JP2018150423A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which may form a hardening film having excellent solvent resistance, heat resistance, transparency and flattening ability, and form a color filter lower layer film which suppress generation of residue of color resist upon forming of a color filter on the hardening film.SOLUTION: There are provided a thermosetting resin composition, a producing method for a hardening film, a protect film, a flattening film or a color filter lower layer film using the thermosetting resin composition, a formation method for a color filter, in which the thermosetting resin composition contains a self crosslinking copolymer and solvent. The self crosslinking copolymer includes structural units represented by a specific general structural formula having a carboxyl group and structural units represented by a specific general structural formula having a glycidyl group.SELECTED DRAWING: Figure 1

Description

The present invention relates to a thermosetting resin composition, a thermosetting resin composition for a protective film, a thermosetting resin composition for a flattening film, a thermosetting resin composition for a color filter underlayer film, and the thermosetting resin. The present invention relates to a method for producing a cured film, a protective film, a planarizing film, or a color filter underlayer film using the composition.

Electronic devices such as CCD / CMOS image sensors, liquid crystal displays, and organic EL displays are exposed to high temperatures such as processing exposed to chemicals such as solvents or acids or alkali solutions, sputtering, dry etching, solder reflow, etc. in the manufacturing process. The process exposed to is performed. In order to prevent the element from being deteriorated or damaged by such treatment, a cured film having resistance to such treatment is formed on the element as a protective film. Such a protective film is required to have solvent resistance, high transparency, heat resistance, and the like.

The electronic device has unevenness caused by, for example, a color filter, a circuit wiring portion, a light shielding film, or an inner lens. For this reason, the cured film is also required to have level difference flatness from the viewpoint of ensuring a process margin when manufacturing an electronic device and ensuring uniformity of device characteristics. Further, when a color filter is formed on the cured film, the cured film is also required to have a property of suppressing the generation of a color resist residue (Patent Documents 1 to 4).

For the formation of the color filter, for example, color resists of three colors of red, green and blue containing pigments or dyes are generally used. In the method of forming a color filter using three color resists, first, a first color resist is applied, and exposure, development, and heat treatment are performed to form a first color resist pattern. Thereafter, similarly to the first color resist pattern, second and third color resist patterns are formed to form a color filter.

In such a color filter forming method, it is important to suppress the generation of color resist residues during the formation of the color resist pattern in order to suppress the deterioration of the color reproducibility of the color filter and the decrease in the yield of the device equipped with the color filter. Become. For this reason, when a color filter is formed on the cured film, the cured film is required to have a property of suppressing the generation of the color resist residue as described above.

JP 2000-344866 A JP 2008-031370 A Japanese Patent No. 4222457 International Publication No. 2013/005619

The present invention has been made based on the above circumstances, and its purpose is to form a cured film having excellent solvent resistance, heat resistance, transparency and flatness, and on the cured film. An object of the present invention is to provide a thermosetting resin composition capable of forming a color filter underlayer film capable of suppressing the generation of a color resist residue when forming a color filter. Another object of the present invention is to provide a cured film, a protective film, a planarizing film and a color filter underlayer film having excellent solvent resistance, heat resistance and transparency.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention is a self-crosslinkable copolymer having at least one of structural units represented by the following formulas (1-1) to (1-5) and a structural unit represented by the following formula (2). And a thermosetting resin composition containing a solvent.
(In the formula, X represents an alkylene group having 1 to 6 carbon atoms, Z represents a glycidyl group, a glycidyloxyethyl group, a glycidyloxypropyl group, a glycidyloxybutyl group, a 3,4-epoxycyclohexyl group, 3 , 4-epoxycyclohexylmethyl group, 3,4-epoxycyclohexylethyl group, 3,4-epoxycyclohexylmethyloxyethyl group, 3,4-epoxycyclohexylmethyloxypropyl group or 3,4-epoxycyclohexylmethyloxybutyl group Represents.)

The structural unit represented by the formula (2) is, for example, at least one of the structural units represented by the following formulas (2-1) to (2-7).

The self-crosslinking copolymer may further be a copolymer having at least one of structural units represented by the following formulas (3) and (4).
(Wherein R ⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, and the alkyl group, the cyclohexyl group, the phenyl group and the benzyl group are A part or all of the hydrogen atoms may be substituted with a hydroxy group or a carboxyl group, R ⁵ represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 5.)

The present invention also provides a cured film, a protective film, a planarizing film, or a color filter lower layer by applying the thermosetting resin composition onto a substrate and then baking the thermosetting resin composition using a heating means. This is a method for producing a film.

The present invention also includes a step of applying the thermosetting resin composition on a substrate and then heating to form a color filter underlayer film, applying a color resist on the color filter underlayer film and heating to form a color resist film And a color filter forming method including a step of performing exposure, development and rinsing on the color resist film to form a color resist pattern.

The thermosetting resin composition of the present invention has at least one of the structural units represented by the formulas (1-1) to (1-5) and the structural unit represented by the formula (2). Since it contains a self-crosslinkable copolymer, a cured film prepared from the composition that does not contain a curing agent as an essential component has excellent solvent resistance, heat resistance, transparency, and flatness. Thereby, the cured film produced from the thermosetting resin composition of the present invention is exposed to a solvent or a chemical solution such as an acid or alkali solution in the production process or the formation process of peripheral devices such as wiring. In addition, when a process exposed to a high temperature such as sputtering, dry etching, or solder reflow is performed, the possibility that the element is deteriorated or damaged can be significantly reduced.
In addition, when a protective film or a flattened film is prepared from the thermosetting resin composition of the present invention and a resist is applied thereon, and when an electrode / wiring forming step is performed, there is a problem of mixing with the resist. In addition, problems such as deformation and peeling of the protective film or flattening film due to chemicals can be significantly reduced.
Further, when a color filter underlayer film is formed from the thermosetting resin composition of the present invention and a color resist is applied thereon, the problem of color resist residue generation can be significantly reduced.
Furthermore, for example, when a planarizing film is produced from the thermosetting resin composition of the present invention on a substrate having unevenness caused by a color filter, a circuit wiring portion, a light shielding film or an inner lens, It is possible to ensure a process margin and uniformity of device characteristics.
Therefore, the thermosetting resin composition of the present invention is suitable as a material for forming a protective film, a planarizing film, or a color filter underlayer film.

