group. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2014/091818

[The problem that the invention is trying to solve]

However, the resin film with good transparency and developing properties formed by using the conventional resin composition is required to further improve the heat resistance. The present invention is completed in view of the above situation, and its purpose is to provide a resin composition that can form a resin film with excellent transparency, developing properties and heat resistance. In addition, the purpose of the present invention is to provide a resin film, which includes a cured product of the resin composition of the present invention, and has excellent transparency, developing properties and heat resistance. [Means for Solving the Problem]

The inventors of the present invention have devoted themselves to research to solve the above problems. As a result, they have found that a resin film having excellent transparency, developing properties and heat resistance can be obtained by curing a resin composition containing a polymer (A), wherein the polymer (A) has at least a constituent unit derived from hydroxyphenyl (meth)acrylate and a constituent unit derived from phenyl di(meth)acrylate, and have come up with the present invention. That is, the present invention relates to the following matters.

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

[2] The resin composition as described in [1], wherein the molar ratio of the constituent units derived from hydroxyphenyl (meth)acrylate to the constituent units derived from phenyl di(meth)acrylate is 99.99:0.01 to 99.00:1.00. [3] The resin composition as described in [1] or [2], wherein the polymer (A) further comprises constituent units derived from monomers having a hydroxyalkyl group and an ethylenically unsaturated group.

[4] The resin composition as described in [1] or [2], wherein the total content of the constituent units derived from hydroxyphenyl (meth)acrylate and the constituent units derived from phenyl di(meth)acrylate in the polymer (A) is 40 to 100 mol%. [5] The resin composition as described in [3], wherein the total content of the constituent units derived from hydroxyphenyl (meth)acrylate and the constituent units derived from phenyl di(meth)acrylate in the polymer (A) is 50 to 90 mol%, and the content of the constituent units derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group is 1 to 20 mol%.

[6] The resin composition as described in any one of [1] to [5], which contains a photosensitive component (B). [7] The resin composition as described in [6], wherein the photosensitive component (B) is a compound containing a quinonediazide group.

[8] The resin composition as described in [6] or [7], wherein the photosensitive component (B) is contained in an amount of 5 to 60 parts by weight relative to 100 parts by weight of the polymer (A). [9] The resin composition as described in any one of [1] to [8], which contains a thermosetting resin (C).

[10] A resin film comprising a cured product of the resin composition of any one of [1] to [9]. [Effect of the invention]

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

[Form of implementing the invention]

The resin composition and resin film of the present invention are described in detail below. In addition, the present invention is not limited to the embodiments shown below. [Resin composition] The resin composition of the present embodiment contains a polymer (A). The resin composition of the present embodiment may contain a polymer (A) together with a photosensitive component (B) and/or a thermosetting resin (C).

(Polymer (A)) The polymer (A) contained in the resin composition of this embodiment contains at least a constituent unit derived from hydroxyphenyl (meth)acrylate and a constituent unit derived from diphenyl (meth)acrylate. Polymer (A) may also contain a constituent unit derived from a monomer unit having a hydroxyalkyl group and an ethylenically unsaturated group or other monomers as needed. In the present invention, the so-called "(meth)acrylate" means at least one selected from methacrylate and acrylate.

In the resin composition of the present embodiment, the polymer (A) is provided with a constituent unit derived from hydroxyphenyl (meth)acrylate, thereby imparting alkali solubility. Specifically, as the constituent unit derived from hydroxyphenyl (meth)acrylate, there can be cited a constituent unit derived from o-hydroxyphenyl (meth)acrylate, a constituent unit derived from m-hydroxyphenyl (meth)acrylate, and a constituent unit derived from p-hydroxyphenyl (meth)acrylate. The polymer (A) may have only one constituent unit derived from hydroxyphenyl (meth)acrylate in which the bonding position of the substituent is different, or may have two or more constituent units. Among the constituent units derived from hydroxyphenyl (meth)acrylate, constituent units derived from p-hydroxyphenyl (meth)acrylate are particularly preferred from the viewpoint of developing properties when the resin composition of the present embodiment is used as a photosensitive resin composition and reactivity when synthesizing the polymer (A).

In the polymer (A), the content of the constituent unit derived from hydroxyphenyl (meth)acrylate is preferably 39.5 to 99.95 mol%, more preferably 44.5 to 94.9 mol%, and particularly preferably 49.6 to 89.8 mol%. If the content of the above constituent unit is 39.5 mol% or more, it has better alkali solubility and becomes a resin composition capable of forming a resin film with a good pattern shape. If the content of the above constituent unit is 99.95 mol% or less, the content of the constituent unit derived from phenyl di(meth)acrylate can be fully ensured, thereby obtaining better heat resistance.

