JP6912695B2 - Composite resin composition and cured composite resin - Google Patents

Description

The present invention relates to a composite resin composition and a cured composite resin.

In recent years, with the increasing functionality and diversification of electronic devices, display devices in which display elements such as liquid crystals are provided with touch panel / touch sensor functions have rapidly become widespread. In these devices, functional layers such as an insulating film and a protective film are provided in order to accurately recognize the contact position. The functional layer must have characteristics such as transparency, light resistance, heat resistance, adhesion to the base material and other adjacent layers, as well as moldability and flexibility to ensure design freedom. Is increasing year by year. Further, it may be necessary to perform a patterning process on the functional layer itself, and a material exhibiting good patterning property with respect to a developing solution or the like is required. Further, since the transparent electrode may be patterned and formed using ITO or the like after the functional layer is formed, even if it is exposed to a chemical solution (resist developer, ITO etching solution, resist stripping solution, etc.) necessary for forming an ITO pattern. In some cases, it is preferable to have resistance to prevent film slippage (chemical resistance). Further, when the ITO pattern is formed, a difference in refractive index is generated, the pattern becomes easy to see, and the visibility of the display screen is lowered. Therefore, the functional layer is required to be made of a material having a high refractive index. ing.

In order to meet these required characteristics, it has been proposed to use a cured product composed of a composite resin composition in which an organic material and an inorganic material are composited as a functional layer. For example, as in Patent Document 1, a dispersion system material in which nano-sized inorganic fine particles are uniformly dispersed is being studied, and an inorganic fine particle is finely dispersed in an organic material on the order of several tens of nano particles to provide a uniform and stable dispersion system. A composite resin composition in which a large amount of a dispersant or a surface treatment agent is added to a compounding system is known in order to construct the above.

However, when a large amount of dispersant or surface treatment agent is blended, the particles can be uniformly dispersed, but due to the problems of light resistance and heat resistance of the dispersant and surface treatment agent itself, the light resistance of the cured composite resin obtained is obtained. It may reduce the property and heat resistance. Further, when the compatibility between the dispersant or surface treatment agent and other compounding components is poor, the obtained cured composite resin may become cloudy and transparency may not be ensured. Further, since the dispersant and the surface treatment agent present in a large amount cause a decrease in the refractive index, there is a problem that the visibility of the display screen is deteriorated.

On the other hand, Patent Document 2 proposes a composite resin composition which does not contain a dispersant and / or a surface treatment agent at all and has a high refractive index. However, the cured product obtained from the composite resin composition described in Patent Document 2 may have a film stickiness when forming an electrode pattern with ITO or the like, and has a problem of insufficient chemical resistance. ..

Japanese Unexamined Patent Publication No. 2011-116943 International Publication No. 2015/087946

The present invention provides a composite resin composition having excellent dispersion stability and uniformity of inorganic fine particles, which provides a cured composite resin having excellent optical properties (high refractive index), developability, and chemical resistance. The purpose is to provide.

As a result of diligent studies, the present inventor has found that the chemical resistance of the obtained cured composite resin is improved by blending the compound having one or more epoxy groups with the composite resin composition described in Patent Document 2. The heading, the present invention was completed.

That is, the composite resin composition of the present invention is
Inorganic particles,
solvent,
A condensed ring structure-containing resin having a condensed ring structure derived from at least one selected from the group consisting of inden, tetralin, fluorene, xanthene, anthracene, and benzanthracene, and
Contains compounds with one or more epoxy groups
The average particle size of the inorganic fine particles after dispersion is 10 to 70 nm.

The composite resin composition of the present invention further contains a dispersant and / or a surface treatment agent.
The total content of the dispersant and the surface treatment agent is preferably 5 parts by weight or less in terms of the weight of the active ingredient with respect to 100 parts by weight of the inorganic fine particles.

In the composite resin composition of the present invention, the inorganic fine particles are preferably at least one selected from the group consisting of zirconium oxide, titanium oxide and barium titanate.

In the composite resin composition of the present invention, it is preferable that the condensed ring structure-containing resin has a condensed ring structure derived from fluorene and a (meth) acryloyl group.

In the composite resin composition of the present invention, the water content of the compound having one or more epoxy groups is preferably 0 to 70% by weight.

In the composite resin composition of the present invention, the epoxy equivalent of the compound having one or more epoxy groups is 100 to 1000 g / eq, and the content of the compound having one or more epoxy groups is 0.1 in the total solid content. It is preferably ~ 45% by weight.