 The present invention is a thermosetting resin composition containing a self-crosslinkable copolymer and a solvent. Hereinafter, details of each component will be described. The solid content obtained by removing the solvent from the thermosetting resin composition of the present invention is usually 0.01% by mass to 50% by mass.

<Self-crosslinking copolymer>
The self-crosslinking copolymer contained in the thermosetting resin composition of the present invention includes at least one of structural units represented by the above formulas (1-1) to (1-5) containing a carboxyl group and It is a copolymer having a structural unit represented by the formula (2) containing an epoxy group. From the viewpoint of the excellent flatness that is the object of the present invention and the suppression of color residue generation, structural units formed from acrylic acid or acrylate are preferred to structural units formed from methacrylic acid or methacrylate.

Specific examples of the compound (monomer) forming the structural unit represented by the formula (1-1) to the formula (1-5) include acrylic acid, 2-carboxyethyl acrylate, 2-carboxypropyl acrylate, 3- Carboxypropyl acrylate, 2-carboxybutyl acrylate, 3-carboxybutyl acrylate, 4-carboxybutyl acrylate, 5-carboxypentyl acrylate, 6-carboxyhexyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, 2-acryloyloxybutyl succinic acid, 2-acryloyloxypentyl succinic acid, 2-acryloyloxyhexyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl Sahydrophthalic acid, 2-acryloyloxybutylhexahydrophthalic acid, 2-acryloyloxypentylhexahydrophthalic acid, 2-acryloyloxyhexylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxypropylphthalic acid, Examples include 2-acryloyloxybutylphthalic acid, 2-acryloyloxypentylphthalic acid, and 2-acryloyloxyhexylphthalic acid. These compounds may be used alone or in combination of two or more.

Specific examples of the compound (monomer) forming the structural unit represented by the formula (2) include glycidyl acrylate, 2-hydroxyethyl acrylate glycidyl ether, 2-hydroxypropyl acrylate glycidyl ether, and 3-hydroxypropyl acrylate glycidyl ether. 2-hydroxybutyl acrylate glycidyl ether, 3-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 2- (3,4-epoxy Cyclohexyl) ethyl acrylate, 2- (3,4-epoxycyclohexylmethyloxy) ethyl acrylate, 2- (3,4-epoxycyclo) Xylmethyloxy) propyl acrylate, 3- (3,4-epoxycyclohexylmethyloxy) propyl acrylate, 2- (3,4-epoxycyclohexylmethyloxy) butyl acrylate, 3- (3,4-epoxycyclohexylmethyloxy) butyl Acrylate and 4- (3,4-epoxycyclohexylmethyloxy) butyl acrylate. These monomers may be used alone or in combination of two or more.

Among these compounds (monomers), glycidyl acrylate, 2-hydroxyethyl acrylate glycidyl ether, 2-hydroxypropyl acrylate glycidyl ether, 3-hydroxypropyl acrylate glycidyl ether, 2-hydroxybutyl acrylate glycidyl ether, 3-hydroxybutyl acrylate glycidyl Ether and 4-hydroxybutyl acrylate glycidyl ether are preferable because desired effects are obtained, and 4-hydroxybutyl acrylate glycidyl ether is preferable from the viewpoint of availability.

The self-crosslinking copolymer contained in the thermosetting resin composition of the present invention includes at least one of the structural units represented by the formulas (1-1) to (1-5) and the formula (2). In addition to the structural unit represented by (), at least one of the structural units represented by the formula (3) and the formula (4) may be included. By adjusting the content of the structural unit represented by the above formulas (3) and (4), the optical characteristics, dry etching rate, thermal characteristics, and step flatness of the cured film can be adjusted in a wider range. Is possible.

Specific examples of the compound (monomer) that forms the structural unit represented by the formula (3) and the compound (monomer) that forms the structural unit represented by the formula (4) include maleimide, N-methylmaleimide, N -Ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N-hydroxymaleimide, N-hydroxymethylmaleimide, N- (2-carboxyethyl) maleimide, N- (4-carboxyphenyl) maleimide, 4-maleimidobutyric acid, 2-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2,3-dihydroxyphenyl (meta ) Acrylate, 2,4-dihydroxy Phenyl (meth) acrylate, 3,4-dihydroxyphenyl (meth) acrylate, 3,5-dihydroxyphenyl (meth) acrylate, 2,3,4-trihydroxyphenyl (meth) acrylate, 3,4,5-trihydroxy Examples include phenyl (meth) acrylate and pentahydroxyphenyl (meth) acrylate. These compounds may be used alone or in combination of two or more. In the present specification, (meth) acrylate means methacrylate and acrylate.

In the self-crosslinkable copolymer having at least one of the structural units represented by the formulas (1-1) to (1-5) and the structural unit represented by the formula (2), these structures The content of at least one of the structural units represented by the formulas (1-1) to (1-5) is 20 mol% to 80 mol%, preferably 30 mol% to 100 mol% of the sum of the units. 70 mol%, more preferably 40 mol% to 60 mol%. The content of the structural unit represented by the formula (2) is 20 mol% to 80 mol%, preferably 30 mol% to 70 mol%, more preferably 40 mol% to 60 mol%.

