JP2007291263A - Thermosetting resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having excellent transparency and flattening performance, exhibiting high stability at high temperature, and suitable for the protection of a functional film, especially a colored resin film. <P>SOLUTION: The thermosetting resin composition comprises (A) a cocondensation product of a silicon compound having epoxy group and expressed by formula (1) or (2) and/or a compound expressed by formula (3), (B) a phenolic compound, (C) a cure accelerator and (D) a solvent. In the formulas, X is a 2-5C alkylene which may be interrupted with ether group (-O-) or ester group (-OCO-); R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are each a 1-4C alkyl group; and Z is methyl or phenyl group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition suitable for forming a protective film and a cured product thereof. More specifically, an epoxy-based thermosetting resin composition for a protective film suitable as a protective film provided on a functional film (for example, a colored resin film such as a color filter) formed on the surface of a glass substrate or the like, and a cured product thereof About.

  A color filter in a liquid crystal display element is immersed in a solvent, an acid, an alkali solution, or the like during the manufacturing process, and the surface of the element is locally exposed to a high temperature by sputtering when forming an ITO (Indium Tin Oxide) layer. In order to prevent element deterioration and damage from such severe conditions, a protective film having resistance to these elements is generally formed. In addition, when the liquid crystal display element requires high performance such as high viewing angle and high speed response, the flatness of the color filter is important, so it is necessary to provide a protective film with high flattening ability. It is said. In addition to the above required characteristics, such a protective film has a low degree of liquid crystal contamination, excellent smoothness, and good adhesion to the substrate on which the protective film is formed and the layer formed on the protective film. It has high visible light transmittance so as not to reduce the brightness of the liquid crystal display, the protective film itself does not change over time such as coloring, whitening, and yellowing, and has toughness that can withstand impact, strain, etc. Etc. are required.

  Conventionally, acrylic resins, melamine resins, polyimide resins, etc. have been proposed as protective film materials for functional films, but materials that satisfy all of the above required properties in a well-balanced manner have still been found. The current situation is not. For example, although acrylic resin is excellent in visible light transmittance, heat resistance is insufficient, and there is a problem that wrinkles and cracks are generated on the film surface when an ITO film or the like is formed. In addition, melamine resin has good heat resistance, but has extremely poor adhesion to a glass substrate, and has a problem that repelling is likely to occur on the substrate or filter. Furthermore, while polyimide resin has high heat resistance, it is insufficiently transparent and lacks the storage stability of the resin, and its solubility is poor, and usable organic solvents attack the color filter (colored resin film) itself. There is a problem that it becomes such a solvent. In Patent Document 1, a protective film using a polyhydric phenol-based curing agent having an epoxy resin and a terpene skeleton has been studied. However, they have insufficient adhesion, or in recent years ITO Along with the high temperature during film formation, there are problems that wrinkles and cracks occur during the film formation, and yellowing due to heat occurs. In order to overcome this yellowing, attempts have been made to use acid anhydrides as curing agents. However, there are problems in storage stability due to its reactivity and hygroscopicity, and there are still problems such as the limited organic solvent to be dissolved and the safety of the solvent.

JP 2004-315657 A

  An object of the present invention is to provide a protective film resin composition for a functional film that has improved the above-described drawbacks in the prior art, that is, satisfying adhesion, visible light transmittance, etc., and planarizing ability of the substrate surface, Provided is a protective film-forming resin composition that can form a protective film with high surface smoothness and has excellent high-temperature resistance, particularly when used as a protective film for a color filter (colored resin film) for liquid crystal display. There is.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a thermosetting resin composition containing a condensate of a silicon compound having an epoxy group having a specific skeleton, a phenolic compound, a curing accelerator, etc. The present invention has been completed by finding that the product satisfies the above-mentioned problems.