The composite resin composition of the present invention preferably further contains an aliphatic polyfunctional acrylate.

In the composite resin composition of the present invention, the content of the inorganic fine particles is preferably 30 to 80% by weight based on the total solid content.

The cured composite resin of the present invention is characterized by thermosetting and photocuring the composite resin composition of the present invention.

The cured composite resin product of the present invention is preferably a thin film or a molded product.

The optical film of the present invention is characterized by comprising the cured composite resin of the present invention.

The display element of the present invention is characterized by comprising the cured composite resin of the present invention.

Since the composite resin composition of the present invention contains a compound having one or more epoxy groups, it is excellent in dispersion stability and uniformity of inorganic fine particles, and is excellent in optical properties (high refractive index), developability, and chemical resistance. A cured composite resin can be given.

<< Composite resin composition >>
The composite resin composition of the present invention
Inorganic particles,
solvent,
A condensed ring structure-containing resin having a condensed ring structure derived from at least one selected from the group consisting of inden, tetralin, fluorene, xanthene, anthracene, and benzanthracene, and
Contains compounds with one or more epoxy groups
The average particle size of the inorganic fine particles after dispersion is 10 to 70 nm.

<Inorganic fine particles>
The inorganic fine particles are not particularly limited, and examples thereof include metal oxide fine particles, nitrides, composite oxides composed of two or more kinds of metal elements, and compounds in which metal oxides are doped with different elements. ..

The metal oxide fine particles are not particularly limited, but are, for example, zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O). ₃ , FeO, Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ) , Indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ) , Bismus oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₅ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO) and the like.

As the metal oxide fine particles, those dispersed in various solvents in advance may be used. The solvent is not particularly limited, and is, for example, alcohols such as methanol, ethanol, 2-propanol and butanol, esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate and γ-butyrolactone, and diethyl ether. , Ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, ethers such as diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone. , Ketones such as cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and amides such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The mixing ratio of the solvent and the metal oxide fine particles is not particularly limited, but is preferably 30:70 to 90:10.

The nitride is not particularly limited, and examples thereof include silicon nitride and boron nitride.

The composite oxide composed of two or more kinds of metal elements is not particularly limited, and examples thereof include titanates such as barium titanate, titanium / silicon composite oxides, and yttria-stabilized zirconia. Such a composite oxide has a core-shell structure in which not only a compound or a solid solution composed of a multi-component element but also a metal oxide composed of other metal elements is used to surround the core metal oxide fine particles. It includes one having a multi-component dispersion type structure in which a plurality of other metal oxide fine particles are dispersed in one metal oxide fine particle.

The compound in which a metal oxide is doped with a different element is not particularly limited, and examples thereof include tantalum-doped titanium oxide and niob-doped titanium oxide.

These inorganic fine particles may be used alone or in combination of two or more. Further, the method for producing the inorganic fine particles is not particularly limited. The inorganic fine particles are preferably at least one selected from the group consisting of zirconium oxide, titanium oxide and barium titanate because they are easily available and their optical properties such as refractive index can be easily adjusted.

The primary particle size of the inorganic fine particles is not particularly limited, but is preferably 1 to 70 nm, more preferably 1 to 50 nm. If it is less than 1 nm, the specific surface area of the inorganic fine particles is large and the aggregation energy is high, so that it may be difficult to maintain dispersion stability. On the other hand, if it exceeds 70 nm, light is scattered violently by the inorganic fine particles in the thin film or the molded product, and high transparency may not be maintained. The primary particle size can be measured by a device such as a dynamic light scattering method, a laser diffraction method, or an ultracentrifugation method.

The average particle size after dispersion of the inorganic fine particles, that is, the average particle size in the composite resin composition of the present invention is not particularly limited as long as it is 10 to 70 nm, but is preferably 10 to 50 nm. In order to make it less than 10 nm, it is necessary to use particles having a small primary particle diameter, which may make dispersion difficult. On the other hand, if it exceeds 70 nm, it may become cloudy when it is made into a cured product such as a thin film or a molded product.