The self-crosslinkable copolymer contained in the thermosetting resin composition of the present invention is at least one of the structural units represented by the formula (1-1) to the formula (1-5) and the formula (2). In addition to the structural unit represented by formula (3), when having at least one of the structural units represented by formula (3) and formula (4), the formula (1) The content of at least one of the structural units represented by -1) to formula (1-5) is 10 mol% to 60 mol%, preferably 20 mol% to 50 mol%. The content of the structural unit represented by the formula (2) is 10 mol% to 60 mol%, preferably 20 mol% to 50 mol%. The content of at least one of the structural units represented by the formulas (3) and (4) is 5 mol% to 80 mol%, preferably 10 mol% to 70 mol%.

The weight average molecular weight of the self-crosslinkable copolymer is usually 1,000 to 100,000, preferably 3,000 to 50,000. The weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).

The content of the self-crosslinking copolymer in the thermosetting resin composition of the present invention is, for example, 1% by mass to 99% by mass based on the content in the solid content of the resin composition. Or 5 mass% to 95 mass%, or 50 mass% to 100 mass%.

In the present invention, the method for obtaining the self-crosslinkable copolymer is not particularly limited, but generally, at least one of the structural units represented by the formulas (1-1) to (1-5) is used. The compound (monomer) that forms the compound and the compound (monomer) that forms the structural unit represented by the formula (2), or the compound (monomer) and the structural unit represented by the formula (3) and the formula (4) Of these, the compound (monomer) forming at least one of them is usually obtained by a polymerization reaction in a solvent in the presence of a polymerization initiator at a temperature of usually 50 ° C to 120 ° C. The self-crosslinkable copolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the thermosetting resin composition of the present invention without isolation in this state.

Further, the solution of the self-crosslinkable copolymer obtained as described above is put into a poor solvent such as hexane, diethyl ether, toluene, methanol, water and the like which has been stirred to reprecipitate the copolymer, The formed precipitate is decanted or filtered, and after washing as necessary, the copolymer can be made into an oily product or powder by drying at room temperature or heating under normal pressure or reduced pressure. By such an operation, the unreacted compound coexisting with the copolymer and the polymerization initiator can be removed. In the present invention, the oily product or powder of the copolymer may be used as it is, or the oily product or powder may be used, for example, as a solution by re-dissolving in a solvent described later. .

The method for preparing the thermosetting resin composition of the present invention is not particularly limited. For example, at least one of the structural units represented by the formula (1-1) to the formula (1-5) and the formula ( 2) a self-crosslinkable copolymer having a structural unit represented by formula (2), or at least one of the structural units represented by formula (1-1) to formula (1-5) and formula (2). And a method of dissolving a self-crosslinkable copolymer having at least one of the structural units represented by formula (3) and formula (4) in a solvent to obtain a uniform solution. It is done. Furthermore, in an appropriate stage of this preparation method, there may be mentioned a method in which other additives are further added and mixed as necessary.

<Solvent>
The solvent contained in the thermosetting resin composition of the present invention is not particularly limited as long as it dissolves the self-crosslinking copolymer contained in the resin composition. Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxy Ethyl loxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Mention may be made of ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, γ-butyrolactone, N-methylpyrrolidone, and N-ethylpyrrolidone. it can. These solvents may be used alone or in combination of two or more.

Among the solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl from the viewpoint of improving the leveling property of the coating film formed by applying the thermosetting resin composition of the present invention on the substrate. Ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, methyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclopentanone, cyclohexanone and γ-butyrolactone are preferred.

Moreover, the thermosetting resin composition of this invention can also contain a hardening accelerator in order to improve sclerosis | hardenability. Examples of the curing accelerator include triphenylphosphine, tributylphosphine, tris (4-methylphenyl) phosphine, tris (4-nonylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxy). Phenyl) phosphine, phosphines such as triphenylphosphine triphenylborane, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, tetra Phenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (4-methylphenyl) borate, tetrafe Quaternary phosphonium salts such as ruphosphonium tetra (4-methoxyphenyl) borate, tetraphenylphosphonium tetra (4-fluorophenyl) borate, tetraethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethyl Quaternary ammonium salts such as ammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, 2-methylimidazole, 2-ethyl-4 -Imidazoles such as methylimidazole, -Imidazolium salts such as ethyl-4-methylimidazole tetraphenylborate, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc. Diazabicycloalkenes and formate of 1,8-diazabicyclo [5.4.0] -7-undecene, 2-ethylhexanoic acid of 1,8-diazabicyclo [5.4.0] -7-undecene Salt, p-toluenesulfonate of 1,8-diazabicyclo [5.4.0] -7-undecene, 2-ethylhexanoate of 1,5-diazabicyclo [4.3.0] -5-nonene, etc. And organic acid salts of diazabicycloalkene.