That is, the present invention
(1) A thermosetting resin composition containing the following (A), (B), (C), (D),
(A) The following (a-1) and / or (a-2)
(A-1) A silicon compound having an epoxy group represented by the following formula (1) and / or a silicon compound having an epoxy group represented by formula (2) or a self-condensed product (a-2) ) A silicon compound having an epoxy group represented by formula (2) and / or a co-condensate of a silicon compound having an epoxy group represented by formula (2) and a compound represented by formula (3) below (B) phenolic compound (C) Curing accelerator (D) solvent

(In the formula (1), formula (2) and formula (3), X represents a C2-C5 alkylene group optionally interrupted by an ether group (—O—) or an ester group (—OCO—), R ₁ , R ₂ and R ₃ each represent a C1-C4 alkyl group, and Z represents a methyl group or a phenyl group.)
(2) The thermosetting resin composition according to (1), wherein the phenolic compound is a compound represented by the following formula (4) or formula (5):

(3) The thermosetting resin composition according to (2), wherein the phenolic compound represented by the formula (4) is a compound represented by the following formula (6):

(4) A protective film agent for a functional film comprising the thermosetting resin composition according to any one of (1) to (3),
(5) The functional film protective film agent according to (4), wherein the functional film is a colored resin film,
(6) A cured resin film obtained by curing the protective film agent for functional film according to (4) or (5),
(7) A color filter comprising a colored resin film having the cured resin film according to (6) (8), a liquid crystal display device comprising the color filter according to (7),
About.

  The epoxy thermosetting resin composition of the present invention is excellent in transparency and flattening ability, has particularly high heat resistance, has high stability at high temperature, and is advantageous for protection of a colored resin film. In the production of color filters used in liquid crystal display devices, the reliability can be improved.

The present invention will be described in detail below.
The thermosetting resin composition of the present invention is a thermosetting resin composition characterized by containing the following (A), (B), (C), and (D).
(A) The following (a-1) and / or (a-2)
(A-1) a silicon compound having an epoxy group represented by the following formula (1) and / or a self- or cocondensate of a silicon compound having an epoxy group represented by formula (2),
(A-2) Cocondensate of a silicon compound having an epoxy group represented by the following formula (1) and / or a silicon compound having an epoxy group represented by the formula (2) and a compound represented by the following formula (3) ,
(B) phenolic compound (C) curing accelerator (D) solvent

  First, (a-1) a silicon compound having an epoxy group represented by the following formula (1) and / or a silicon compound having an epoxy group represented by formula (2) used in the present invention, or a self-condensation product of ( a-2) Cocondensate of a silicon compound having an epoxy group represented by the following formula (1) and / or a silicon compound having an epoxy group represented by the formula (2) and a compound represented by the following formula (3) explain.

(In the formulas (1), (2) and (3), X represents a C2-C5 alkylene group optionally interrupted by an ether group (—O—) or an ester group (—OCO—), R ₁ , R ₂ and R ₃ each represent a C1-C4 alkyl group, and Z represents a methyl group or a phenyl group.)

  Specific examples of the alkoxysilicon compound having an epoxy group represented by the formula (1) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxymethyldimethoxysilane are preferred.

  Specific examples of the alkoxysilicon compound having an epoxy group represented by the formula (2) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Etc. Of these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.

Furthermore, specific examples of the alkoxysilicon compound represented by the formula (3) include phenyltrimethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, and methyltriethoxysilane. Of these, preferred are phenyltrimethoxysilane and methyltrimethoxysilane.
Any of the silicon compounds represented by the above formulas (1) to (3) can be easily obtained from the market.

  The condensate (A) used in the present invention includes (a-1) a silicon compound having an epoxy group represented by the above formula (1) and / or a silicon compound having an epoxy group represented by (2). Or even if it is a cocondensate, the silicon compound which has an epoxy group shown by (a-2) Formula (1) and / or the silicon compound which has an epoxy group shown by (2), and said Formula (3) Or a co-condensate with a compound represented by the formula (a-1) and (a-2) can be used in combination. In (a-1), the usage ratio of both in the case of carrying out a cocondensate in combination with a silicon compound having an epoxy group represented by the above formula (1) and a silicon compound having an epoxy group represented by the formula (2) Is appropriately selected according to the desired physical properties of the product. For example, when a low viscosity property is desired for the condensation product, co-condensation is performed by increasing the proportion of the component represented by the formula (1). In (a-2), both a silicon compound having an epoxy group represented by formula (1) and / or a silicon compound having an epoxy group represented by (2) and a compound represented by (3) are used. When preparing a cocondensate, the total number of moles of the silicon compound having an epoxy group represented by formula (1) and / or the silicon compound having an epoxy group represented by (2) and the compound represented by (3) However, it is preferable to prepare the cocondensate in such a ratio that the number of moles of the compound represented by (3) is less than 80 mol%.