In the composite resin composition of the present invention, a large amount of inorganic fine particles can be blended. For example, it can be blended with respect to 100 parts by weight of the condensed ring structure-containing resin, which will be described later, even if it is 200 parts by weight or more, or even 500 parts by weight or more, which is usually difficult to mix. The content of the inorganic fine particles is not particularly limited, but is preferably 0.1 to 5000 parts by weight, more preferably 1 to 2000 parts by weight, still more preferably 5 to 1000 parts by weight, based on 100 parts by weight of the condensed ring structure-containing resin. .. If the content is less than 0.1 parts by weight, the characteristics of the inorganic fine particles are not sufficiently exhibited, and if it exceeds 5000 parts by weight, the film forming property is deteriorated.

In the composite resin composition of the present invention, the content of the inorganic fine particles is not particularly limited, but is preferably 30 to 80% by weight, more preferably 45 to 75% by weight, based on the total solid content. If the content of the inorganic fine particles is less than 30% by weight in the total solid content, the visibility of the display screen may be deteriorated, and if it exceeds 80% by weight, the film forming property may be deteriorated.

<Solvent>
The solvent is not particularly limited, but for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether. Classes; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and diethylene glycol ethyl methyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol. Diethylene glycol monoalkyl ethers such as monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol mono Alkylene glycol monoalkyl ether acetates such as ethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy- Ketones such as 4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, succinate Examples thereof include esters such as dimethyl acid acid, diethyl succinate, diethyl adipate, diethyl malonate, and dibutyl oxalate. Among these, ethylene glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferable, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl are preferable. Ether acetate and methyl amyl ketone are more preferred. These solvents may be used alone or in combination of two or more.

In the composite resin composition of the present invention, the content of the solvent with respect to the inorganic fine particles is not particularly limited, but is preferably 50 to 2000 parts by weight, preferably 80 to 2000 parts by weight, based on 100 parts by weight of the inorganic fine particles. Is more preferable. If the content of the solvent is less than 50 parts by weight with respect to 100 parts by weight of the inorganic fine particles, the dispersion stability of the inorganic fine particles may decrease, and if it exceeds 2000 parts by weight, it may be difficult to thicken the film. be.

<Resin containing condensed ring structure>
Epoxy ester resin (E) and polyvalent carboxylic acid are examples of the condensed ring structure-containing resin having a condensed ring structure derived from at least one selected from the group consisting of inden, tetraline, fluorene, xanthene, anthracene, and benzanthracene. Acid resin (G) or the like can be used.
The epoxy ester resin (E) is represented by reacting the epoxy resin (A) represented by the following general formula (1) with the monobasic carboxylic acid (B), or by the following general formula (10). It can be obtained by reacting the alcohol compound (C) with the glycidyl ester compound (D). The epoxy ester resin (E) is preferably one having a condensed ring structure derived from xanthene or fluorene because it is excellent in dispersibility and heat resistance.

In the general formula (1), Y _{1 to 4} are groups independently represented by the following general formula (2) or the following general formula (3), and p _{1 to 4} are independently from 0. It is an integer of 4.

In the general formula (2), Y _{5 to 6} are groups represented by the general formula (2) or the following general formula (3) _{independently, and p 5 to 6} are independently 0 to 4 respectively. Is an integer of. When Y ₁ to 4 are the groups represented by the general formula (2) in the general formula (1), and Y ₅ to 6 are the groups represented by the general formula (2) in the general formula (2). _{, Y1 to 4} in the general formula (1) form an oligomer having a group represented by the general formula (2) as a constituent unit.

In the general formulas (1) and (2), Z is at least selected from the group consisting of inden, tetraline, fluorene, xanthene, anthracene, and benzanthracen as shown in the following formulas (4) to (9). It is a divalent group containing a fused ring structure derived from one kind, and R _{1 to 6} are independently linear, branched or cyclic alkyl or alkenyl groups having 1 to 10 carbon atoms, and carbon atoms. It is an alkoxy group of 1 to 5, a phenyl group which may have a substituent, or a halogen atom, q _{1 to 6} are each independently an integer of 0 to 4, and s _{1 to 2} are Each is an integer from 0 to 10 independently. Further, in the general formulas (1) to (3), R _{7 to 14} are independently hydrogen atoms or methyl groups, and m _{1 to 8} are independently integers from 0 to 10. Here, a plurality of R _{1 to 14} and Y _{1 to 6} may be the same or different. Further, in the general formula (1), the structural formula may be symmetrical or asymmetrical.