Examples of commercially available curing accelerators include Hishicolin (registered trademark) PX-4C, PX-4B, PX-4MI, PX-412B, PX-416B, PX-2B, and PX-82B. PX-4BT, PX-4MP, PX-4ET, PX-4PB (manufactured by Nippon Chemical Industry Co., Ltd.), Hokuko TPP (registered trademark), TPTP (registered trademark), DPCP (registered trademark), TPP-EB (registered trademark), TPP-ZC (registered trademark), DPPB (registered trademark), EMZ-K (registered trademark), DBNK (registered trademark), TPP-MK (registered trademark), TPP-K (registered trademark) ], TPP-S [registered trademark], TPP-SCN [registered trademark], TPP-DCA [registered trademark], TPPB-DCA [registered trademark], TPP-PB [registered trademark], Hokuko TBP-BB [registered trademark] Mark], TBPDA (registered trademark), TPPO (registered trademark), PPQ (registered trademark), TOTP (registered trademark), TMTP (registered trademark), TPAP (registered trademark), DPCP (registered trademark), TCHP (registered trademark) , Hokuko TBP (registered trademark), TTBuP (registered trademark), TOPP (registered trademark), DPPST (registered trademark), TBPH (registered trademark), TPP-MB (registered trademark), TPP-EB (registered trademark), TPP- BB [Registered Trademark], TPP-MOC [Registered Trademark], TPP-ZC [Registered Trademark], TTBuP-K [Registered Trademark] (made by Hokuko Chemical Co., Ltd.), Curazole [Registered Trademark] SIZ, 2MZ -H, C11Z, 1.2DEMZ, 2E4MZ, 2PZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN C11Z-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZA-PW, C11Z-A, 2E4MZ-A, 2MA-OK, 2PZ-OK, 2PHZ -PW, 2P4MHZ, TBZ, SFZ, 2PZL-T (manufactured by Shikoku Kasei Kogyo Co., Ltd.), U-CAT [registered trademark] SA 1, SA 102, SA 102-50, SA 106, SA 112, SA 506, SA 603, SA 810, SA 810, SA 831, SA 841, SA 851, 881, 5002, 5003, 3512T, 3513N, 18X, 410 1102, 2024, 2026, 2030, 2110, 2313, 651M, 660M, 420A, DBU [ Recorded trademark], DBN, POLYCAT 8 (or more, Apro Co., Ltd.) can be mentioned. These curing accelerators may be used alone or in combination of two or more.

When the curing accelerator is used, the content in the thermosetting resin composition of the present invention is 0.1% by mass to 10% by mass based on the content in the solid content of the resin composition. The content is preferably 0.5% by mass to 8% by mass, and more preferably 1% by mass to 6% by mass.

Moreover, the thermosetting resin composition of this invention can also contain surfactant for the purpose of improving applicability | paintability. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like.

Commercially available surfactants include, for example, Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (registered trademark) F-171, F- 173, R-30, R-40, R-40-LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Corporation), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX 240G, DFX-18, etc. Ftergent Series (or, Co. Neos Co., Ltd.) of can be mentioned fluorine-based surfactants such as, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.). These surfactants may be used alone or in combination of two or more.

When the surfactant is used, the content in the thermosetting resin composition of the present invention is usually 0.001% by mass to 5% by mass based on the content in the solid content of the resin composition. Yes, preferably 0.01% to 4% by mass, more preferably 0.03% to 3% by mass.

As long as the effects of the present invention are not impaired, the thermosetting resin composition of the present invention can be used as necessary with a curing agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, an adhesion aid, and an antifoaming agent. Additives such as agents can be included.

The thermosetting resin composition of the present invention can be prepared, for example, by dissolving the above-described components in a solvent, and is used in a uniform solution state. The prepared composition is preferably used after being filtered using a filter or the like.

<Method for producing cured film, protective film and planarizing film>
A method for producing a cured film, a protective film, or a planarizing film using the thermosetting resin composition of the present invention will be described. The heat of the present invention is applied to a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or a color filter are formed) by an appropriate coating method such as a spinner or a coater. After applying the curable resin composition, it is baked and cured using a heating means such as a hot plate or an oven to produce a cured film, a protective film, or a flattened film. The baking conditions are appropriately selected from a baking temperature of 80 ° C. to 300 ° C. and a baking time of 0.5 minutes to 3 hours. You may bake 2 steps or more at different baking temperature. The film thickness of the film produced from the thermosetting resin composition of the present invention is, for example, 0.001 μm to 100 μm, and preferably 0.01 μm to 10 μm.

<Method for producing color filter underlayer film>
A method for producing a color filter underlayer film using the thermosetting resin composition of the present invention will be described. The present invention is applied to a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer and a substrate on which various metal films, a planarizing film, etc. are formed) by an appropriate coating method such as a spinner or a coater. After applying the thermosetting resin composition, it is baked and cured using a heating means such as a hot plate or an oven to produce a color filter underlayer film. The baking conditions are appropriately selected from a baking temperature of 80 ° C. to 300 ° C. and a baking time of 0.5 minutes to 3 hours. You may bake 2 steps or more at different baking temperature. The film thickness of the film produced from the thermosetting resin composition of the present invention is, for example, 0.001 μm to 100 μm, and preferably 0.01 μm to 10 μm.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.
[Measurement of Weight Average Molecular Weight of Copolymer Obtained in Synthesis Example below]
Apparatus: GPC system column manufactured by Shimadzu Corporation Column: Shodex [registered trademark] KF-804L and 803L
Column oven: 40 ° C
Flow rate: 1 mL / min Eluent: Tetrahydrofuran

[Synthesis of copolymer]
<Synthesis Example 1>
5.0 g of acrylic acid, 13.9 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 1.1 g of 2,2′-azobisisobutyronitrile were added to 37.2 g of propylene glycol monomethyl ether. Then, this solution was dropped into a flask in which 22.9 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction was further continued for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1) and formula (2-1) (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained polymer was 13,600.

<Synthesis Example 2>
4.0 g of propylene glycol monomethyl ether was added to 4.0 g of acrylic acid, 16.7 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 1.0 g of 2,2′-azobisisobutyronitrile. Then, this solution was dropped into a flask in which 24.8 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction was further continued for 18 hours to obtain a polymer solution having a structural unit represented by the formula (1-1) and formula (2-1) (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained polymer was 16,200.