Since the polymer (A) of the resin composition of this embodiment has a constituent unit derived from phenylene di(meth)acrylate, the degree of polymerization of the polymer (A) becomes high, and the polymer (A) has a high polymer purity. Therefore, the resin film formed by curing the resin composition of this embodiment has good heat resistance.

Specific examples of the phenylene di(meth)acrylate-derived constituent unit include a 1,2-phenylene di(meth)acrylate-derived constituent unit, a 1,3-phenylene di(meth)acrylate-derived constituent unit, and a 1,4-phenylene di(meth)acrylate-derived constituent unit. The polymer (A) may have only one or more phenylene di(meth)acrylate-derived constituent units having substituents at different bonding positions. Among the phenylene di(meth)acrylate-derived constituent units, 1,4-phenylene di(meth)acrylate is preferred from the viewpoint of reactivity when synthesizing the polymer (A).

In the polymer (A), the content of the constituent unit derived from hydroxyphenyl di(meth)acrylate is preferably 0.05-0.5 mol%, more preferably 0.1-0.45 mol%, and particularly preferably 0.15-0.4 mol%. It may also be 0.15-0.25 mol% or 0.25-0.4 mol%, etc. as required. If the content of the above constituent unit is 0.05 mol% or more, the resin composition has better heat resistance in the resin film formed by curing the resin composition. If the content of the above constituent unit is 0.5 mol% or less, the content of the constituent unit derived from hydroxyphenyl (meth)acrylate can be sufficiently ensured, thereby becoming a resin composition capable of forming a resin film with a good pattern shape.

The molar ratio of the constituent units derived from hydroxyphenyl (meth)acrylate to the constituent units derived from phenylene di(meth)acrylate in the polymer (A) (constituent units derived from hydroxyphenyl (meth)acrylate:constituent units derived from phenylene di(meth)acrylate) is preferably 99.99:0.01 to 99.00:1.00, and more preferably 99.95:0.05 to 99.50:0.50. When the molar ratio of the constituent units derived from hydroxyphenyl (meth)acrylate is 99.00 or more, the polymer has better alkali solubility and can form a resin film having a good pattern shape. When the molar ratio of the constituent units derived from phenylene di(meth)acrylate is 0.01 or more, the effect of improving the heat resistance of a resin film formed by a cured product of the resin composition becomes significant.

In the polymer (A), the total content of the constituent units derived from hydroxyphenyl (meth)acrylate and the constituent units derived from phenylene di(meth)acrylate is preferably 40 to 100 mol%, more preferably 50 to 90 mol%, and particularly preferably 60 to 85 mol%. If necessary, it may be 60 to 70 mol% or 70 to 85 mol%. If the total content of the above constituent units is 40 mol% or more, the resin composition has better alkali solubility and can form a resin film with a good pattern shape.

The polymer (A) preferably contains a constituent unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group, in order to obtain a polymer having high polymer purity and to obtain a resin film having excellent properties such as transparency, heat resistance, and developability.

The hydroxyalkyl group in the aforementioned constituent unit derived from a 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. Specifically, there can be mentioned a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and the like.

Specific examples of the constituent units derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group include 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, -dihydroxypropyl ester, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene and 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.

The polymer (A) may have only one or more constituent units derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group. Among the constituent units derived from the monomer having a hydroxyalkyl group and an ethylenically unsaturated group, the constituent units derived from 2-hydroxyethyl (meth)acrylate and/or the constituent units derived from 2,3-dihydroxypropyl (meth)acrylate are particularly preferred because of the good availability of the monomers and the good polymerizability when synthesizing the polymer (A).

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

In polymer (A), the content of the aforementioned constituent units derived from monomers having hydroxyalkyl groups and ethylenically unsaturated groups is preferably 1 to 20 mol%, more preferably 5 to 15 mol%. It may also be 5 to 10 mol% or 10 to 15 mol% as required. If the total content of the aforementioned constituent units is 1 mol% or more, the polymer purity is high, and it is preferably a resin composition with good developing properties. If the total content of the aforementioned constituent units is 20 mol% or less, it is preferably to relatively increase the content of the aforementioned constituent units derived from hydroxyphenyl (meth)acrylate and the aforementioned constituent units derived from phenyl di(meth)acrylate to ensure good heat resistance.

The polymer (A) may contain constituent units derived from monomers containing ethylenically unsaturated groups other than the above three in order to adjust transparency, heat resistance, adhesion, chemical resistance, electrical properties, refractive index, coating properties, developing properties, storage stability, mechanical strength, etc.