  The self or co-condensate proceeds by heating the mixture of the raw material compounds to cause a dealcoholization reaction and a dehydration reaction in the presence of an alkali agent and water. The amount of water used in this condensation reaction is usually 0.1 to 1.5 mol, preferably 0.2 to 1.2 mol, with respect to 1 mol of alkoxy groups in the entire reaction system. As the alkali agent used for the self- or co-condensation, any compound that is basic in water can be used. Specific examples of alkali agents that can be used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Inorganic bases such as alkali metal carbonates; ammonia; organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, the use of an inorganic base or ammonia is preferable because the catalyst can be easily removed from the reaction product. The amount of these alkali agents added is usually 0.001 to 7.5% by weight, preferably 0.01 to 5% by weight, based on the total weight of the raw material silicon compound in the reaction system.

  The condensation reaction can be carried out without a solvent, but is preferably carried out in a solvent. As the solvent, any solvent that can dissolve the silicon compounds of the formulas (1) to (3) can be used without particular limitation. Specific examples of the solvent that can be used include dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, Examples include aprotic polar solvents such as methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, and the like. Of these, aprotic polar solvents are preferred. Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is preferable to use normally 50-900 weight part with respect to 100 weight part of total weight of the silicon compound of Formula (1) thru | or Formula (3).

  The reaction temperature in the condensation reaction is usually 20 to 160 ° C., preferably 40 to 140 ° C., although it depends on the amount of catalyst. The reaction time is usually 1 to 12 hours. Mw (weight average molecular weight) of the reaction product (condensate) can be measured by GPC (gel permeation chromatography). When the reaction is completed, the heating is stopped, the solvent and water are added, liquid separation is performed, the organic layer is taken and the used solvent is removed under reduced pressure to obtain the desired condensate. If necessary, the obtained condensate can be purified by gel filtration or the like.

  The condensate (A) used in the present invention obtained as described above is considered to be a polymer compound having the following repeating units.

(In Formula (7), X and Z represent the same meaning as in Formula (1) to Formula (3).)

Next, the phenolic compound (B) used in the present invention will be described.
In the present invention, the phenolic compound (B) serves as a curing agent, and any compound can be used as long as it can react with the condensate (A) to form a transparent cured film having excellent heat resistance. Is possible. Specific examples of phenolic compounds (curing agents) that can be used include tris (4-hydroxyphenyl) phosphine oxide; bisphenol A, bisphenol F, 2,4-bisphenol S, 2,2-bisphenol S, 2,3. -Bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl -4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-Methyl-6-tert-buty Ruphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton; 1,1-di- Phenols having a fluorene skeleton such as 4-hydroxyphenylfluorene; various phenols such as phenolized polybutadiene, phenol, cresol, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols Novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, Examples include various novolak resins such as a phenolic novolac resin containing a fluorene skeleton and a phenol novolac resin containing a furan skeleton.
Among these, a phenolic compound represented by the following formula (4) and tris (4-hydroxyphenyl) phosphine oxide represented by the following formula (5) are preferable because they are particularly excellent in transparency and heat resistance. Of the phenolic compounds represented by formula (4), the phenolic compound represented by formula (6) is particularly preferred.