<Synthesis Example 3>
7.5 g of acrylic acid, 13.9 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 1.1 g of 2,2′-azobisisobutyronitrile were added to 41.7 g of propylene glycol monomethyl ether. Then, this solution was dropped into a flask in which 25.7 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction was further continued for 18 hours to obtain a polymer solution having a structural unit represented by the formula (1-1) and formula (2-1) (solid content concentration 25% by mass). The weight average molecular weight Mw of the obtained polymer was 13,100.

<Synthesis Example 4>
Propylene glycol containing 2.8 g of acrylic acid, 12.5 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 10.6 g of maleimide and 1.1 g of 2,2′-azobisisobutyronitrile. After being dissolved in 41.3 g of monomethyl ether, this solution was dropped into a flask in which 25.4 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1), and formula (3-1) (solid content concentration: 25% by mass) ) The weight average molecular weight Mw of the obtained polymer was 4,900.

<Synthesis Example 5>
4.5 g of acrylic acid, 12.5 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 4.2 g of N-methylmaleimide and 1.1 g of 2,2′-azobisisobutyronitrile Was dissolved in 41.4 g of propylene glycol monomethyl ether, and this solution was dropped into a flask in which 25.5 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1) and formula (3-2) (solid content concentration: 25% by mass) ) The weight average molecular weight Mw of the obtained polymer was 9,500.

<Synthesis Example 6>
4.4 g of acrylic acid, 12.2 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 4.8 g of N-hydroxymaleimide and 1.1 g of 2,2′-azobisisobutyronitrile Was dissolved in 40.8 g of propylene glycol monomethyl ether, and this solution was dropped into a flask in which 25.1 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1) and formula (3-3) (solid content concentration: 25% by mass) ) The weight average molecular weight Mw of the obtained polymer was 37,000.

<Synthesis Example 7>
4.5 g of acrylic acid, 12.5 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 4.2 g of N-phenylmaleimide and 1.1 g of 2,2′-azobisisobutyronitrile Was dissolved in 41.4 g of propylene glycol monomethyl ether, and this solution was dropped into a flask in which 25.5 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1) and formula (3-4) (solid content concentration: 25% by mass) ) The weight average molecular weight Mw of the obtained polymer was 6,000.

<Synthesis Example 8>
2.0 g of acrylic acid, 5.6 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 7.6 g of N- (4-hydroxyphenyl) maleimide and 2,2′-azobisisobuty After 0.8 g of ronitrile was dissolved in 47.6 g of propylene glycol monomethyl ether, this solution was dropped into a flask in which 15.9 g of propylene glycol monomethyl ether was maintained at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1) and formula (3-5) (solid content concentration 20% by mass). ) The weight average molecular weight Mw of the obtained polymer was 3,400.

<Synthesis Example 9>
2.5 g of acrylic acid, 7.0 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)), 9.4 g of 4-hydroxyphenyl methacrylate, and 2,2′-azobisisobutyronitrile After 9 g was dissolved in 36.8 g of propylene glycol monomethyl ether, this solution was dropped into a flask in which 22.7 g of propylene glycol monomethyl ether was maintained at 80 ° C. over 4 hours. After completion of the dropwise addition, the mixture is further reacted for 18 hours to obtain a polymer solution having a structural unit represented by the following formula (1-1), formula (2-1) and formula (4-1) (solid content concentration: 25% by mass) ) The weight average molecular weight Mw of the obtained polymer was 15,500.

<Synthesis Example 10>
12.0 g of 2-acryloyloxyethyl succinic acid, 11.1 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 1.2 g of 2,2′-azobisisobutyronitrile were added to propylene glycol After being dissolved in 36.4 g of monomethyl ether, this solution was dropped into a flask in which 20.2 g of propylene glycol monomethyl ether was kept at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction was further continued for 18 hours to obtain a polymer solution (solid content concentration of 30% by mass) having structural units represented by the following formulas (1-3-1) and (2-1). The weight average molecular weight Mw of the obtained polymer was 7,600.

<Synthesis Example 11>
5.0 g of 2-carboxyethyl acrylate, 7.0 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 0.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) After being dissolved in 29.3 g of propylene glycol monomethyl ether, this solution was dropped into a flask in which 41.8 g of propylene glycol monomethyl ether was kept at 65 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a polymer solution having a structural unit represented by the following formula (1-2-1) and formula (2-1) (solid content concentration: 15% by mass). The weight average molecular weight Mw of the obtained polymer was 15,600.

<Synthesis Example 12>
After dissolving 4.0 g of methacrylic acid, 6.6 g of glycidyl methacrylate, and 0.6 g of 2,2′-azobisisobutyronitrile in 33.7 g of propylene glycol monomethyl ether, this solution was added to 30. propylene glycol monomethyl ether. 0 g was dropped into a flask maintained at 65 ° C. over 2 hours. After completion of the dropwise addition, the reaction is further performed for 6 hours, and a polymer solution having neither the structural unit represented by the formula (1-1) to the formula (1-5) nor the structural unit represented by the formula (2). (Solid concentration 15% by mass) was obtained. The weight average molecular weight Mw of the obtained polymer was 26,800.