As the constituent units derived from other monomers containing ethylenic unsaturated groups, for example, there can be cited styrene compounds derived from styrene, methylstyrene, methoxystyrene, etc.; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-octadecyl (meth)acrylate; (meth)acrylate glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, and vinylbenzyl glycidyl ether, etc.; unsaturated monomers; alicyclic ethylene unsaturated monomers containing epoxy groups such as vinyl cyclohexene monoxide and 3,4-epoxycyclohexylmethyl (meth)acrylate; (meth)acrylic acid; crotonic acid, maleic acid, fumaric acid, liraconic acid, mesaconic acid, itaconic acid, vinylbenzoic acid, carboxyphenyl (meth)acrylate, (meth)acryloylcarboxyanilide, succinic acid mono[2-(meth)acryloyloxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate, 5-carboxybicyclo[2.2.1]hept-2-ene or anhydrides thereof; dicyclopentyl (meth)acrylate, (meth)acrylic acid (Meth)acrylates containing cyclic hydrocarbon groups such as dicyclopentyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, and isoborneol (meth)acrylate; 2,2-(meth)acryloyloxyethyl glycoside; (meth)acrylates containing aromatic groups such as phenyl (meth)acrylate, benzyl (meth)acrylate, methoxyphenyl (meth)acrylate, and 3-methyl-4-hydroxyphenyl (meth)acrylate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5- Cycloolefin compounds such as phenoxycarbonylbicyclo[2.2.1]hept-2-ene; polyolefins such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; constituent units of (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, etc.

The polymer (A) may contain only one constituent unit derived from other monomers containing ethylenically unsaturated groups, or may contain two or more constituent units. Among the constituent units derived from other monomers containing ethylenically unsaturated groups, from the viewpoint of adjusting the alkali developing property, it is preferred to contain one or more constituent units selected from styrene compounds, (meth)acrylic acid esters, and glycidyl (meth)acrylate, and it is particularly preferred to contain one or more constituent units selected from styrene, methyl (meth)acrylate, and glycidyl (meth)acrylate.

In the polymer (A), the content of the constituent units derived from other monomers containing ethylenically unsaturated groups is preferably 5 to 45 mol %, more preferably 10 to 30 mol %.

The mass average molecular weight Mw of polymer (A) is preferably 1500~20000, more preferably 3000~10000, and particularly preferably 5000~8000. It can also be 5000~6500 or 6500~8000 as required. If the mass average molecular weight is above 1500, a flat coating film can be obtained by applying a resin composition containing polymer (A). Furthermore, it becomes a resin composition with excellent developability and good pattern shape. Moreover, it becomes a resin composition that obtains a resin film with good heat resistance. In addition, if the mass average molecular weight is below 20000, it becomes a resin composition with good sensitivity, 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 particularly preferably 1.1 to 2.5. It may also be 1.1 to 1.8 or 1.8 to 2.5, etc., as required. If the molecular weight distribution is within 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 the monomers of the raw materials of the polymer (A) by using free radical polymerization, cationic polymerization, anionic polymerization, coordinated anionic polymerization, etc. Specifically, a method of using free radical polymerization is preferred: a polymerization initiator is added to a solution of the monomers of the raw materials of the polymer (A) mixed at a concentration of 10 to 50% by mass with a solvent inert to the polymerization reaction, and the mixture is reacted at a temperature of 70 to 120° C. for 5 to 10 hours.

The content (molar ratio) of the constituent units from each monomer in the polymer (A) corresponds to the molar ratio of the monomers of the raw materials of the polymer (A). Therefore, by adjusting the types and molar ratios of the monomers of the raw materials of the polymer (A), a polymer (A) containing a specified constituent unit at a specified 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), 2,2'-azobis(2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate and 1,1'-azobis(cyclohexane-1-carbonitrile); and organic peroxides such as benzoyl peroxide, lauryl peroxide, octyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butyl isopropyl peroxide, diisopropyl 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 weight, more preferably 1 to 13 parts by weight, and particularly preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers of the raw materials of the polymer (A). It may also be 1 to 5 parts by weight, 5 to 8 parts by weight, or 8 to 12 parts by weight, etc., as required.

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, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene 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, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylformamide, and ethyl lactate.

When polymerizing 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 this embodiment may contain a photosensitive component (B) as needed. The resin composition of this embodiment may be used as a photosensitive resin composition by containing a photosensitive component (B).

