JP2009221270A - Thermosetting resin composition, manufacturing method of protective film of color filter, and protective film of color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which can be forming a highly flat cured film on a substrate, even on a substrate with low surface flatness, and be suitably used for manufacturing a protective film of a color filter which is highly transparent and enables good patterning of a wiring electrode. <P>SOLUTION: The thermosetting resin composition includes [A] a polymer having a bicyclo-orthoester structure and [B] a thermosensitive acid generator. The thermosetting resin composition optionally further includes [C] a copolymer of a polymerizable unsaturated compound comprising (c1) at least one chosen from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride and (c2) at least one chosen from the group consisting of a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated compound having an oxetanyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, a method for producing a color filter protective film, and a color filter protective film. More specifically, a composition suitable as a material for producing a protective film for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD), a method for producing a protective film using the composition, And a protective film produced from the composition.

Radiation devices such as LCD and CCD are soaked in a display element with a solvent, acid or alkali solution during the manufacturing process, and when the wiring electrode layer is formed by sputtering, the element surface is localized. Exposed to high temperatures. Accordingly, in order to prevent the device from being deteriorated or damaged by such treatment, a protective film made of a thin film having resistance to these treatments is provided on the surface of the device.
Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film, the film itself is smooth and tough, transparent It has excellent heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, and has excellent water resistance, solvent resistance, acid resistance, and alkali resistance. Performance is required. As a material for forming a protective film satisfying these various properties, for example, a thermosetting composition containing a polymer having a glycidyl group is known (see Patent Document 1 and Patent Document 2).

In addition, when such a protective film is used as a protective film for a color liquid crystal display device or a color filter of a charge coupled device, it is generally required that the step formed by the color filter formed on the base substrate can be flattened. The
Further, in a color liquid crystal display device, for example, a STN (Super Twisted Nematic) type or TFT (Thin Film Transistor) type color liquid crystal display element, a bead-shaped spacer is provided on the protective film in order to keep the cell gap of the liquid crystal layer uniform. The panels are pasted together after spraying. After that, the liquid crystal cell is sealed by thermocompression bonding with a sealing material, but the heat and pressure applied at that time show a phenomenon that the protective film in the part where the beads exist is recessed, and the cell gap may be distorted. It is a problem.
In particular, when manufacturing STN color liquid crystal display elements, the accuracy of bonding between the color filter and the counter substrate must be extremely strict, and the protective film has a very high leveling flatness and heat resistance. Performance is required.

  In recent years, a method of forming a wiring electrode (indium tin oxide: ITO or indium zinc oxide: IZO) on a protective film of a color filter by sputtering and patterning ITO or IZO with an acid or alkali has been adopted. Yes. For this reason, the surface of the color filter protective film is locally exposed to high temperatures during sputtering, and various chemical treatments are performed. Therefore, during these treatments, the patterning characteristics of the wiring electrode are good, such as the ITO or IZO pattern line width not becoming thinner than necessary, and the wiring is made so that ITO or IZO does not peel off from the protective film during chemical treatment. Adhesion with the electrode is also required.

For the formation of such a protective film, it is convenient to use a thermosetting composition having an advantage that a protective film having excellent hardness can be formed by a simple method. The protective film resin composition has a reactive cross-linking group or catalyst that forms a strong cross-linked structure, which causes a problem that the shelf life of the composition itself is very short, and handling is very difficult. It was troublesome. That is, not only the coating performance deteriorates with time due to the thickening of the composition, but also frequent maintenance and cleaning of the coating machine are required, and the work is complicated.
A material that can easily form a protective film that satisfies the above-mentioned general performance requirements as a protective film, such as transparency, and that has excellent storage stability as a composition is still known. Absent.

  By the way, it is known that a bicycloorthoester undergoes ring-opening polymerization in the presence of an acid catalyst (see Non-Patent Document 1 and Non-Patent Document 2). However, there is no report on a thermosetting composition containing a bicycloorthoester suitable for producing a protective film for a color filter.

JP-A-5-78453 JP 2001-91732 A K. Saigo, W. et al. J. et al. Bailey, T .; Endo, and M.M. Okawara: J.A. Polym. Chem. Ed. , 21, 1435 (1983) Macromolecules, 15, 11 (1982)

The present invention has been made on the basis of the above circumstances, and the object thereof is to form a cured film having high flatness on the substrate even if the substrate has low surface flatness. And a thermosetting resin composition suitably used for producing a color filter protective film having high transparency and good patterning characteristics of the wiring electrode, and a color filter protective film using the resin composition And a protective film for a color filter manufactured from the resin composition.
Still other objects and advantages of the present invention will become apparent from the following description.