<Synthesis Example 13>
Propylene glycol monomethyl ether containing 8.0 g of 4-hydroxyphenyl methacrylate, 11.0 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE (manufactured by Nippon Kasei Co., Ltd.)) and 0.8 g of 2,2′-azobisisobutyronitrile. After being dissolved in 36.8 g, this solution was dropped into a flask in which 22.6 g of propylene glycol monomethyl ether was maintained at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction was further continued for 18 hours to obtain a polymer solution (solid content concentration 25% by mass) having no structural unit represented by the above formulas (1-1) to (1-5). The weight average molecular weight Mw of the obtained polymer was 11,000.

<Synthesis Example 14>
After dissolving 10.0 g of 4-hydroxyphenyl methacrylate, 8.0 g of glycidyl methacrylate, and 1.1 g of 2,2′-azobisisobutyronitrile in 35.4 g of propylene glycol monomethyl ether, this solution was added to propylene glycol monomethyl. 21.8 g of ether was dropped into a flask maintained at 80 ° C. over 4 hours. After completion of the dropwise addition, the reaction is further continued for 18 hours, and a polymer solution having neither the structural unit represented by the formula (1-1) to the formula (1-5) nor the structural unit represented by the formula (2). (Solid content concentration 25 mass%) was obtained. The weight average molecular weight Mw of the obtained polymer was 18,000.

<Synthesis Example 15>
After dissolving 20.0 g of methyl methacrylate, 2.4 g of 2-hydroxyethyl methacrylate, 1.2 g of methacrylic acid and 1.7 g of 2,2′-azobisisobutyronitrile in 37.8 g of propylene glycol monomethyl ether acetate, This solution was dropped into a flask in which 21.0 g of propylene glycol monomethyl ether acetate was maintained at 70 ° C. over 4 hours. After completion of the dropwise addition, the reaction is further continued for 18 hours, and a polymer solution having neither the structural unit represented by the formula (1-1) to the formula (1-5) nor the structural unit represented by the formula (2). (Solid content concentration 30.0 mass%) was obtained. The weight average molecular weight Mw of the obtained polymer was 8,200.

<Synthesis Example 16>
8.0 g of styrene, 3.2 g of 2-hydroxyethyl acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Karenz [registered trademark] MOI-BP (manufactured by Showa Denko KK)) After 8 g and 1.4 g of 2,2′-azobisisobutyronitrile were dissolved in 39.8 g of propylene glycol monomethyl ether, this solution was placed in a flask in which 24.5 g of propylene glycol monomethyl ether was kept at 70 ° C. It was dripped over 4 hours. After completion of the dropwise addition, the reaction is further continued for 18 hours, and a polymer solution having neither the structural unit represented by the formula (1-1) to the formula (1-5) nor the structural unit represented by the formula (2). (Solid content concentration 25.0 mass%) was obtained. The weight average molecular weight Mw of the obtained polymer was 19,000.

[Preparation of thermosetting resin composition]
<Example 1>
A solution of 4.0 g of the polymer obtained in Synthesis Example 1 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 2>
A solution of 4.0 g of the polymer obtained in Synthesis Example 2 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 3>
A solution of 4.0 g of the polymer obtained in Synthesis Example 3 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 4>
A solution of 4.0 g of the polymer obtained in Synthesis Example 4 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 5>
A solution of 4.0 g of the polymer obtained in Synthesis Example 5 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 6>
A solution of 4.0 g of the polymer obtained in Synthesis Example 6 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 7>
4.0 g of the polymer solution obtained in Synthesis Example 7 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 8>
A solution of 5.0 g of the polymer obtained in Synthesis Example 8 was dissolved in 30.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 9>
4.0 g of the polymer solution obtained in Synthesis Example 9 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 10>
4.0 g of the polymer solution obtained in Synthesis Example 1 and 0.01 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 31.6 g of propylene glycol monomethyl ether and 14.8 g of ethyl lactate. It was set as the solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 11>
4.0 g of the polymer solution obtained in Synthesis Example 1 and 0.04 g of tris (4-methoxyphenyl) phosphine as a curing accelerator were dissolved in 29.4 g of propylene glycol monomethyl ether and 13.9 g of propylene glycol monomethyl ether acetate. To make a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 12>
4.0 g of the polymer solution obtained in Synthesis Example 1 and 0.04 g of 2-ethyl-4-methylimidazole as a curing accelerator were dissolved in 32.7 g of propylene glycol monomethyl ether and 15.3 g of ethyl lactate to obtain a solution. did. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 13>
4.0 g of the polymer solution obtained in Synthesis Example 1 and 0.04 g of U-CAT (registered trademark) SA 102 (manufactured by San Apro Co., Ltd.) as a curing accelerator, 32.7 g of propylene glycol monomethyl ether and ethyl lactate 15 Dissolved in 3 g to give a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 14>
4.0 g of the polymer solution obtained in Synthesis Example 1, 0.04 g of U-CAT (registered trademark) SA 603 (manufactured by San Apro Co., Ltd.) as a curing accelerator, and DFX-18 (Neos Co., Ltd.) as a surfactant. 0.01 g) was dissolved in 32.3 g of propylene glycol monomethyl ether and 15.1 g of ethyl lactate to prepare a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 15>
4.0 g of the polymer solution obtained in Synthesis Example 4 and 0.04 g of tris (4-methoxyphenyl) phosphine as a curing accelerator were dissolved in 29.4 g of propylene glycol monomethyl ether and 13.9 g of propylene glycol monomethyl ether acetate. To make a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 16>
4.0 g of the polymer solution obtained in Synthesis Example 7 and 0.03 g of tris (4-methoxyphenyl) phosphine as a curing accelerator were dissolved in 29.1 g of propylene glycol monomethyl ether and 13.7 g of propylene glycol monomethyl ether acetate. To make a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 17>
4.0 g of the polymer solution obtained in Synthesis Example 7 and 0.02 g of U-CAT [registered trademark] 18X (manufactured by San Apro Co., Ltd.) as a curing accelerator, 32.0 g of propylene glycol monomethyl ether and 15. A solution was prepared by dissolving in 0 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 18>
4.0 g of the polymer solution obtained in Synthesis Example 7 and 0.01 g of Hishicolin (registered trademark) PX-4BT (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator, 31.6 g of propylene glycol monomethyl ether and ethyl lactate A solution was prepared by dissolving in 14.8 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 19>
A solution of 3.3 g of the polymer obtained in Synthesis Example 10 and 0.01 g of DFX-18 (manufactured by Neos) as a surfactant were dissolved in 32.0 g of propylene glycol monomethyl ether and 14.7 g of ethyl lactate. It was set as the solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Example 20>
6.5 g of the polymer solution obtained in Synthesis Example 11 and 0.01 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in 28.3 g of propylene glycol monomethyl ether and 14.5 g of ethyl lactate. It was set as the solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Comparative Example 1>
A solution of 6.0 g of the polymer obtained in Synthesis Example 12 was dissolved in 25.8 g of propylene glycol monomethyl ether and 13.2 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Comparative Example 2>
A solution of 4.0 g of the polymer obtained in Synthesis Example 13 was dissolved in 28.1 g of propylene glycol monomethyl ether and 13.3 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Comparative Example 3>
A solution of 4.0 g of the polymer obtained in Synthesis Example 14 was dissolved in 28.1 g of propylene glycol monomethyl ether and 13.3 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Comparative example 4>
2.3 g of the polymer solution obtained in Synthesis Example 15 and methylated melamine resin (Nicarac [registered trademark] MX-706 (2-propanol solution, solid concentration 70% by mass)) as a crosslinking agent (Sanwa Chemical Co., Ltd.) 0.2 g) was dissolved in 11.2 g of propylene glycol monomethyl ether and 23.9 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