In the general formula (10), Z is the same as described above, and _{R15 to 16} are independently linear, branched or cyclic alkyl or alkenyl groups having 1 to 10 carbon atoms, and have 1 to 10 carbon atoms. It is an alkoxy group of 5, a phenyl group which may have a substituent, or a halogen atom, f _{1 to 2} are each independently an integer of 0 to 4, and R _{17 to 18} are independent of each other. Therefore, m _{9 to 10} are independently integers from 0 to 10, and r _{1 to 2} are independently integers from 1 to 5. Here, the plurality of Rs _{15 to 18} may be the same or different. Further, in the general formula (10), the structural formula may be symmetrical or asymmetrical.

The monobasic carboxylic acid (B) is not particularly limited as long as it is a compound having one carboxyl group, and for example, (meth) carboxylic acid, cyclopropanecarboxylic acid, 2,2,3,3-tetramethyl-. 1-Cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenylcarboxylic acid, 2-furancarboxylic acid, 2-tetracarboxylic acid, cyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4 -Pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexane-1-carboxylic acid, 4-hydroxycyclohexanecarboxylic acid, 1,3,4,5-tetrahydroxycyclohexane- 1-Carboxylic acid, 2- (1,2-dihydroxy-4-methylcyclohexyl) propionic acid, shikimic acid, 3-hydroxy-3,3-diphenylpropionic acid, 3- (2-oxocyclohexyl) propionic acid, 3- Cyclohexene-1-carboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid hydrogen alkyl, cycloheptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic acid, 1-adamantancarboxylic acid, (4-tricyclo [5.2] .1.0 ^2.6 ] Carboxylic acid, p-methylbenzoic acid, p-ethyl benzoic acid, p-octyl benzoic acid, p-decyl benzoic acid, p-dodecyl benzoic acid, p-methoxy benzoic acid Acids, p-ethoxybenzoic acid, p-propoxybenzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid, p-hexyloxybenzoic acid, p-fluorobenzoic acid, p-chlorobenzoic acid, p-chloromethyl Benzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid, 4-acetoxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, o-benzoylbenzoic acid, o- Nitrobenzoic acid, o- (acetoxybenzoyloxy) benzoic acid, terephthalic acid monomethyl ester, isophthalic acid monomethyl ester, isophthalic acid monocyclohexyl ester, phenoxyacetic acid, chlorophenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2-oxo-3-phenylpropi Onic acid, o-bromophenylacetic acid, o-iodophenylacetic acid, methoxyphenylacetic acid, 6-phenylhexanoic acid, biphenylcarboxylic acid, α -Naftoeic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid, indancarboxylic acid, 1,4-dioxo-1,4-dihydronaphthalene-2-carboxylic acid, 3,3- Examples thereof include diphenylpropionic acid, nicotinic acid, isonicotinic acid, silicic acid, 3-methoxysilicic acid, 4-methoxycineric acid, quinolinecarboxylic acid and the like. These may be used alone or in combination of two or more. As a particularly suitable monobasic carboxylic acid (B), one containing an unsaturated group capable of introducing a radiopolymerizable functional group is preferable, and for example, (meth) acrylic acid is preferable. Here, the radiopolymerizable functional group refers to a functional group having a property of causing a polymerization reaction by various types of radiation. "Radiation" includes visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, proton beam rays and the like.

The glycidyl ester compound (D) is not particularly limited, and examples thereof include glycidyl (meth) acrylate, glycidyl acetate, glycidyl butyrate, glycidyl benzoate, glycidyl p-ethylbenzoate, and glycidyl (tere) phthalate. .. These may be used alone or in combination of two or more. Among these, glycidyl monobasic carboxylate is particularly preferable, and among these, those containing an unsaturated group capable of introducing a radiopolymerizable functional group are preferable, and for example, glycidyl (meth) acrylate is preferable.

The reaction between the epoxy resin (A) represented by the general formula (1) and the monobasic carboxylic acid (B), and the alcohol compound (C) and the glycidyl ester compound (D) represented by the general formula (10). The reaction with is carried out in a temperature range of 50 to 120 ° C. for 5 to 30 hours, using an appropriate solvent as needed. Examples of the solvent include alkylenes such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and 3-methoxybutyl-1-acetate. Monoalkyl ether acetates; alkylene monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether; ketones such as methyl ethyl ketone and methyl amyl ketone; dimethyl succinate, diethyl succinate, diethyl adipate, malonic acid Examples thereof include esters such as diethyl and dibutyl oxalate. Among these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferable. Further, a catalyst and a polymerization inhibitor can be used if necessary. Examples of the catalyst include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds and the like, and the blending amount thereof is not particularly limited, but 0. It is preferably 01 to 10% by weight. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, 2,6-diisobutylphenol, 2,6-di-tert-butyl-4-methylphenol and the like. The blending amount thereof is usually 5% by weight or less of the total reaction product.