The above objects and advantages of the present invention are as follows. [A] a polymer having a bicycloorthoester structure (hereinafter sometimes referred to as “[A] polymer”), and [B] a thermosensitive acid generator. It is achieved by a thermosetting resin composition for producing a protective film for a color filter, characterized in that
The above objects and advantages of the present invention are secondly achieved by a method for producing a protective film for a color filter, characterized in that a coating film is formed using the resin composition, followed by heat treatment.
Thirdly, the above objects and advantages of the present invention are achieved by a color filter protective film formed from the resin composition.
Still other objects and advantages of the present invention will become apparent from the following description.

  According to the thermosetting resin composition of the present invention, a cured film having high flatness can be formed on the substrate even if the substrate has low surface flatness, and the transparency is high. A protective film for a color filter having good electrode patterning characteristics can be produced. Furthermore, the thermosetting resin composition of the present invention is excellent in storage stability.

Hereinafter, the present invention will be described in detail.
<Thermosetting resin composition>
[A] Polymer The [A] polymer used in the present invention is a polymer having a bicycloorthoester structure. [A] The polymer is not particularly limited as long as it has a bicycloorthoester structure in its side chain or main chain, but preferably the following formula (1)

(In Formula (1), R < ¹ > -R < ⁶ > is a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, or a C6-C20 aryl group mutually independently. R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “*” represents a bond.)
It is a polymer which has the structure represented by these.
In the above formula (1), examples of the alkyl group having 1 to 4 carbon atoms of R ^{1 to} R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , Sec-butyl group, t-butyl group and the like.
Examples of the fluoroalkyl group having 1 to 4 carbon atoms of R ^{1 to} R ⁶ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, and 1,1-difluoroethyl. Group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro- A sec-butyl group, a nonafluoro-t-butyl group, etc. can be mentioned. Examples of the aryl group having 6 to 20 carbon atoms of R ^{1 to} R ⁶ include a phenyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group.
As a polymer having the structure represented by the above formula (1), for example, the following formula (2)

(In the formula (2), ^{R 8} represents a hydrogen atom or a methyl ^group, R 1 to R ⁷ have the same meanings as ^R 1 to R ⁷ in each formula (1).)
And a polymer having a repeating unit represented by the formula (hereinafter sometimes referred to as “polymer α”).
The content ratio of the repeating unit represented by the above formula (2) in the polymer α is preferably 5 to 95% by weight, more preferably 20 to 80% by weight, particularly 30 to 60% by weight. It is preferable.

  Polymer (alpha) can have another repeating unit different from this with the repeating unit represented by the said Formula (2). Examples of other repeating units include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compound, maleimide compound, unsaturated Aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds (hereinafter collectively referred to as “other polymerizable unsaturated compounds”) There may be mentioned a repeating unit derived from.

Specific examples thereof include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) as (meth) acrylic acid alkyl ester. Acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) Acrylate, n- stearyl (meth) acrylate;
Examples of (meth) acrylic acid cyclic alkyl esters include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, Tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl (meth) acrylate, isobornyl (meth) acrylate and the like;
Examples of (meth) acrylic acid aryl esters include phenyl (meth) acrylate and benzyl (meth) acrylate;
As unsaturated dicarboxylic acid diesters, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;
Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 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, 5,6-di (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-ene 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methyl Bicyclo [2.2.1] hept-2-ene and the like;
Examples of maleimide compounds include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3- Maleimide propionate, N- (9-acridinyl) maleimide and the like;
Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;
As unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As unsaturated dicarboxylic acid anhydride, for example, each anhydride of the above unsaturated dicarboxylic acid;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.
Among these, polymer α is styrene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2- It is preferable to have a repeating unit derived from methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, or N-cyclohexylmaleimide.
The polymer α can have a repeating unit derived from any one or more of other polymerizable unsaturated compounds.

  The polymer α may be produced by any method. For example, the following formula (3)

(In the formula ^(3), R 1 to R ⁸ have the same meanings as ^R 1 to R ⁸ in each formula (2).)
It is obtained after radical polymerization of a polymerizable unsaturated compound comprising a compound represented by the formula (hereinafter sometimes referred to as “unsaturated oxetane compound”) in the presence of a suitable solvent and a polymerization initiator. A method of cyclizing and isomerizing a polymer (hereinafter sometimes referred to as “polymer β”) in the presence of a heteropolyacid, and cyclizing the compound represented by the above formula (3) in the presence of a heteropolyacid. Isomerized into the following formula (4)

(In the formula ^(4), R 1 to R ⁸ have the same meanings as ^R 1 to R ⁸ in each formula (2).)
Then, the polymerizable unsaturated compound containing the compound can be produced by radical polymerization in the same manner.

The reaction to cyclize and isomerize the polymer β or the compound represented by the above formula (3) is the synthesis of the 57th Network Polymer Lecture Meeting “Synthesis of polymers having bicycloorthoesters in the side chain and its light. As described in “Crosslinking reaction and refractive index characteristics before and after photocrosslinking”, the reaction can be performed in a suitable organic solvent in the presence of a heteropolyacid such as phosphotungstic acid.