Next, the curing accelerator (C) used in the present invention will be described.
Any curing accelerator (C) may be used as long as it has a function of accelerating the condensation reaction between the epoxy resin and the phenolic compound, and imidazole-based curing acceleration. Examples thereof include phosphine-based curing accelerators, ammonium-based curing accelerators, Lewis acid-based curing accelerators, and the like. In the present invention, the use of imidazole-based curing accelerators is particularly preferable. Specific examples of imidazole curing accelerators that can be used include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4. -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,3-dihydro-1H-pyrrolo- [1,2-a] benzimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino- 6 (2′-Undecylimidazole (1 ′)) ethyl-s-triazine 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s -Triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Examples include various imidazole compounds such as 5-hydroxymethylimidazole or 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole. Among these, 2,3-dihydro-1H-pyrrolo- [1,2-a] benzimidazole and 2-phenyl-4-methylimidazole are particularly preferable examples.

Furthermore, the solvent (D) used by this invention is demonstrated.
The solvent used in the thermosetting resin composition of the present invention has a high solubility in the above (A), (B) and (C) and does not show reactivity with these. Any of them can be used without limitation. Specific examples of solvents that can be used include alcohols such as methanol, ethanol, propanol, butanol, preferably lower alcohols having 1 to 4 carbon atoms, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene. Glycol ethers such as glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, preferably a lower ether having 1 to 4 carbon atoms of alkylene glycol having 1 to 4 carbon atoms, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate Alkylene glycol ether acetates such as tate, 3-methyl-3-methoxybutyl acetate, ethyl ethoxypropiolate, etc., preferably C 1-4 lower ether acetates of alkylene glycols having 1 to 4 carbon atoms, toluene, xylene, etc. Aromatic hydrocarbons, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Chill, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, propyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2 -Butyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Esters such as ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, etc., preferably a hydroxy group, and a C2-C4 optionally substituted with a lower alkyl group having 1 to 4 carbon atoms C1-C4 alkyl ester of fatty acid, ethers, such as tetrahydrofuran, etc. are mentioned.

  Among these, in consideration of solubility in the self- or co-condensate, phenolic compound, curing accelerator, concentration change with time due to volatilization, toxicity to human body, etc., propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether C2-C4 lower ether acetate of C2-C3 alkylene glycol such as acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, esters A preferred example is given.

  In the thermosetting resin composition of the present invention, the contents of the components (A) self or cocondensate, (B) phenolic compound, (C) curing accelerator and (D) solvent are usually (A ) 5-50 wt%, (B) 4-30 wt%, (C) 0.1-3.0 wt%, (D) 30-90 wt%, preferably (A) 10-20 wt%, ( B) 5 to 15% by weight, (C) 0.1 to 0.3% by weight, and (D) 70 to 80% by weight.

  To the thermosetting resin composition of the present invention, if necessary, an epoxy resin other than the above may be added within a range that does not substantially deteriorate physical properties such as transparency, heat resistance, chemical resistance, and flatness. Can do.

Examples of other epoxy resins that can be used include, for example, epoxy resins that are glycidyl etherified products of phenolic compounds, epoxy resins that are glycidyl etherified products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic types Examples thereof include epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like.
Among the above, as an epoxy resin which is a glycidyl etherified product of a phenol compound, 2- [4- (2,3-hydroxyphenyl) -2- [4- [1,1-bis [4- (2,3- Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl Bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl ) Phenyl] propane, 2,2′-methylene-bis (4- Methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglicinol, diisopropylidene skeleton Examples include phenols, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins that are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  In addition, epoxy resins which are glycidyl etherified products of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. Glycidyl etherification products of various novolac resins such as novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, and fluorene skeleton-containing phenol novolak resin.

  Furthermore, as an alicyclic epoxy resin, an alicyclic epoxy resin having an aliphatic ring skeleton such as cyclohexane, and as an aliphatic epoxy resin, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, pentaerythritol Glycidyl ethers of polyhydric alcohols such as: heterocyclic epoxy resins having heterocyclic rings such as isocyanuric rings and hydantoin rings; and glycidyl ester epoxy resins such as diglycidyl esters of hexahydrophthalic acid Epoxy resins composed of carboxylic acid esters, glycidylamine-based epoxy resins as epoxy resins obtained by glycidylation of amines such as aniline and toluidine, and halogenated phenols as glycidylated epoxy resins as brominated bisphenol A, Lom bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated bisphenol S, and halogenated phenols glycidylated epoxy resins such as chlorinated bisphenol A.