The photosensitive component (B) is not particularly limited as long as it is a component having photosensitivity, but preferably a compound containing a quinonediazide group is used. The compound containing a quinonediazide group suppresses the alkali solubility in the unexposed part of the coating film formed by coating the resin composition. In addition, the compound containing a quinonediazide group generates carboxylic acid in the exposed part of the coating film formed by coating the resin composition to increase the alkali solubility of the coating film, thereby enabling the formation of positive pattern.

As a preferred example of a quinone diazide-containing compound, a condensate of a hydroxyl-containing compound having a phenolic hydroxyl group or an alcoholic hydroxyl group and 1,2-naphthoquinone diazide sulfonyl halide can be cited. Specifically, 1,2-naphthoquinone diazide sulfonate of 2,3,4-trihydroxydiphenyl ketone, 1,2-naphthoquinone diazide sulfonate of 2,2',4,4'-tetrahydroxydiphenyl ketone, 1,2-naphthoquinone diazide sulfonate of 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl ketone, 1,2-naphthoquinone diazide sulfonate of 2,4,6,3',4',5'-hexahydroxydiphenyl ketone, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-1,2-naphthoquinone diazide sulfonate ... 1,2-naphthoquinone diazide sulfonate of 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl]phenol, 1,2-naphthoquinone diazide 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 ,2-naphthoquinone diazide sulfonate, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxyphenyl bis(2,4-dihydroxyphenyl)methane 1,2-naphthoquinone diazide sulfonate, bis(p-hydroxyphenyl)methane 1,2-naphthoquinone diazide sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane 1,2-naphthoquinone diazide sulfonate, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane 1,2-naphthoquinone diazide sulfonate Azosulfonate, 1,2-naphthoquinone diazide sulfonate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, 1,2-naphthoquinone diazide sulfonate of 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol, 1,2-naphthoquinone diazide sulfonate of 2,2,4-trimethyl-7,2',4'-trihydroxyflavane, etc., can be used alone or in combination of two or more.

In particular, as the quinonediazide group-containing compound, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene-1,2-naphthoquinonediazide-5-sulfonate is preferably used because of its high photosensitivity.

The content of the photosensitive component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the polymer (A). It may also be 10 to 15 parts by mass, 15 to 25 parts by mass, 25 to 35 parts by mass, 35 to 50 parts by mass, etc. as required. If the content of the photosensitive component (B) is 5 parts by mass or more, better developing properties are obtained. Moreover, if the content of the photosensitive component (B) is 60 parts by mass or less, the transparency, insulation, flatness, etc. of the coating formed by the resin composition are improved.

(Thermosetting resin (C)) The resin composition of this 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 resins, hydroxymethylated melamine resins, hydroxymethylated urea resins, hydroxymethylated benzoguanamine resins, alkoxyalkylated melamine resins, alkoxyalkylated urea resins, alkoxyalkylated benzoguanamine resins, hydroxymethylated phenol resins, alkoxyalkylated phenol resins, epoxy compounds, aziridine compounds, cyanate compounds, isocyanate compounds, oxazoline compounds, acid anhydride group-containing compounds, formyl group-containing compounds, and the like.

Among these thermosetting resins (C), nitrogen-containing compounds and/or epoxy compounds such as alkoxyalkylated urea resins or alkoxyalkylated melamine resins are preferred in terms of providing a resin composition with 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, relative to 100 parts by mass of the polymer (A). It may also be 5 to 10 parts by mass or 10 to 15 parts by mass, etc., as required. If the content of the thermosetting resin (C) is 1 part by mass or more, the heat resistance, chemical resistance, insulation, etc. of the resin film formed by coating the resin composition are improved. Furthermore, if the content of the thermosetting resin (C) is 20 parts by mass or less, the developing property of the resin composition is improved.

(Other components) The resin composition of the present invention may contain other components such as solvent, ultraviolet absorber, sensitizer, sensitizing aid, plasticizer, thickener, dispersant, defoamer, surfactant, adhesion aid, thermosensitive acid generating compound, colorant, etc., in addition to the polymer (A), optional photosensitive component (B), and optional thermosetting resin (C).

As the solvent, a solvent that uniformly dissolves each component and does not react with each component contained in the resin composition can be used. Specifically, as the solvent, the same as the solvent exemplified in the production of the above-mentioned polymer (A) can be cited. Among the above-mentioned solvents, in terms of the solubility of each component contained in the resin composition, the non-reactivity with each component, the ease of forming a coating film formed by the resin composition, etc., it is preferable to use diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl methoxypropionate, and ethyl ethoxypropionate. Furthermore, together with these solvents, in order to improve the in-plane uniformity of the film thickness of the coating formed by coating the resin composition, a high boiling point solvent such as N-methylpyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, etc. can also be used.