  Specific examples of the unsaturated oxetane compound used in the production of the polymer α include, for example, 3-[(meth) acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -2-methyl. Oxetane, 3-[(meth) acryloyloxymethyl] -3-methyloxetane, 3-[(meth) acryloyloxymethyl] -2-ethyloxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3-[(meth) acryloyloxymethyl] -2-pentafluoroethyloxetane, 3-[(meth) acryloyloxymethyl] -2-phenyl Oxetane, 3-[(meth) acryloyloxymethyl] -2,2-diph Olooxetane, 3-[(meth) acryloyloxymethyl] -2,2,4-trifluorooxetane, 3-[(meth) acryloyloxymethyl] -2,2,4,4-tetrafluorooxetane Can do. These unsaturated oxetane compounds can be used alone or in admixture of two or more.

Moreover, as a solvent that can be used for radical polymerization in the production of the polymer α, for example,
Alcohols such as methanol, ethanol, diacetone alcohol;
Ethers such as tetrahydrofuran, tetrahydropyran, dioxane;
Ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetates such as mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol ethyl monoether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene, xylene, nitrobenzene;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, n-lactic acid Butyl, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, Ethoxyacetic acid n- Chill, n-propoxyacetate methyl, n-propoxyacetate ethyl, n-propoxyacetate n-propyl, n-propoxyacetate n-butyl, n-butoxyacetate methyl, n-butoxyacetate, n-butoxyacetate n-propyl, n-Butoxyacetate n-butyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate n-propyl, 2-methoxypropionate n-butyl, 2-ethoxypropionate methyl, 2-ethoxy Ethyl propionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate N-butyl 2-n-propoxypropionate, -Methyl n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-ethoxypropionate n -Butyl, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3-n-butoxypropionic acid Methyl, ethyl 3-n-butoxypropionate, 3- Examples thereof include esters such as n-propyl n-butoxypropionate and n-butyl 3-n-butoxypropionate.
These solvents can be used alone or in admixture of two or more.

Examples of the polymerization initiator used for radical polymerization in the production of the polymer α include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 Azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile);
Organic peroxides such as cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t-butylperoxy) cyclohexane;
Hydrogen peroxide etc. can be mentioned.
When a peroxide is used as the polymerization initiator, a redox initiator may be used in combination with a reducing agent.

The weight average molecular weight (Mw) of the polymer α is preferably from 500 to 150,000, more preferably from 1,000 to 100,000, as a value in terms of polystyrene measured by gel permeation chromatography. The molecular weight distribution of the polymer α, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is preferably 1.0 to 5. 0.0, more preferably 1.0 to 3.0.
By using such a polymer α, a protective film with good flatness and heat resistance can be produced, and the resulting resin composition has excellent storage stability.

[B] Thermosensitive acid generator Examples of the thermosensitive acid generator include known onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and diaryliodonium salts.
Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4 Alkylsulfonium salts such as-(benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Such as benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salt;
Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Substituted benzylsulfonium salts such as hexafluoroantimonate;
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxy Phenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4 -Methoxy Phenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfone And triarylsulfonium salts such as 4-phenylthiophenyldiphenyltrifluoroacetate and 4-phenylthiophenyldiphenyl-p-toluenesulfonate.
Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate Nate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and triphenylsulfonium trifluoromethanesulfonate are preferably used.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p -Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate and other benzylbenzothiazo Examples thereof include nium salts.
Of these, 3-benzylbenzothiazonium hexafluoroantimonate is preferably used.
Specific examples of the phosphonium salt include diarylphosphonium salts such as (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphonate.

Specific examples of the diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. 4-methoxyphenyl phenyl iodonium tetrafluoroborate, 4-methoxyphenyl phenyl iodonium hexafluorophosphonate, 4-methoxyphenyl phenyl iodonium hexafluoroarsenate, 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyl iodonium tri Fluoro Cetate, 4-methoxyphenylphenyl iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert- Examples thereof include butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, and bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate.
Of these, diphenyliodonium hexafluorophosphonate is preferably used.

  In the present invention, the amount of the [B] heat-sensitive acid generator used is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the [A] polymer. . By setting the amount used within this range, a protective film having sufficient hardness can be obtained.

[C] Component The thermosetting resin composition of the present invention has [C] (c1) unsaturated carboxylic acid and unsaturated carboxylic acid anhydride to further improve the hardness and heat resistance of the protective film obtained. And (c2) a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated compound having an oxetanyl group selected from the group consisting of the above-mentioned compounds (hereinafter sometimes referred to as “compound (c1)”). A copolymer of a polymerizable unsaturated compound containing at least one selected from the group (hereinafter sometimes referred to as “compound (c2)”) (hereinafter referred to as “copolymer [C]”). Can be included).