Among these epoxy resins, considering heat resistance and transparency, 2- [4- (2,3-hydroxyphenyl) -2- [4- [1,1-bis [4- (2,3-hydroxy] ) Phenyl] ethyl] phenyl] propane, bisphenol A, a fluorene skeleton-containing phenol novolak resin, an alicyclic epoxy resin having an aliphatic ring skeleton such as cyclohexane, and a glycidyl ether of a polyhydric alcohol such as pentaerythritol.
Other epoxy resins as described above are added in an amount of 0 to 10 parts by weight, if necessary, with respect to 100 parts by weight of the thermosetting resin composition of the present invention.

  Furthermore, the thermosetting resin composition of the present invention of the present invention includes a coupling agent, a surfactant, an oxidation stabilizer, a light stabilizer, a moisture resistance improver, a thixotropy imparting agent, and an antifoaming agent as necessary. Various other resins, tackifiers, antistatic agents, lubricants, ultraviolet absorbers and other additives can also be blended. These are added to the thermosetting resin composition of the present invention by a method known per se.

  For example, examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Silane coupling agents such as rolopropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate , Titanium-based coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneo Decanoyl zirconate, Neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, Neoalkoxytris (ethylenediaminoethyl) zirconate, Neoa Examples thereof include zirconium such as lucoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, and aluminum coupling agents. Of these, silane coupling agents are preferred, and silane coupling agents having an epoxy group are more preferred. By using the coupling agent, the adhesion to the substrate is improved, and a protective film excellent in moisture resistance reliability can be obtained.

  The amount of the coupling agent used is 0.1 to 5 parts by weight, preferably 100 parts by weight of the thermosetting resin composition of the present invention containing (A), (B), (C) and (D). Is 0.5 to 4 parts by weight.

Similarly, the surfactant is added to improve the coating suitability of the thermosetting resin composition. Specific examples of the surfactant that can be used include silicon-based surfactants, fluorine-based surfactants, and organic-based surfactants. For example, BM-1000, BM-1100 (manufactured by BMCHEMIE), MegaFuck F470. F472, BL-20, R-0, R-30, R-30, R-90 (manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-381, S-382, SC -101, SC-102, SC-103, SC-104, SC-105, SC-106, KH-40 (manufactured by Asahi Glass Co., Ltd.), Ftop EF301, 303, 352 ( Shin-Akita Kasei ( )), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), PolyFOXPF-636, PF-651, PF-652, PF-3320 (manufactured by OMNOVA), Granol 400, Granol 420, Granol 440, Talen KY-5020, Florene DOPA-15BHFS, DOPA17HF, DOPA-33, DOPA-44, TG-720W TG-750W, Polyflow KL-245, KL-260, KL-500, KL-600, WS-30 (manufactured by Kyoeisha Chemical Co., Ltd.), Unidyne DS-403, DS-451, NS-1602, NS-1603, NS-1605 (manufactured by Daikin Industries, Ltd.), etc. Silicone surfactants, fluorine surfactants or organic surfactants are used as appropriate.
The amount added is usually 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the thermosetting resin composition of the present invention containing (A), (B), (C) and (D). Preferably it is 0.08-0.3 weight part.

  The thermosetting resin composition of the present invention uniformly dissolves the (A) condensate, (B) phenolic compound, (C) curing accelerator and (D) solvent, and, if necessary, the various additives. Can be obtained as a varnish. In this case, it is preferable to adjust so that the solid concentration is usually 15 to 50% by weight, preferably 20 to 40% by weight. Moreover, the thermosetting resin composition of the present invention obtained as described above may be subjected to microfiltration using, for example, a 0.05 to 1 μm filter, if necessary.