The polyvalent carboxylic acid resin (G) can be obtained by reacting the epoxy ester resin (E) with the polybasic carboxylic acid or its anhydride (F).

The polybasic carboxylic acid or its anhydride (F) is not particularly limited as long as it is a carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid and tetracarboxylic acid or an anhydride thereof, and for example, maleic acid and succinic acid. , Itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid and other dicarboxylic acids or anhydrides thereof; Trimerit Acids or anhydrides thereof; tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid and the like, and dianhydrides thereof and the like can be mentioned.

Examples of the polyvalent carboxylic acid resin (G) include resins represented by the following general formula (11) or the following general formula (12).

In the general formulas (11) and (12), Z is a divalent group containing a fused ring structure derived from at least one selected from the group consisting of inden, tetralin, fluorene, xanthene, anthracene, and benzanthracene. Yes, A ₁ and A ₃ are residues of tetracarboxylic dianhydride, and A ₂ and A ₄ are residues of dicarboxylic acid anhydride. Further, u and u ₂ are average values, which are 0 to 130.

In the general formulas (11) and (12), Z is preferably a divalent group containing a fused ring structure derived from xanthene or fluorene. This is because the polyvalent carboxylic acid resin (G) has a high refractive index and is advantageous in that the difference in refractive index from the inorganic fine particles can be reduced.

The polyvalent carboxylic acid resin (G) is obtained by reacting the epoxy ester resin (E) with the polybasic carboxylic acid or its anhydride (F). In this reaction, polyhydric alcohols can coexist in order to improve the heat resistance and heat-resistant yellowing of the obtained resin.

The polyhydric alcohols are not particularly limited, but for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, and 1,4-butanediol. , Neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol, 1,9-nonanediol and other fats Group diols, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, alicyclic diols such as hydrogenated bisphenol A, aromatic diols such as ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, glycerin, Examples thereof include trihydric or higher alcohols such as trimethylolpropane, trimethylolethane, ditrimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol. These may be used alone or in combination of two or more.

In this reaction, the order of addition of the epoxy ester resin (E), the polyhydric alcohols, and the polybasic carboxylic acid or its anhydride (F) is not particularly limited. For example, these may be mixed and reacted at the same time, or the epoxy ester resin (E) and the polyhydric alcohol may be mixed, and then the polybasic carboxylic acid or its anhydride (F) may be added and mixed. Is also good. Further, a polybasic carboxylic acid may be further added to these reaction products to cause a reaction.

By appropriately selecting the type of the polybasic carboxylic acid or its anhydride (F), the polyvalent carboxylic acid resin (GA) having various condensed ring structures having different structures and the polyhydric alcohol were reacted. A polyvalent carboxylic acid resin (Gb) can be produced. Specifically, for example, the first to sixth multivalues shown in (G-a-i) to (G-a-iii) and (G-bi) to (G-b-iii) below. Carboxylic acid resins are prepared, which are exemplary.

(G-a-i) First Polyvalent Carboxylic Acid Resin: A resin obtained by mixing an epoxy ester resin (E) with one kind of polybasic carboxylic acid or an anhydride thereof (F) and reacting them. (G-a-ii) Second polycarboxylic acid resin: A mixture of an epoxy ester resin (E) and two or more types of polybasic carboxylic acids or anhydrides (F) thereof (for example, dicarboxylic acid anhydride). And a mixture of tetracarboxylic acid dianhydride) and reacting them; and (G-a-iii) third polycarboxylic acid resin: epoxy ester resin (E) and tetracarboxylic acid. A resin obtained by reacting an acid or a dianhydride thereof with a reaction product obtained by further reacting a dicarboxylic acid or an anhydride thereof.

(G-bi) Fourth polyvalent carboxylic acid resin: An epoxy ester resin (E), a polyhydric alcohol, and one kind of polybasic carboxylic acid or its anhydride (F) are mixed and reacted. Resin obtained by ) (For example, a mixture of dicarboxylic acid anhydride and tetracarboxylic acid dianhydride) and reacting them; and (G-b-iii) sixth polyvalent carboxylic acid resin: A resin obtained by reacting an epoxy ester resin (E), a polyhydric alcohol, a tetracarboxylic acid or a dianhydride thereof, and further reacting the obtained reaction product with a dicarboxylic acid or an anhydride thereof.