As the compound (c1), for example,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Mention may be made of dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; acid anhydrides of said dicarboxylic acids.
Of these compounds (c1), acrylic acid, methacrylic acid, and maleic anhydride are preferred from the viewpoint of copolymerization reactivity and easy availability.
In the copolymer [C], the compound (c1) can be used alone or in admixture of two or more.
When the compound (c1) has a carboxyl group, the carboxyl group may be regenerated by protecting it and then subjecting it to polymerization, followed by deprotection. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known protecting group for the carboxyl group can be used. Specific examples thereof include a trialkylsilyl group, a 1-alkoxyalkyl group, and a cyclic 1-alkoxyalkyl group. More specifically, for example, a trimethylsilyl group, dimethylbutylsilyl group, 1-ethoxyethyl group, 1-propoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, triphenylmethyl group and the like can be mentioned.

Moreover, as a compound (c2), for example,
(Meth) acrylic acid glycidyl, (meth) acrylic acid 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3,4-epoxybutyl, (meth) acrylic acid 6,7-epoxy (Meth) acrylic acid epoxy (cyclo) alkyl esters such as heptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3 -Ethyloxy Tan, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxy) Ethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2 Methacrylic acid ester having an oxetanyl group such as 1,2,4,4-tetrafluorooxetane;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra An acrylic acid ester having an oxetanyl group such as fluorooxetane can be given.

Among these compounds (c2), from the viewpoint of copolymerization reactivity, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methyl -3-Methacryloyloxymethyl oxetane and 3-ethyl-3-methacryloyloxymethyl oxetane are preferred.
In the copolymer [C], the compound (c2) can be used alone or in admixture of two or more.

In the present invention, the copolymer [C] is a copolymer of the compound (c1), the compound (c2) and other polymerizable unsaturated compounds (hereinafter sometimes referred to as “compound (c3)”). It is preferably a coalescence. Examples of the compound (c3) include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, and (meth) acrylic acid 5-hydroxy. Pentyl ester, (meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid 9-hydroxynonyl ester, (meth) (Meth) acrylic acid hydroxyalkyl esters such as acrylic acid 10-hydroxydecyl ester, (meth) acrylic acid 11-hydroxyundecyl ester, (meth) acrylic acid 12-hydroxydodecyl ester;
Methyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t- (meth) acrylic acid (Meth) acrylic acid alkyl esters such as butyl;
(Meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, (meth) acrylic acid alicyclic esters such as isobornyl (meth) acrylate;
(Meth) acrylic acid phenyl ester, (meth) acrylic acid aryl ester or aralkyl ester such as benzyl (meth) acrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
(Meth) tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate, or the like, and having an oxygen-containing hetero 6-membered ring (meta) ) Acrylic acid ester;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Of these, n-butyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, p-methoxystyrene, from the viewpoint of copolymerization reactivity. , Tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.
In the copolymer [C], the compound (c3) can be used alone or in admixture of two or more.

In the copolymer [C], the copolymerization ratio of the compound (c1) is preferably 5 to 40% by weight, more preferably 10 based on the total of the compound (c1), the compound (c2) and the compound (c3). ~ 30% by weight. If the copolymerization ratio of the compound (c1) is less than 5% by weight, the hardness of the resulting protective film tends to decrease, whereas if it exceeds 40% by weight, the thermosetting resin composition containing the copolymer is stored. Stability may be reduced.
In the copolymer [C], the copolymerization ratio of the compound (c2) is preferably 10 to 70% by weight, more preferably 20 based on the total of the compound (c1), the compound (c2) and the compound (c3). ~ 60% by weight. When the content of the repeating unit of the compound (c2) is less than 10% by weight, the heat resistance and hardness of the protective film tend to be reduced. On the other hand, when the content exceeds 70% by weight, the thermosetting resin composition containing the copolymer is included. There is a risk that the storage stability of the product may be reduced.

The copolymer [C] can be produced by polymerizing in a suitable solvent in the presence of a radical polymerization initiator. As the solvent and the polymerization initiator used for radical polymerization of the copolymer [C], the same compounds as those mentioned in the production of the polymer α can be exemplified.
The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [C] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50, 000. If Mw is less than 2,000, the heat resistance and the like of the resulting protective film may be impaired, while if it exceeds 100,000, the storage stability of the thermosetting resin composition solution may be reduced. There is.

  In the present invention, the amount of the copolymer [C] used is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 100 parts by weight of the [A] polymer. 3 to 30 parts by weight. When the amount of the copolymer [C] used is less than 0.5 parts by weight, the effect of improving the hardness and heat resistance of the protective film is small, while when it exceeds 50 parts by weight, the thermosetting resin composition containing the copolymer There is a risk of reducing the storage stability of the object.