The coating film formed by the thermosetting resin composition of the present invention thus obtained has excellent adhesion to functional films provided on various substrates such as glass, wood, metal, and plastic. Coatings in fields where high visible light transmittance is required, such as organic EL devices and plasma display panels (high visible light transmission). In addition, it is particularly useful as a protective film agent for functional films, for example, when a protective film is formed on a colored resin film such as a color filter for liquid crystal display.
In the present invention, the most preferable functional film provided on the substrate is a colored resin layer for producing a color filter for liquid crystal display.

  When used as a protective film for a functional film including a colored resin layer, coating is usually performed by a spin coating method. The film thickness is usually applied under the condition of 0.1 to 10 μm, preferably 0.5 to 8 μm after heat curing. At this time, in order to efficiently perform the coating operation, the viscosity at 25 ° C. of the thermosetting resin composition or the functional film protective film agent of the present invention is 2 to 30 mPa · s, preferably 3 to 10 mPa · s. It is preferable to adjust as follows.

  It is necessary to appropriately select the optimum conditions depending on the component ratio blending ratio in the composition solution and the type of the solvent for drying and curing after coating, but usually after pre-baking at 70 to 100 ° C. to remove the solvent, Post bake at 150 to 250 ° C. for 10 minutes to 1.5 hours to cure. The curing temperature may not be constant, for example, curing may be performed while raising the temperature. Solvent removal by pre-baking and post-baking curing can be performed using an oven, a hot plate, or the like. In this way, the cured film of the present invention is formed.

  The functional film on which the protective film of the present invention is formed as described above is used for the preparation of various equipment according to each film.

Next, the case where the thermosetting resin composition or the functional film protective film agent of the present invention is used as a protective film for a colored resin film for a color filter will be described in detail.
A normal color filter used for a liquid crystal display element is one in which colored transparent patterns such as red, blue, and green are regularly arranged on a transparent substrate such as a glass substrate. For the formation of a colored transparent pattern, a photolithographic method using a color resist composed of pigments of various colors, binder resins, reactive diluents, photopolymerization agents, solvents and the like is widely used. In the photolithographic method, after applying the resist on a substrate, the resist is exposed through a photomask having a predetermined pattern, and then unnecessary portions are developed and removed, and this step is colored at least in red, blue, and green. A colored resin film patterned by repeating three times for each pattern is manufactured. The protective film of the present invention is provided on the patterned colored resin film by the method as described above to form a color filter, and then a transparent electrode as described below is provided.

  A normal liquid crystal display device is composed of a color filter part (ITO film formation and ITO patterning is performed if necessary), a liquid crystal part, a backlight part, and a polarizing film part. By using a color filter provided with a protective film, the liquid crystal display device of the present invention can be obtained.

  The thermosetting resin composition of the present invention is excellent in transparency, has a particularly high heat-resistant temperature, has high stability at high temperatures, and is advantageous as a protective film for functional films such as colored resin films. It can be suitably used as a protective film for a color filter, and the reliability of the liquid crystal display device using the color filter provided with such a protective film can be improved.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “part” means part by weight, and “%” means weight%.

Synthesis Example 1 (Synthesis of Silicon Compound (A-1) Having Epoxy Group)
94.4 parts of γ-glycidoxypropyltrimethoxysilane (compound of formula (1), manufactured by Shin-Etsu Chemical Co., Ltd.) and 188.8 parts of methyl isobutyl ketone were charged into the reactor, and the temperature was raised to 80 ° C. Subsequently, 10.8 parts of 0.1% potassium hydroxide aqueous solution was continuously dripped over 30 minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours by return distillation (80 ° C.).
After completion of the reaction, 45 parts of methyl isobutyl ketone and 113 parts of water were added for liquid separation, and the organic layer was taken and washed with water until the washing liquid became neutral. The organic layer was removed under reduced pressure to obtain 66 parts of an epoxy group-containing silicon compound (A-1). The epoxy equivalent of this silicon compound (A-1) was 170 g / eq, and the weight average molecular weight (Mw) in GPC analysis was 2300.