The polyvalent carboxylic acid resin (GA) or (Gb) thus obtained having various condensed ring structures having different structures is used depending on the intended use.

The term "multibasic carboxylic acid or its anhydride (F)" means "at least one of a specific polybasic carboxylic acid and its corresponding anhydride", and for example, a polybasic carboxylic acid. If the acid is phthalic acid, it refers to at least one of phthalic acid and phthalic anhydride. Further, "a mixture of two or more kinds of polybasic carboxylic acids or their anhydrides (F)" means that at least two kinds of polybasic carboxylic acids or their anhydrides are present at the same time. Therefore, in the methods (G-a-ii) and (G-b-ii), at least two types of polybasic carboxylic acids or their anhydrides (F) are involved in the reaction.

In any of the above methods, the polyvalent carboxylic acid resin (G) uses the epoxy ester resin (E), the polyhydric alcohol, the polybasic carboxylic acid or its anhydride (F) in the above-exemplified method (order). It is produced by dissolving (suspending) in a solvent and heating to react. Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, ester-based solvents of alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate and acetic acid, methyl ethyl ketone and methyl isobutyl ketone. , Ketone solvent such as cyclohexanone and the like. In addition, a catalyst can be added as needed. Examples of the catalyst include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, and imidazole compounds, and the amount thereof is not particularly limited, but 0.01 of the entire reaction product. It is preferably 10% by weight.

The reaction temperature of the above reaction is not particularly limited, but is preferably 50 to 130 ° C, more preferably 70 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction does not proceed smoothly, and unreacted polybasic carboxylic acid or its anhydride (F) may remain. On the other hand, if the temperature exceeds 130 ° C., some condensation of the carboxyl group and the hydroxyl group may occur, and the molecular weight may increase rapidly.

When a polyhydric alcohol is used in the production of the polyvalent carboxylic acid resin (G), the molar ratio of the hydroxyl group of the epoxy ester resin (E) to the hydroxyl group of the polyhydric alcohol (hydroxyl group of the epoxy ester resin (E) / polyhydric). The hydroxyl group of the alcohol) is not particularly limited, but is preferably 99/1 to 50/50, and more preferably 95/5 to 60/40. If the molar ratio of the hydroxyl groups of the polyhydric alcohol exceeds 50, the molecular weight of the polyvalent carboxylic acid resin (G) rapidly increases, and there is a risk of gelation. Further, when the molar ratio is less than 1, it tends to be difficult to improve heat resistance and heat discoloration.

The blending amount of the polybasic carboxylic acid or its anhydride (F) is not particularly limited, but the hydroxyl group of the epoxy ester resin (E) (when a polyhydric alcohol is used, the total with the hydroxyl group of the polyhydric alcohol) 1 It is preferably 0.1 to 1 equivalent, more preferably 0.4 to 1 equivalent, relative to the equivalent (molar) in terms of acid anhydride group. If the blending amount is less than 0.1 equivalent, the molecular weight of the polyvalent carboxylic acid resin (G) is not sufficiently high, and the heat resistance of the cured product of the composite resin composition containing the polyvalent carboxylic acid resin (G) is insufficient. In some cases, the composite resin composition may remain on the substrate even after development. On the other hand, when the blending amount exceeds 1 equivalent, the unreacted polybasic carboxylic acid or its anhydride (F) remains, the molecular weight of the polyvalent carboxylic acid resin (G) becomes low, and the polyvalent carboxylic acid The developability of the composite resin composition containing the resin (G) may be inferior. The acid anhydride group conversion indicates the amount when all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid used or its anhydride (F) are converted into acid anhydride groups.

In the production of the second, third, fifth and sixth polyvalent carboxylic acid resins (G), two or more kinds of polybasic carboxylic acids or their anhydrides (F) are used. Generally, a dicarboxylic acid anhydride and a tetracarboxylic dianhydride are used. The ratio of the dicarboxylic acid anhydride to the tetracarboxylic dianhydride (dicarboxylic acid anhydride / tetracarboxylic dianhydride) is preferably 1/99 to 90/10 in terms of molar ratio, and 5/95 to 80. More preferably, it is / 20. If the proportion of dicarboxylic acid anhydride is less than 1, the resin viscosity may increase and workability may decrease. Further, since the molecular weight of the polyvalent carboxylic acid resin (G) becomes too large, when a coating film is formed on a substrate using a composite resin composition containing the polyvalent carboxylic acid resin (G) and exposure is performed. , The exposed portion tends to be difficult to dissolve in the developing solution, and it tends to be difficult to obtain the desired pattern. On the other hand, if the ratio of the dicarboxylic acid anhydride exceeds 90, the molecular weight of the polyvalent carboxylic acid resin becomes too small. Therefore, when a coating film is formed on the substrate using a composite resin composition containing the polyvalent carboxylic acid resin. In addition, problems such as sticking remaining on the coating film after prebaking are likely to occur.