[D] Polyfunctional monomer [D] The polyfunctional monomer used in the present invention includes a compound having two or more oxiranyl groups or oxetanyl groups in the molecule (the above-mentioned [A] heavy monomer). Polymers and copolymers [C] are excluded.) And / or polyfunctional (meth) acrylic compounds are used.
Examples of the compound having two or more oxiranyl groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl. Diglycidyl ethers of bisphenol compounds such as ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Epoxidized soybean oil, epoxidized linseed oil;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3 , 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3, 4-D Carboxymethyl epoxycyclohexylmethyl-3 ', compound having two or more 3,4-epoxycyclohexyl groups in a molecule, such as 4'-epoxycyclohexane carboxylate, can be mentioned known compounds.
Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

On the other hand, as a polyfunctional (meth) acrylate compound, for example,
Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol Full orange acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, triacryloyloxypentaerythritol succinic acid {also known as: 3-acryloyloxy-2,2-bi Acryloyloxymethyl-propyl) ester}, diacryloyloxypentaerythritol succinic acid {alias: 3-acryloyloxy-2-acryloyloxymethyl-propyl) ester}, pentaacryloyloxydipentaerythritol succinic acid {alias: [3 -(3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acryloyloxymethyl-propyl] ester}, tetraacryoyloxydipentaerythritol succinic acid {alias: [3 -(3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2-acryloyloxymethyl-propyl] ester} and the like.
[D] Polyfunctional monomers can be used alone or in combination of two or more.

[E] Adhesion aid The resin composition of the present invention may contain [E] an adhesion aid in order to improve the adhesion between the protective film to be formed and the substrate.
As such [E] adhesion assistant, for example, a functional silane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
[E] Specific examples of the adhesion assistant include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Examples thereof include glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
The amount of the [E] adhesion assistant used is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. [E] When the amount of the adhesion assistant exceeds 30 parts by weight, the heat resistance of the obtained protective film may be insufficient.

[F] Surfactant The resin composition of the present invention can further contain [F] surfactant in order to improve the coating performance.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and other surfactants.
Examples of the fluorosurfactant include BM CHEMIE, trade names: BM-1000, BM-1100, Dainippon Ink and Chemicals, Inc. Product name: Florard FC-135, FC-170C, FC-430, FC-431, Asahi Glass Co., Ltd. Product names: Surflon S-112, S-113, S -131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, etc. Product.
As said silicone type surfactant, for example, Toray Dow Corning Silicone Co., Ltd. trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- 190, Shin-Etsu Chemical Co., Ltd. product name: KP341, Shin-Akita Kasei Co., Ltd. product name: Ftop EF301, EF303, EF352, and other commercial products.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, and the like.
Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like. Examples of the polyoxyethylene aryl ether include polyoxyethylene octyl phenyl ether, Examples include polyoxyethylene nonylphenyl ether, and examples of the polyoxyethylene dialkyl ester include polyoxyethylene dilaurate and polyoxyethylene distearate.
As said other surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic acid type copolymer polyflow No. 57, no. 90 etc. can be mentioned.
The amount of the [F] surfactant used is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the [A] polymer. When the amount of the surfactant exceeds 5 parts by weight, the coating film may be easily roughened in the coating process.

The resin composition of the present invention is prepared by uniformly dissolving or dispersing each of the above components in a suitable solvent. As the solvent to be used, a solvent in which each component of the composition is dissolved or dispersed and does not react with each component is preferably used.
Such solvents include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic Group hydrocarbons, ketones, esters and the like.
Specific examples thereof include alcohol, methanol, ethanol, benzyl alcohol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .;
As diethylene glycol monoalkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;
As diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;
As propylene glycol monoalkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;
As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;
As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;
As esters, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyacetic acid Ethyl, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy- Methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, propoxyacetic acid Chill, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropio Acid butyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid Examples thereof include propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.
Of these, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether are preferred, and in particular, benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether are preferred.
The amount of the solvent used is preferably 1 to 50% by weight, more preferably 5% by weight, based on the total solid content in the composition of the present invention (the amount obtained by removing the amount of the solvent from the total amount of the composition including the solvent). It is the range which becomes -40 weight%.
A high boiling point solvent can be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination here include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate , Phenyl cellosolve acetate and the like.
The amount of the high-boiling solvent used in combination is preferably 90% by weight or less, more preferably 80% by weight or less based on the total amount of the solvent.
The composition prepared as described above can be used after being filtered using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm. .

<Method for producing protective film of color filter>
Next, a method for producing a protective film for a color filter using the resin composition of the present invention will be described.
After the resin composition solution of the present invention is applied to the surface of the substrate and pre-baked to remove the solvent to form a coating film, a heat treatment is performed to produce a protective film for the target color filter. .
Examples of the substrate that can be used include substrates such as glass, quartz, silicon, and resin. Examples of the resin include resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, and cyclic olefin ring-opening polymers and hydrogenated products thereof.
As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a bar coating method, an ink jet method, or the like can be adopted. Can be suitably used.
Although the prebaking conditions vary depending on the types and blending ratios of the respective components, conditions of usually about 1 to 15 minutes at 70 to 90 ° C. can be adopted. The thickness of the coating film is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm, and still more preferably 0.15 to 4.5 μm. In addition, the thickness of a coating film here should be understood as thickness after solvent removal.
The heat treatment after the coating film is formed can be carried out by an appropriate heating device such as a hot plate or a clean oven. The treatment temperature is preferably about 150 to 250 ° C., and the heating time can be 5 to 30 minutes when using a hot plate, and 30 to 90 minutes when using an oven.
In addition, when a radiation sensitive acid generator is used for the resin composition, the resin composition is applied to the substrate surface, the solvent is removed by pre-baking to form a coating film, and then a radiation irradiation treatment (exposure treatment). The target protective film can be manufactured by applying If necessary, a heat treatment may be further performed after the exposure processing.
Examples of the radiation that can be used in the radiation irradiation treatment include visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, and the like, and ultraviolet light including light having a wavelength of 190 to 450 nm is preferable.
The exposure amount is preferably 100~20,000J / ^{m 2,} more preferably 150~10,000J / ^{m 2.}