<Comparative Example 5>
A solution of 4.0 g of the polymer obtained in Synthesis Example 16 was dissolved in 31.3 g of propylene glycol monomethyl ether and 14.7 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the thermosetting resin composition.

[Solvent resistance test]
Each of the thermosetting resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 5 was applied onto a silicon wafer using a spin coater, and then on a hot plate at 100 ° C. for 1 minute. Baking was performed at 230 ° C. for 1.5 minutes to form a film having a thickness of 0.06 μm. For these membranes, an aqueous solution of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, 2-propanol and tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) having a concentration of 2.38% by mass. Each was immersed for 5 minutes under a temperature condition of 23 ° C., and then dried and baked at 100 ° C. for 1 minute. The film thickness was measured before immersion and after dry baking, and the change in film thickness was calculated. Even if one of the immersion solvents has a film thickness increase / decrease of 10% or more with respect to the film thickness before immersion, “x” indicates that the film thickness increase / decrease is less than 10% for all solvents. The solvent resistance was evaluated as “○”. The evaluation results are shown in Table 1.

[Transmittance measurement]
Each of the thermosetting resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 5 was applied onto a quartz substrate using a spin coater, and then on a hot plate at 100 ° C. for 1 minute. Baking was performed at 230 ° C. for 1.5 minutes to form a film having a thickness of 0.06 μm. The transmittance of these films was measured using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation) by changing the wavelength by 2 nm in the wavelength range of 400 nm to 800 nm. Further, after heating this film at 260 ° C. for 5 minutes, the transmittance was measured again by changing the wavelength by 2 nm in the wavelength range of 400 nm to 800 nm. When the minimum transmittance measured in the wavelength range of 400 nm to 800 nm before and after heating at 260 ° C. for 5 minutes was 90% or more, “◯”, and when it was less than 90%, “X” As a result, the transmittance was evaluated. The evaluation results are shown in Table 1.

[Color resist residue]
Each of the thermosetting resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 5 was applied onto a silicon wafer using a spin coater, and then on a hot plate at 100 ° C. for 1 minute. Baking was performed at 230 ° C. for 1.5 minutes to form a film having a thickness of 0.06 μm. On this film, C.I. I. Pigment Blue 15: 6 and C.I. I. A photo-radically polymerizable pigment-dispersed blue color resist solution containing Pigment Violet 23 was applied and baked on a hot plate at 100 ° C. for 1 minute to form a blue color resist film having a thickness of 0.5 μm. Next, the blue color resist film was exposed through a mask using an i-line stepper NSR-2205i12D (NA = 0.63) (manufactured by Nikon Corporation), and 60% of 2.38 mass% TMAH aqueous solution was used. Developed for 2 seconds, rinsed with ultrapure water for 20 seconds, and then dried to form a rectangular pattern of 100 μm × 100 μm. Using a scanning electron microscope S-9260 (manufactured by Hitachi High-Technologies Corporation), the blue color resist residue on the film around the rectangular pattern was observed. Table 1 shows the residue level evaluation results when compared with Comparative Example 1. Further, photographs taken around the rectangular pattern at a magnification of 25,000 times are shown in FIGS. The level of residue of the blue color resist observed on the film was evaluated at three levels of “less”, “more”, and “equivalent” than in Comparative Example 1.