In the composite resin composition of the present invention, the polyvalent carboxylic acid resin (G) preferably contains a radiopolymerizable functional group, and specifically, contains an unsaturated group such as a (meth) acryloyl group. Is preferable. When the polyvalent carboxylic acid resin (G) is a resin containing a radiation-polymerizable functional group, the composite resin composition of the present invention has photocurability and is therefore used as a photosensitive composite resin composition (H). Can be done. Here, photosensitivity refers to the property of causing a chemical reaction by various types of radiation, and such radiation includes visible light, ultraviolet rays, electron beams, X-rays, α-rays, and β-rays in order from the one having the longest wavelength. , And γ-rays. Of these, ultraviolet rays are the most preferable radiation in practical terms from the viewpoint of economy and efficiency. As the ultraviolet rays, ultraviolet light oscillated from lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, arc lamps, and xenon lamps can be preferably used. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

In the composite resin composition of the present invention, the content of the condensed ring structure-containing resin with respect to the inorganic fine particles is not particularly limited, but is preferably 5 to 300 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the inorganic fine particles. It is more preferable that it is a part. If the content of the condensed ring structure-containing resin is less than 5 parts by weight with respect to 100 parts by weight of the inorganic fine particles, the dispersion stability of the inorganic fine particles may decrease, and if it exceeds 300 parts by weight, the refractive index of the cured product May decrease.

In the composite resin composition of the present invention, from the viewpoint of heat resistance and dispersibility, it is preferable that the condensed ring structure-containing resin has a condensed ring structure derived from fluorene. Further, from the viewpoint of photocurability, it is preferable that the condensed ring structure-containing resin has a (meth) acryloyl group.

<Compound having one or more epoxy groups>
The composite resin composition of the present invention contains a compound having one or more epoxy groups. When patterning is performed using a negative photoresist resin, the solvent component is heat-removed (prebaked), irradiated with radiation such as ultraviolet rays, and then the unexposed portion is dissolved with a developing solution to remove it. When the composite resin composition of the present invention is thermoset, the carboxyl group remaining in the fused ring structure-containing resin reacts with the epoxy group of the compound having one or more epoxy groups, whereby the cured composite resin obtained. Chemical resistance can be improved.

The compound having one or more epoxy groups is not particularly limited, and for example, polybutadiene diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl. Examples include ether. These may be used alone or in combination of two or more.

The water content of the compound having one or more epoxy groups is not particularly limited, but is preferably 0 to 70% by weight, more preferably 0 to 60% by weight. If the water content of the compound having one or more epoxy groups exceeds 70% by weight, film blistering may occur when exposed to a chemical solution such as a resist developer, an ITO etching solution, or a resist stripping solution.

As used herein, the term "water-soluble" refers to the dissolution rate when 10 parts by weight of a compound having one or more epoxy groups is dissolved in 90 parts by weight of water at room temperature.

The epoxy equivalent of the compound having one or more epoxy groups is not particularly limited, but is preferably 100 to 1000 g / eq, and more preferably 100 to 250 g / eq. If the epoxy equivalent is less than 100 g / eq, film burr may occur in the exposed portion, and if it exceeds 1000 g / eq, a residue may be generated in the unexposed portion during development and the developability may be deteriorated.

The molecular weight of the compound having one or more epoxy groups is not particularly limited, but is preferably 100 to 3500, and more preferably 110 to 1000. If the molecular weight is less than 100, the chemical resistance may be lowered, and if it exceeds 3500, a residue may be generated in the unexposed portion during development and the developability may be lowered.

In the composite resin composition of the present invention, the content of the compound having one or more epoxy groups is not particularly limited, but is preferably 0.1 to 45% by weight based on the total solid content.