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

[Resin film] The resin film of the present embodiment includes 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 to cure the resin composition.

When a resin film having a predetermined pattern shape such as an interlayer insulating film is formed by using a resin composition comprising a polymer (A), a photosensitive component (B) and a thermosetting resin (C) as the resin composition of the present embodiment, for example, the following steps (1) to (7) can be performed in order. In the following steps (1) to (7), steps (4) and (6) are arbitrary steps and can be performed as required.

Step (1): Apply a resin composition on a substrate so that the thickness after curing (thickness of the resin film) becomes a desired thickness. Step (2): Form a coating by baking (pre-baking) the substrate on which the resin composition is applied. Step (3): Expose a portion of the coating formed by the resin composition by irradiating active light or radiation. Step (4): Post-heat the substrate with the exposed coating. Step (5): Develop the exposed coating using a developer. Step (6): Fully expose the developed coating. Step (7): Heat the substrate with the developed coating to thermally cure the coating (post-baking).

The substrate used in step (1) can be selected according to the purpose of the resin film. As the substrate, for example, a semiconductor substrate such as a silicon wafer, a ceramic substrate, a glass substrate, a metal substrate, a resin substrate, etc. can be used. As a method for applying the resin composition, a well-known method can be used. For example, as a method for applying the resin composition, a spray method, a roller coating method, a spin coating method, a rod coating method, etc. can be cited. The thickness of the applied resin composition can be, for example, such that the thickness after curing (the thickness of the resin film) becomes 0.1~30μm.

Step (2) is performed to evaporate the solvent in the resin composition coated on the substrate. The temperature and time of pre-baking can be appropriately determined according to the type and content ratio of each component in the resin composition, the thickness of the coated resin composition, etc. Pre-baking is preferably performed by heating at a temperature of 60 to 130° C. for 30 seconds to 15 minutes. When forming an interlayer insulating film formed by the resin film of this embodiment, the film thickness at the time point when the pre-baking is completed is preferably in the range of 1 to 6 μm, for example.

In step (3), the coating film formed by the resin composition after step (1) and step (2) is exposed to active light or radiation through a mask having a specified pattern. Examples of active light or radiation include g-ray (wavelength 436nm), i-ray (wavelength 365nm), KrF excimer laser, ArF excimer laser, X-ray, electron beam, etc. Examples of the light source of active light or radiation include low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, chemical lamp, excimer laser generating device, etc. The exposure energy is generally 10mJ/cm ² ~1000mJ/cm ² , preferably 20mJ/cm ² ~500mJ/cm ² .

By performing exposure in step (3), the coating on the substrate forms an area developed by the developer and an area not developed by the developer. When the coating formed by a positive resin composition using a quinonediazide group-containing compound as a photosensitive component (B) is exposed, the exposed portion becomes the area developed by the aqueous developer.

In step (4), post-heating is performed at a temperature of 70-130° C. for a few seconds to a few minutes, for example, as needed.

In step (5), the exposed coating is developed using a developer. As a result, the area developed by the developer is dissolved, and the area not developed by the developer remains on the substrate. As a result, a coating having a desired pattern shape is formed.

As the developer used in step (5), for example, an aqueous developer such as an aqueous solution of an alkali (alkaline compound) such as 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 or the like can be used.

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

In step (5), as a developing method, a coating method, an immersion method, a shaking immersion method, a spray method, etc. can be appropriately used. The developing time can be appropriately determined according to the composition of the resin composition and the type of the developer. The developing time can be set to 30 to 120 seconds, for example. In this embodiment, the coating film patterned into the desired pattern shape is preferably rinsed by washing with running water, for example.

Step (6) is performed as needed. By fully exposing the developed coating, the residual photosensitive component (B) in the patterned coating can be decomposed. By performing step (6), the light transmittance of the coating is increased. The exposure energy for full exposure is preferably 100-1000 mJ/cm ² .

In step (7), the developed coating is heated by a hot plate, an oven, etc., so that the developed coating is thermally hardened (post-baking). In order to thermally harden the developed coating, the post-baking temperature is preferably 120~250°C. The post-baking time is appropriately determined according to the type of heating machine, etc. For example, when the substrate with the developed coating is heated on a hot plate, it is appropriate to heat it for 5 to 30 minutes. For example, when the substrate with the developed coating is heated in an oven, it is appropriate to heat it for 30 to 90 minutes.