<Protective film of color filter>
The protective film thus manufactured has a thickness of preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm. In addition, when the protective film of this invention is formed on the board | substrate which has the level | step difference of a color filter, said film thickness should be understood as the thickness from the uppermost part of a color filter.
The protective film of the present invention is excellent in transparency, ITO etching resistance, etc., as is clear from the examples described below, and also has excellent performance in flattening the step of the color filter formed on the base substrate. Suitable as a membrane.

Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples.
[A] Synthesis of polymer Synthesis Example 1
In a rubbing test tube, 2.0 parts by weight of 3-acetyloxymethyl-3-ethyloxetane, 0.20 part by weight of dehydrated 12-phosphotungstic acid and 18.0 parts by weight of chlorobenzene were charged, and the temperature was maintained at 80 ° C. in a nitrogen atmosphere. For 80 hours. After completion of the reaction, the solid content was filtered off with a filter, and the solvent was distilled off from the resulting solution under reduced pressure. Next, the obtained slightly viscous liquid product is further recrystallized to obtain the following formula (5).

(Hereinafter referred to as “unsaturated bicycloorthoester compound (5)”).

Synthesis example 2
In an ampule tube, 0.025 part by weight of cumene hydroperoxide as a polymerization initiator, 0.48 part by weight of the unsaturated bicycloorthoester compound (5) obtained in Synthesis Example 1 and 0.065 part by weight of methyl methacrylate were placed. Then, after freeze-deaeration was performed three times, the tube was sealed and reacted at 120 ° C. for 20 hours. Next, the reaction product was dissolved in 5 parts by weight of tetrahydrofuran and added dropwise to excess n-hexane. The copolymer containing the solvent was fractionated by decantation. Furthermore, the polymer (A-1) was obtained by removing the solvent from the copolymer containing this solvent under reduced pressure. The weight average molecular weight of the obtained polymer (A-1) was 3,500, and the copolymerization ratio examined by ¹ H-NMR spectrum was unsaturated bicycloorthoester compound (5) / methyl methacrylate = 30 / It was 70 (molar ratio).

Synthesis example 3
In an ampule tube, 0.025 part by weight of cumene hydroperoxide as a polymerization initiator and 0.40 part by weight of unsaturated bicycloorthoester compound (5) in Synthesis Example 1 and 0.11 part by weight of methyl methacrylate were placed. After performing freeze deaeration three times, the tube was sealed and reacted at 120 ° C. for 20 hours. Next, the reaction product was dissolved in 5 parts by weight of tetrahydrofuran and added dropwise to excess n-hexane. The copolymer containing the solvent was fractionated by decantation. Furthermore, the polymer (A-2) was obtained by removing the solvent from the copolymer containing this solvent under reduced pressure. The weight average molecular weight of the obtained polymer (A-2) is 4,800, and the copolymerization ratio examined by ¹ H-NMR spectrum is unsaturated bicycloorthoester compound (5) / methyl methacrylate = 20 / It was 80 (molar ratio).

Synthesis example 4
In an ampule tube, 0.027 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator and 0.54 parts by weight of 3-acetyloxymethyl-3-ethyloxetane and 0.033 parts by weight of methyl methacrylate Was further dissolved in 1.20 parts by weight of chlorobenzene, freeze-deaerated three times, sealed, reacted at 60 ° C. for 3 hours, and the resulting reaction solution was cooled to room temperature. Next, the reaction product was dissolved in 5 parts by weight of tetrahydrofuran and added dropwise to excess n-hexane. The copolymer containing the solvent was fractionated by decantation. Further, the copolymer containing this solvent was removed under reduced pressure to obtain an intermediate polymer. The weight average molecular weight of the obtained intermediate polymer was 36,000.
Next, 0.11 part by weight of the above intermediate polymer, 0.006 part by weight of dehydrated 12-phosphotungstic acid and 0.54 part by weight of nitrobenzene are charged into a rubbed test tube, and a nitrogen atmosphere is maintained at 30 ° C. for 30 hours. Reacted. Next, the reaction product was dissolved in 3 parts by weight of tetrahydrofuran and added dropwise to excess n-hexane. The copolymer containing the solvent was fractionated by decantation. Furthermore, the polymer (A-3) was obtained by removing the solvent from the copolymer containing this solvent under reduced pressure. ^When the existence ratio of the structure represented by the above formula (2) was examined by ¹ H-NMR spectrum, the unsaturated bicycloorthoester compound (5) / methyl methacrylate = 10/90 (moles) in terms of copolymerization ratio. Ratio).