Synthesis Example 2 (Synthesis of silicon compound (A-2) having an epoxy group)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (compound of formula (2), Shin-Etsu Chemical Co., Ltd.) 58.5 parts, phenyltrimethoxysilane (compound of formula (3), Shin-Etsu Chemical 109.9 parts manufactured by Kogyo Co., Ltd.) and 339 parts of methyl isobutyl ketone were charged into a reaction vessel and heated to 80 ° C. After the temperature increase, 19.5 parts of a 0.5% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C. under reflux for 5 hours.
After completion of the reaction, 80 parts of methyl isobutyl ketone and 200 parts of water were added for liquid separation, and the organic layer was taken and washed with water until the washing liquid became neutral. Subsequently, 106 parts of silicon compounds (A-2) were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained silicon compound was 507 g / eq and Mw = 1500.

Examples 1 to 3 and Comparative Example 1
Each component shown in Table 1 was dissolved in a solvent (propylene glycol monomethyl ether acetate) according to the composition shown in the same table to obtain a thermosetting resin composition of the present invention having a solid concentration of 25%. This thermosetting. The viscosity of each of the conductive resin compositions was 5 to 7 mPa · s (measured under the condition of 10 rpm with an R-type viscometer manufactured by Toki Sangyo Co., Ltd.).
Also for the comparative example, a comparative thermosetting resin composition was obtained in the same manner as in Examples 1 to 3 using the following predetermined amounts of each component.

Table 1 Composition table
Example 1 Example 2 Example 3 Comparative Example 1
Silicon compound (A-1) (Note 1) 100 100
Silicon compound (A-2) (Note 2) 100
Epoxy resin (Note 3) 100
Curing agent (B-1) (Note 4) 65.8 39.3
Curing agent (B-2) (Note 5) 75.3
Curing agent (Note 6) 74.2
Curing accelerator (Note 7) 1 1 1 1
Surfactant (Note 8) 1 1 1 1
Solvent (Note 9) 503 424 532 529

Note 1 Silicon compound (A-1): Silicon compound having an epoxy group obtained in Synthesis Example 1 Note 2 Silicon compound (A-2); Silicon compound having an epoxy group obtained in Synthesis Example 2 Note 3 Epoxy resin represented by the formula (epoxy equivalent: 220 g / eq, epoxy resin described in Examples of Patent Document 1)

Note 4 Curing agent (B-1); 2,4-bisphenol S (hydroxyl equivalent: 125 g / eq, compound of formula (6))
* 5 Curing agent (B-2); Tris (4-hydroxyphenyl) phosphine oxide (compound of formula (5))
Note 6 Curing agent: EpiCure MP402FPY (Novolak terpene skeleton-containing phenol resin, manufactured by Nippon Epoxy Resin Co., Ltd.)
Note 7 Curing accelerator; 2,3-dihydro-1H-pyrrolo- [1,2-a] benzimidazole Note 8 Surfactant; Megafac F470 (fluorine surfactant, manufactured by Dainippon Ink Co., Ltd.)
Note 9 Solvent: Propylene glycol monomethyl ether acetate

Examples 4 to 6, Comparative Example 2
Films after curing of the thermosetting resin compositions of the present invention and comparative examples obtained in Examples 1 to 3 and Comparative Example 1 on a 0.7 mm thick glass substrate using a spin coater Apply to a thickness of 1.5 μm (however, in the ITO sputtering resistance test, the film thickness is 2 μm), pre-bake at 85 ° C. for 2 minutes, and then heat cure at 230 ° C. for 40 minutes. The cured film (protective film) for the present invention and for comparison was obtained.