In this way, the resin film formed on the substrate has excellent insulation, transparency, and heat resistance because it contains the cured product of the resin composition of this embodiment. Therefore, the resin film of this embodiment can be used for various purposes such as planarization films, interlayer insulation films, protective films, microlenses, etc. in electronic parts such as organic electroluminescent (EL) display devices, liquid crystal display devices, head components, integrated circuit components, and solid-state imaging components. In particular, the resin film of this embodiment is suitable for planarization films and interlayer insulation films possessed by organic EL display devices and liquid crystal display devices. Furthermore, when the resin composition of the present embodiment contains a coloring agent, the resin film of the present embodiment including the cured product thereof has excellent insulation and heat resistance, and also has good color reproducibility. Therefore, the resin film of the present embodiment can be used as a material for black PDL (Pixel Defining Layer), black matrix, color filter, black column spacer, etc. in electronic parts such as organic display devices (EL) display devices, liquid crystal display devices, magnetic head components, integrated circuit components, solid-state imaging components, etc. [Example]

The present invention is described in more detail below by way of embodiments and comparative examples. Furthermore, the present invention is not limited to the following embodiments.

(Synthesis of polymer [A-1]) In a flask equipped with a reflux cooler 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 added. Then, the atmosphere in the flask was replaced with nitrogen, and the liquid temperature was raised to 85°C while stirring and reacted for 7 hours to obtain a polymer solution containing polymer [A-1].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-1] were measured by the method shown below. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-1] was 7,100, and the molecular weight distribution (Mw/Mn) was 1.9. In addition, the polymer purity of polymer [A-1] was calculated from the area percentage of polymer components other than residual monomers by gel permeation chromatography (GPC). As a result, the polymer purity was 90%.

[Measurement of mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn)] Measured by gel permeation chromatography (GPC) under the following conditions, calculated in terms of polystyrene. Column: 3 pieces of TSK gel Super HM-N manufactured by Tosoh Corporation Column temperature: 40°C Sample: 0.2% tetrahydrofuran solution of polymer (A) Developing solvent: tetrahydrofuran Detector: UV detector (UV-8320 manufactured by Tosoh Corporation) Flow rate: 0.6 mL/min

(Synthesis of polymer [A-2]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-2].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-2] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-2] was 6,800, and the molecular weight distribution (Mw/Mn) was 1.9. In addition, the polymer purity of polymer [A-2] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 91%.

(Synthesis of polymer [A-3]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-3].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-3] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-3] was 6,900, and the molecular weight distribution (Mw/Mn) was 2.0. In addition, the polymer purity of polymer [A-3] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 90%.

(Synthesis of polymer [A-4]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-4].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-4] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-4] was 6,700, and the molecular weight distribution (Mw/Mn) was 1.9. In addition, the polymer purity of polymer [A-4] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 92%.

(Synthesis of polymer [A-5]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-5].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-5] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-5] was 7,100, and the molecular weight distribution (Mw/Mn) was 2.0. In addition, the polymer purity of polymer [A-5] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 95%.

(Synthesis of polymer [A-6]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-6].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-6] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-6] was 7,000, and the molecular weight distribution (Mw/Mn) was 1.8. In addition, the polymer purity of polymer [A-6] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 91%.

(Synthesis of polymer [A-7]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-7].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-7] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-7] was 6,900, and the molecular weight distribution (Mw/Mn) was 1.9. In addition, the polymer purity of polymer [A-7] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 92%.

(Synthesis of polymer [A-8]) In a flask equipped with a reflux cooler and a stirrer, 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 were added. Then, the mixture was reacted in the same manner as polymer [A-1] to obtain a polymer solution containing polymer [A-8].

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-8] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-8] was 6,900, and the molecular weight distribution (Mw/Mn) was 1.8. In addition, the polymer purity of polymer [A-8] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 92%.

(Synthesis of polymer [A-9]) 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 mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-9] were measured in the same manner as for polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-9] was 7,200, and the molecular weight distribution (Mw/Mn) was 2.0. In addition, the polymer purity of polymer [A-9] was calculated in the same manner as for 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 mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-10] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-10] was 7,000, and the molecular weight distribution (Mw/Mn) was 1.9. In addition, the polymer purity of polymer [A-10] was calculated by the same method as 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 instead of p-hydroxyphenyl methacrylate and 1,3-phenylene dimethacrylate was used instead of 1,4-phenylene dimethacrylate.

The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-11] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-11] was 7,100, and the molecular weight distribution (Mw/Mn) was 2.0. In addition, the polymer purity of polymer [A-11] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 89%.