Synthesis of copolymer [C] Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 18 parts of methacrylic acid and tricyclomethacrylate [5 .2.1.0 ^2,6 ] 32 parts of decan-8-yl, 10 parts of styrene and 40 parts of glycidyl methacrylate were substituted with nitrogen, and then the temperature of the solution was raised to 70 ° C. while gently stirring. The copolymer [C-1] solution having a solid content concentration of 31.0% was obtained by polymerization while maintaining this temperature for 5 hours. For the obtained copolymer [C-1], Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (trade name, manufactured by Showa Denko KK) and found to be 11,000. It was.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 16 parts by weight of methacrylic acid, 18 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and 40 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane were added. After replacing the charged nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [C-2]. The solid content concentration of the obtained polymer solution was 33.0%, and Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (trade name, manufactured by Showa Denko KK). 24,000.

Preparation of resin composition and formation of protective film Example 1
100 parts by weight of the copolymer (A-1) (in terms of solid content), 5 parts by weight of triphenylsulfonium trifluoromethanesulfonate as the [B] component, and bisphenol A novolac type epoxy resin (Japan epoxy resin (D) as the component [D] Product name: Epicoat 828) 30 parts by weight, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as [E] component, and silicone-based surfactant (Toray Dow Corning Silicone Co., Ltd.) as [F] component Product name: SH-28PA) Add 0.1 parts by weight, add propylene glycol monomethyl ether acetate to a solid content concentration of 22% by weight, and then filter through a Millipore filter with a pore size of 0.5 μm. A resin composition was prepared.
After applying the above composition on a SiO ₂ dip glass substrate using a spinner, pre-baked on a hot plate at 80 ° C. for 5 minutes to form a coating film, and further heat-treated in an oven at 250 ° C. for 60 minutes. Thus, a protective film having a thickness of 2.0 μm was formed.

Evaluation of Protective Film (1) Evaluation of Transparency About the substrate having the protective film formed as described above, using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), 400 to 800 nm. The Noto rate was measured. Table 1 shows the minimum transmittance of 400 to 800 nm. When this value is 95% or more, it can be said that the transparency of the protective film is good.

(2) Evaluation of ITO patterning characteristics For a substrate having a protective film formed as described above, High, rate, Spu
Using ITO target (ITO filling rate 95% or more, In ₂ O ₃ / SnO ₂ = 90/20 weight ratio) with a tettering device SH-550-C12 (manufactured by Nippon Vacuum Technology Co., Ltd.) Sputtered. At this time, the degree of decompression was 1.0 × 10 ⁻⁵ Pa, the Ar gas flow rate was 3.12 × 10 ⁻³ m ³ / h, and the O ₂ gas flow rate was 1.2 × 10 ⁻⁵ m ³ / h. The sputtered substrate was heated in a clean oven at 240 ° C. for 1 hour.
Next, a positive resist PFR3650 manufactured by JSR Co., Ltd. was applied onto the obtained substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. The ghi line (wavelength 436 nm, 405 nm, intensity ratio of 265 nm = 2.7 nm) using a photomask having a 10 μm / 10 μm line and space pattern and using an exposure machine Canon PLA501F (Canon). 2.5: 4.8) is irradiated with exposure doses of illuminance of 23 mW / m ² and 25 mJ / m ² in terms of i-line, and immersion development is performed for 60 seconds using room temperature or 2.4% TMAH aqueous solution. After rinsing with water for 60 seconds, it was air-dried. Then, it heat-processed at 150 degreeC for 1 hour further in the clean oven, and the board | substrate with which the resist pattern was formed on ITO was created.
Next, ITO was patterned by wet etching using an etchant in which nitric acid / hydrochloric acid was mixed at a weight ratio of 1/3. The obtained substrate is immersed in an etchant, the substrate is taken out every 10 seconds, and the line width of the formed ITO line pattern is measured with an optical microscope, so that the etching time when the line width of the ITO line pattern becomes 10 μm is obtained. It was measured. The line width of the ITO line pattern when immersed in an etchant for a time corresponding to 1.2 times the etching time was measured with an optical microscope, and the results are shown in Table 1. The closer the line width of the formed ITO line pattern is to 10 μm, the better the ITO patterning characteristics.