From the results in Table 1, the film formed from the thermosetting resin composition of the present invention has high solvent resistance and high transparency, and has high heat resistance that does not color even after heating at 260 ° C. there were. Further, on the film formed from the thermosetting resin composition of the present invention, almost no color resist residue is observed, and the film formed from the thermosetting resin composition of the present invention generates color resist residue. It was excellent in the effect which suppresses. On the other hand, the films formed from the thermosetting resin compositions prepared in Comparative Examples 1 to 5 also have high solvent resistance and high transparency, and high heat resistance that is not colored even after heating at 260 ° C. It was what had. However, on the film formed from the thermosetting resin composition prepared in Comparative Examples 1 to 5, the color resist residue is larger than that on the film formed from the thermosetting resin composition of the present invention. Many were observed. That is, it does not include a self-crosslinkable copolymer having at least one of the structural units represented by the formulas (1-1) to (1-5) and the structural unit represented by the formula (2). The film formed from the thermosetting resin composition prepared in Comparative Example 1 to Comparative Example 5 containing a polymer that does not correspond to the self-crosslinkable copolymer has no effect of suppressing the occurrence of color resist residues, or It was insufficient.

The thermosetting resin composition of the present invention forms a protective film, a planarizing film, a color filter underlayer film, a filler-dispersed resist underlayer film, etc. in devices such as CCD image sensors, CMOS image sensors, liquid crystal displays, and organic EL displays. It is suitable as a material to be used. In addition, when a color resist pattern is formed on a film obtained from the thermosetting resin composition of the present invention, the generation of color resist residues can be suppressed, and the quality and yield of devices equipped with color filters can be improved. Useful.

FIG. 1 is an electron micrograph of a blue color resist residue around a rectangular pattern on a film formed from the thermosetting resin composition of Example 1 taken at a magnification of 25,000 times. FIG. 2 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 2 at a magnification of 25,000 times. FIG. 3 is an electron micrograph of a blue color resist residue around a rectangular pattern on a film formed from the thermosetting resin composition of Example 3 taken at a magnification of 25,000 times. FIG. 4 is an electron micrograph of the blue color resist residue around the rectangular pattern on the film formed from the thermosetting resin composition of Example 4 taken at a magnification of 25,000 times. FIG. 5 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 5 at a magnification of 25,000 times. FIG. 6 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 6 at a magnification of 25,000 times. FIG. 7 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 7 at a magnification of 25,000 times. FIG. 8 is an electron micrograph of a blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 8 at a magnification of 25,000 times. FIG. 9 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 9 at a magnification of 25,000 times. FIG. 10 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 10 at a magnification of 25,000 times. FIG. 11 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 11 at a magnification of 25,000 times. FIG. 12 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 12 at a magnification of 25,000 times. FIG. 13 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 13 at a magnification of 25,000 times. FIG. 14 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 14 at a magnification of 25,000 times. FIG. 15 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 15 at a magnification of 25,000 times. FIG. 16 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 16 at a magnification of 25,000 times. FIG. 17 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 17 at a magnification of 25,000 times. FIG. 18 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 18 at a magnification of 25,000 times. FIG. 19 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Example 19 at a magnification of 25,000 times. FIG. 20 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Example 20 at a magnification of 25,000 times. FIG. 21 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Comparative Example 1 at a magnification of 25,000 times. FIG. 22 is an electron micrograph of the blue color resist residue taken around the rectangular pattern on the film formed from the thermosetting resin composition of Comparative Example 2 at a magnification of 25,000 times. FIG. 23 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Comparative Example 3 at a magnification of 25,000 times. FIG. 24 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Comparative Example 4 at a magnification of 25,000 times. FIG. 25 is an electron micrograph of a blue color resist residue taken around a rectangular pattern on a film formed from the thermosetting resin composition of Comparative Example 5 at a magnification of 25,000 times.

Claims (10)

A self-crosslinkable copolymer having at least one of structural units represented by the following formulas (1-1) to (1-5) and a structural unit represented by the following formula (2), and a solvent A thermosetting resin composition.
(In the formula, X represents an alkylene group having 1 to 6 carbon atoms, Z represents a glycidyl group, a glycidyloxyethyl group, a glycidyloxypropyl group, a glycidyloxybutyl group, a 3,4-epoxycyclohexyl group, 3 , 4-epoxycyclohexylmethyl group, 3,4-epoxycyclohexylethyl group, 3,4-epoxycyclohexylmethyloxyethyl group, 3,4-epoxycyclohexylmethyloxypropyl group or 3,4-epoxycyclohexylmethyloxybutyl group Represents.) The thermosetting resin according to claim 1, wherein the structural unit represented by the formula (2) is at least one of the structural units represented by the following formulas (2-1) to (2-7). Composition.
The self-crosslinkable copolymer is a copolymer having at least one of structural units represented by the following formulas (3) and (4). Thermosetting resin composition.
(Wherein R ⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, and the alkyl group, the cyclohexyl group, the phenyl group and the benzyl group are A part or all of the hydrogen atoms may be substituted with a hydroxy group or a carboxyl group, R ⁵ represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 5.) The thermosetting resin composition according to any one of claims 1 to 3, further comprising a curing accelerator. Furthermore, the thermosetting resin composition as described in any one of Claim 1 thru | or 4 containing surfactant. The thermosetting resin composition according to any one of claims 1 to 5, which is used for a protective film. The thermosetting resin composition according to any one of claims 1 to 5, which is used for a planarizing film. The thermosetting resin composition according to any one of claims 1 to 5, which is used for a color filter underlayer film. A cured film and a protection obtained by applying the thermosetting resin composition according to any one of claims 1 to 5 on a substrate and then baking the thermosetting resin composition using a heating unit. A method for producing a film, a planarizing film, or a color filter underlayer film. A step of applying a thermosetting resin composition according to any one of claims 1 to 5 on a substrate and then heating to form a color filter underlayer film, and applying a color resist on the color filter underlayer film A method for forming a color filter, comprising: a step of forming a color resist film by heating and a step of forming a color resist pattern by exposing, developing and rinsing the color resist film.