(Polymer [A-12]) As polymer [A-12], a hydroxystyrene polymer (trade name: Maruka Lyncur MS-2 (manufactured by Maruzen Petrochemical Co., Ltd.)) was used. The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of polymer [A-12] were measured by the same method as polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-12] was 6,700, and the molecular weight distribution (Mw/Mn) was 2.0. In addition, the polymer purity of polymer [A-12] was calculated by the same method as polymer [A-1]. As a result, the polymer purity was 90%.

(Polymer [A-13]) Polymer [A-13] was obtained in the same manner as in Example 1 except that 1,4-phenylene dimethacrylate was not used. The mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained polymer [A-13] were measured in the same manner as for polymer [A-1]. As a result, the polystyrene-equivalent mass average molecular weight (Mw) of polymer [A-13] was 7,000, and the molecular weight distribution (Mw/Mn) was 1.8. In addition, the polymer purity of polymer [A-13] was calculated in the same manner as for polymer [A-1]. As a result, the polymer purity was 87%.

Tables 1 and 2 show the molar ratio, mass average molecular weight (Mw), molecular weight distribution (Mw/Mn), and polymer purity of the monomers used as raw materials for polymers [A-1] to [A-13]. In addition, the polymer purity of polymers [A-1] to [A-13] was evaluated based on the following criteria. ◎: 92% or more ○: 88~91% ×: 87% or less

[Preparation of photosensitive resin composition] (Example 1) 100 parts by mass of the 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-naphthoquinonediazide-5-sulfonate as a photosensitive component, and 2.10 parts by mass of an alkoxymethylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MW-30) as a thermosetting resin were mixed and dissolved in 80 parts by mass of methyl 3-methoxypropionate as a solvent. 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) Except that 100 parts by weight of the polymer solution (35% by weight) containing polymer [A-1] was replaced with a polymer solution (35% by weight) containing polymers [A-2] to [A-11] obtained by the above-mentioned synthesis method, the photosensitive resin compositions of Examples 2 to 11 were prepared in the same manner as in Example 1.

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

(Comparative Example 2) The photosensitive resin composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that 100 parts by weight of the polymer solution (35% by weight) containing polymer [A-1] was replaced with the polymer solution (35% by weight) containing polymer [A-13] obtained by the above-mentioned synthesis method.

[Evaluation of properties] The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were evaluated for transparency, heat-resistant transparency, heat decomposition resistance, and alkali dissolution rate by the following method. The results are shown in Tables 1 and 2.

<Transparency> A photosensitive resin composition is coated on a glass substrate so that the thickness after curing becomes 2.6μm. Then, the glass substrate coated with the photosensitive resin composition is dried (pre-baked) on a hot plate at a temperature of 110°C for 90 seconds to form a coating. Then, an ultra-high pressure mercury lamp is used as a light source to irradiate the dried coating with active light or g-line (436nm) of radiation at an exposure energy of 200mJ/ ^cm2 for full exposure. Then, the glass substrate with the exposed coating is placed in an oven and heated at 200°C for 30 minutes to thermally cure (post-bake) it to obtain a resin film.

For the glass substrate with the resin film thus obtained, a spectrophotometer (UV-1650PC (manufactured by Shimadzu Corporation)) was used to measure the minimum transmittance at a wavelength of 400 to 800 nm with the glass substrate as a blank group, and the evaluation was performed according to the following criteria. ◎(Good): 95% or more ○(Acceptable): 90 to 94% ×(Not Acceptable): 89% or less

<Heat-resistant transparency> The glass substrate with resin film used in the evaluation of <Transparency> was heat treated in air at 230°C for 2 hours and 250°C for 1 hour. Then, a spectrophotometer (UV-1650PC (manufactured by Shimadzu Corporation)) was used to measure the minimum transmittance at a wavelength of 400~800nm with the glass substrate as a blank group, and the evaluation was performed according to the following criteria. ◎(Good): 93% or more ○(Acceptable): 90~92% ×(Not acceptable): 89% or less

<Heat decomposition resistance> The film thickness of the glass substrate with a resin film used in the evaluation of the above <Heat resistance and transparency> was measured. Then, the glass substrate with a resin film used in the evaluation of the above <Heat resistance and transparency> was reheated at 200°C for 30 minutes. Then, the film thickness of the glass substrate with a resin film after reheating was measured, and the film thickness reduction rate of the resin film caused by reheating was calculated using the result, and the evaluation was performed according to the criteria shown below. ◎(Good): 10% or less ○(Acceptable): 11~15% ×(Not acceptable): 16% or more

<Alkali dissolution rate> A photosensitive resin composition is applied to a silicon wafer substrate so that the thickness after curing becomes 2.6μm. Then, the silicon wafer substrate coated with the photosensitive resin composition is dried (pre-baked) on a hot plate at a temperature of 110°C for 90 seconds to form a coating. Then, an ultra-high pressure mercury lamp is used as a light source to irradiate the dried coating with active light or g-ray (435nm) of radiation at an exposure energy of 200mJ/ ^cm2 , and full exposure is performed through a positive pattern mask.