(3) Evaluation of planarization property A pigment-based color resist (trade names “JSR RED 689”, “JSR GREEN 706”, “CR 8200B”, and more, manufactured by JSR Corporation) is applied to a spinner on a SiO ₂ dip glass substrate. And prebaked at 90 ° C. for 150 seconds on a hot plate to form a coating film. Thereafter, ghi rays (intensity ratio of wavelengths 436 nm, 405 nm, and 265 nm = 2.7: 2.5: 4.8) using an exposure machine Canon PLA501F (manufactured by Canon Inc.) through a predetermined pattern mask. Irradiated with an exposure dose of 2,000 J / m ^{2 in} terms of i-line, developed with 0.05% aqueous potassium hydroxide solution, rinsed with ultrapure water for 60 seconds, and further in an oven at 230 ° C. Heat treatment was performed for 30 minutes to form a striped color filter (stripe width 100 μm) of three colors of red, green, and blue.
The unevenness on the surface of the substrate on which the color filter was formed was measured with a surface roughness meter “α-step” (trade name: manufactured by Tencor), and found to be 1.0 μm. However, the measurement was performed with a measurement length of 2,000 μm, a measurement range of 2,000 μm square, and a number of measurement points n = 5. That is, the measurement direction is two directions of the stripe line minor axis direction of red, green, blue direction and the stripe axis major axis direction of red / red, green / green, blue / blue, and n = 5 for each direction. Measured (total n number is 10).
On the obtained stripe color filter, the composition for forming a protective film was applied to a spinner, and then pre-baked on a hot plate at 90 ° C. for 5 minutes to form a coating film, and further in an oven at 230 ° C. And a protective film having a thickness of 2.0 μm from the upper surface of the color filter was formed. However, the film thickness said here means the thickness from the uppermost surface of the color filter formed on the substrate.
About the board | substrate which has a protective film on the color filter formed as mentioned above, the unevenness | corrugation on the surface of a protective film was measured with the contact-type film thickness measuring apparatus alpha-step (made by Tencor Japan Co., Ltd.). However, the measurement was performed with a measurement length of 2,000 μm, a measurement range of 2,000 μm square, and a number of measurement points n = 5. That is, the measurement direction is two directions of the stripe line minor axis direction of red, green, blue direction and the stripe axis major axis direction of red / red, green / green, blue / blue, and n = 5 for each direction. Measured (total n number is 10). Table 1 shows the average value of 10 times of the height difference (nm) between the highest and lowest parts for each measurement. When this value is 300 nm or less, it can be said that the flatness is travel.

(4) Evaluation of Storage Stability The year at 25 ° C. of the resin composition prepared in Example 1 was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the viscosity at 25 ° C. was measured every day while the harmful composition was allowed to stand at 25 ° C. The number of days required to increase the viscosity by 5% based on the viscosity immediately after the preparation was determined, and the number of days is shown in Table 1. When this number of days is 20 days or more, it can be said that the storage stability is good.

Examples 2 to 8 and Comparative Examples 1 and 2
The purpose and composition of each component of the composition are as shown in Table 1, and the composition is the same as in Example 1 except that the solvent shown in Table 1 was used and the solid content concentration shown in Table 1 was used. A product was prepared.
Using the composition for forming a protective film prepared as described above, a protective film was formed in the same manner as in Example 1 and displayed. The results are shown in Table 1.

In Table 1, the abbreviations of [B] to [F] components and the solvent (S) represent the following.
B-1: Triphenylsulfonium trifluoromethanesulfonate B-2: Diphenyliodonium hexafluorophosphonate D-1: Bisphenol A novolak type epoxy resin (trade name: Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.)
D-2: Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
E-1: γ-Glycidoxypropyltrimethoxysilane F-1: Silicone surfactant (trade name: SH-28PA manufactured by Toray Dow Corning Silicone Co., Ltd.)
S-1: Propylene glycol monomethyl ether acetate S-2: Diethylene glycol ethyl methyl ether

Claims (6)

A thermosetting resin composition for producing a protective film for a color filter, comprising: [A] a polymer having a bicycloorthoester structure; and [B] a thermosensitive acid generator. [A] The thermosetting resin composition according to claim 1, wherein the bicycloorthoester structure in the polymer is a structure represented by the following formula (1).

(In Formula (1), R < ¹ > -R < ⁶ > is a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, or C6-C20 mutually independently. Represents an aryl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “*” represents a bond.) [A] The thermosetting resin composition according to claim 2, wherein the polymer has a repeating unit represented by the following formula (2).

(In the formula (2), ^{R 8} represents a hydrogen atom or a methyl ^group, R 1 to R ⁷ have the same meanings as ^R 1 to R ⁷ in each formula (1).) Furthermore, [C] (c1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (c2) a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated group having an oxetanyl group. The thermosetting resin composition in any one of Claims 1-3 containing the copolymer of the polymerizable unsaturated compound containing at least 1 sort (s) chosen from the group which consists of a saturated compound. A method for producing a protective film for a color filter, comprising: forming a coating film on the substrate using the resin composition according to any one of claims 1 to 4; The protective film of the color filter manufactured from the resin composition in any one of Claims 1-4.