○ Evaluation test With respect to each of these cured films, an evaluation test was performed on the following items, and the results shown in Table 2 were obtained.
(1) Transparency
The transmittance at 400 to 800 nm was measured with a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). Table 2 shows the minimum transmittance value. It is preferable that the transmittance is 95% or more in the entire range of 400 to 800 nm.
(2) Heat resistant transparency (coating yellowing test)
The glass substrate provided with each cured film was left in an oven at 250 ° C. for 60 minutes, and the transmittance at 400 to 800 nm was measured. Table 2 shows the minimum transmittance value. It is preferable that the transmittance is 95% or more in the entire range of 400 to 800 nm.
(3) ITO Sputter Resistance Each of the thermosetting resin compositions is applied on a glass substrate so as to have a cured film thickness of 2 μm, prebaked at 85 ° C. for 2 minutes, and then at 230 ° C. for 40 minutes. Thermal curing was performed under the conditions of: On these cured films, the state of the cured film was observed visually at 240 ° C. when ITO was sputtered to a thickness of 2500 mm and a sheet resistance value of 5.7 Ω / cm ² . Evaluation was made according to the following criteria.
○: No change in appearance Δ: Partial occurrence of wrinkles or cracks ×: Wrinkles, cracks or white turbidity occurred in the entire cured film (4) Solvent resistance Each of the above obtained After the glass substrate provided with the cured film was immersed in each solvent of isopropyl alcohol, N-methylpyrrolidone and γ-butyrolactone at 40 ° C. for 45 minutes, the degree of decrease of each cured film was measured with a stylus type surface roughness meter (P- 15 Tencor Co., Ltd.). When the degree of reduction was 5% or less even when immersed in any solvent, it was evaluated as ◯.
(5) Flatness A 1.5-micron-thick blue colored resin film having a hollow portion is provided on a glass substrate, and the thermosetting resin composition is formed thereon with a cured film thickness of 1.5 microns. After being pre-baked under conditions of 85 ° C. for 2 minutes and then thermosetting at 230 ° C. for 40 minutes, the surface flatness is measured with the stylus type surface roughness meter. did. Table 2 shows the maximum step value.

○ Evaluation results Table 2 shows the results obtained in the above evaluation tests.
Table 2 Results of evaluation test
Example 4 Example 5 Example 6 Comparative Example 2
(Note 1) (Example 1) (Example 2) (Example 3) (Comparative Example 1)
Transparency (%) 98 98 98 96
Heat-resistant transparency (%) 95 98 97 84
ITO sputter resistance ○ ○ ○ ×
Solvent resistance ○ ○ ○ ○
Flatness (μm) 0.07 0.08 0.06 0.6

  Note 1: Example number or comparative example of the thermosetting resin composition used is shown.

  As is clear from the results in Table 2, the protective film obtained from the thermosetting resin composition of the present invention is excellent in transparency, has a particularly high heat-resistant temperature, has high stability at high temperatures, Furthermore, it is excellent in solvent resistance and flatness. Therefore, the thermosetting resin composition of the present invention is useful as a protective film agent for a colored resin film, and in particular, when used as a protective film agent for a colored resin film used in a color filter for a liquid crystal display device, Improves reliability and quality in filter manufacturing.

Claims (8)

A thermosetting resin composition comprising the following (A), (B), (C), and (D).
(A) The following (a-1) and / or (a-2)
(A-1) A silicon compound having an epoxy group represented by the following formula (1) and / or a silicon compound having an epoxy group represented by formula (2) or a self-condensed product (a-2) ) A silicon compound having an epoxy group represented by formula (2) and / or a co-condensate of a silicon compound having an epoxy group represented by formula (2) and a compound represented by formula (3) below (B) phenolic compound (C) Curing accelerator (D) solvent

(In the formula (1), formula (2) and formula (3), X represents a C2-C5 alkylene group optionally interrupted by an ether group (—O—) or an ester group (—OCO—), R ₁ , R ₂ and R ₃ each represent a C1-C4 alkyl group, and Z represents a methyl group or a phenyl group.) The thermosetting resin composition according to claim 1, wherein the phenolic compound is a compound represented by the following formula (4) or formula (5).

The thermosetting resin composition according to claim 2, wherein the phenolic compound represented by the formula (4) is a compound represented by the following formula (6).

The protective film agent for functional films which consists of a thermosetting resin composition as described in any one of Claims 1 thru | or 3. The protective film agent for functional film according to claim 4, wherein the functional film is a colored resin film. A cured resin film obtained by curing the protective film agent for a functional film according to claim 4 or 5. A color filter comprising a colored resin film having the cured resin film according to claim 6. A liquid crystal display device comprising the color filter according to claim 7.