Next, the substrate with the exposed coating was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution as a developer and developed. The dissolution rate (nm/s) of the coating per unit time was calculated from the development time of the 2.6μm coating and evaluated according to the following criteria. ◎(Good): 151~500nm/s ○(Acceptable): 101~150nm/s ×(Not Acceptable): 100nm/s or less

As shown in Table 1 and Table 2, the photosensitive resin compositions of Examples 1 to 11 were evaluated as ◎ (good) or ○ (acceptable) for transparency, heat-resistant transparency, heat-decomposition resistance, and alkali dissolution rate. In particular, Examples 4, 5, 7, and 8, which contain polymers [A-4] [A-5] [A-7] [A-8] having more constituent units from monomers having hydroxyalkyl groups and ethylenically unsaturated groups, and Example 9, [A-9], which contains more constituent units from phenyl di(meth)acrylate, were evaluated as ◎ (good) for transparency, heat-resistant transparency, heat-decomposition resistance, and alkali dissolution rate.

In contrast, the photosensitive resin composition of Comparative Example 1, which includes a polymer [A-12] that does not contain a constituent unit derived from hydroxyphenyl (meth)acrylate and a constituent unit derived from phenyl di(meth)acrylate, was evaluated as × (not acceptable) for heat resistance transparency, and the heat resistance was insufficient. In addition, the photosensitive resin composition of Comparative Example 2, which includes a polymer [A-13] that does not contain a constituent unit derived from phenyl di(meth)acrylate, was evaluated as × (not acceptable) for heat decomposition resistance, and the heat resistance was insufficient. [Possibility of Industrial Utilization]

According to the present invention, a resin composition capable of forming a resin film having excellent image development, transparency and heat resistance is provided. The resin film obtained by the present invention can be used for various purposes such as a planarization film, an interlayer insulating film, a protective film, a microlens, etc. used in an organic EL display device and a liquid crystal display device.

Claims (11)

A resin composition characterized by containing a polymer (A) having at least a constituent unit derived from hydroxyphenyl (meth)acrylate and a constituent unit derived from phenyl di(meth)acrylate, and a photosensitive component (B), wherein the polymer (A) further has a constituent unit derived from a monomer having a hydroxyalkyl group and an ethylenically unsaturated group, and the photosensitive component (B) is a compound containing a quinonediazide group. The resin composition of claim 1, wherein the molar ratio of the constituent units derived from hydroxyphenyl (meth)acrylate to the constituent units derived from phenyl di(meth)acrylate is 99.99:0.01~99.00:1.00. The resin composition of claim 1 or 2, wherein the total content of the constituent units derived from hydroxyphenyl (meth)acrylate and the constituent units derived from phenyl di(meth)acrylate in the aforementioned polymer (A) is 40 to 100 mol%. The resin composition of claim 1 or 2, wherein the total content of the constituent units derived from hydroxyphenyl (meth)acrylate and the constituent units derived from phenyl di(meth)acrylate in the aforementioned polymer (A) is 50-90 mol%, and the content of the constituent units derived from monomers having hydroxyalkyl groups and ethylenically unsaturated groups is 1-20 mol%. The resin composition of claim 1 or 2 contains 5 to 60 parts by weight of the aforementioned photosensitive component (B) relative to 100 parts by weight of the aforementioned polymer (A). The resin composition of claim 1 or 2 contains a thermosetting resin (C). A resin film comprising a cured product of a resin composition as described in any one of claims 1 to 6. The resin composition of claim 1 or 2, wherein the content of the constituent units derived from the aforementioned di(meth)acrylate phenyl ester in the aforementioned polymer (A) is 0.15~0.5 mol%. The resin composition of claim 1 or 2, wherein the aforementioned polymer (A) further has one or more constituent units selected from styrene compounds and ethylenically unsaturated monomers containing glyoxypropyl groups. The resin composition of claim 1 or 2, wherein the mass average molecular weight Mw of the aforementioned polymer (A) is 1500~20000. The resin composition of claim 1 or 2, wherein the molecular weight distribution (Mw/Mn) of the aforementioned polymer (A) is 1.1~2.5.