In the composite resin composition of the present invention, the content of the compound having one or more epoxy groups with respect to the condensed ring structure-containing resin is not particularly limited, but is 0.01 to 100 with respect to 100 parts by weight of the condensed ring structure-containing resin. It is preferably parts by weight, more preferably 1 to 50 parts by weight. If the content of the compound having one or more epoxy groups is less than 0.01 parts by weight with respect to 100 parts by weight of the condensed ring structure-containing resin, the chemical resistance may decrease, and if it exceeds 100 parts by weight, Developability may decrease.

The composite resin composition of the present invention may optionally contain other components in addition to the inorganic fine particles, the solvent, the condensed ring structure-containing resin, and the compound having one or more epoxy groups. Other components include, for example, dispersants and / or surface treatment agents, aliphatic polyfunctional acrylates, curing agents, leveling agents, resin components, thermal polymerization inhibitors, adhesion aids, epoxy group curing accelerators, surfactants. , Antifoaming agent and the like.

<Dispersant and / or surface treatment agent>
The composite resin composition of the present invention shows good dispersibility even when it does not contain any dispersant and / or surface treatment agent, but may contain a small amount of dispersant and / or surface treatment agent.
The dispersant is not particularly limited, and examples thereof include a polyacrylic acid-based dispersant, a polycarboxylic acid-based dispersant, a phosphoric acid-based dispersant, and a silicon-based dispersant. These dispersants may be used alone or in combination of two or more.

The inorganic fine particles may be surface-treated. The surface treatment refers to a treatment of binding a compound that can react with a hydroxyl group existing on the surface of fine particles, such as a coupling agent. The surface treatment can be carried out by dispersing the inorganic fine particles in a solvent, mixing the coupling agent under acidic conditions, and allowing the coupling agent to act. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent and a titanium coupling agent. For example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane and the like. (Meta) acryloxysilanes; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilanes such as ethyltrimethoxysilane; vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, dimethylvinylmethoxysilane, vinyltrichlorosilane, dimethylvinylchlorosilane; N-2- Aminosilanes such as (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane; N- (vinylbenzyl) -2 Tertiary ammonium salts such as the hydrochloride salt of −aminoethyl-3-aminopropyltrimethoxysilane; p-styryltrimethoxysilane; phenyltrimethoxysilane; titanates such as isopropyldimethacrylisostearoyl titanate and isopropyldiacylisostearoyl titanate. Kind; etc. These surface treatment agents may be used alone or in combination of two or more. Among these surface treatment agents, epoxy silanes and (meth) acryloxisilanes have a reactive functional group and can be cured together with a fused ring structure-containing resin to immobilize inorganic fine particles in the cured product. preferable.

When the composite resin composition of the present invention contains a dispersant and / or a surface treatment agent, the total content of the dispersant and the surface treatment agent is not particularly limited, but is based on the weight of the active ingredient with respect to 100 parts by weight of the inorganic fine particles. It is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less. If the total content of the dispersant and the surface treatment agent exceeds 5 parts by weight, the refractive index, heat resistance, and light resistance of the cured product of the composite resin composition may decrease. When the composite resin composition of the present invention contains a dispersant and / or a surface treatment agent, the lower limit of the total content of the dispersant and the surface treatment agent is not particularly limited, but for example, the active ingredient is based on 100 parts by weight of the inorganic fine particles. The weight is preferably 0.1 part by weight or more.

<Aliphatic polyfunctional acrylate>
From the viewpoint of photocurability, the composite resin composition of the present invention preferably further contains an aliphatic polyfunctional acrylate. The aliphatic polyfunctional acrylate is not particularly limited, but for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; ethylene. Glycoldi (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, Trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , (Meta) acrylic acid esters such as glycerol (meth) acrylate and the like. These may be used alone or in combination of two or more.

When the composite resin composition of the present invention contains an aliphatic polyfunctional acrylate, the content thereof with respect to the inorganic fine particles is not particularly limited, but may be 0.1 to 40 parts by weight with respect to 100 parts by weight of the inorganic fine particles. It is preferably 1 to 30 parts by weight, more preferably 1 to 30 parts by weight. If the content is less than 0.1 parts by weight with respect to 100 parts by weight of the inorganic fine particles, curing may be insufficient, and if it exceeds 40 parts by weight, the developability may be lowered.

The method for producing the composite resin composition of the present invention is not particularly limited, and for example, a method of dispersing inorganic particles, a solvent, a resin containing a condensed ring structure, and a compound having one or more epoxy groups using a bead mill, etc. Can be mentioned. When the dispersion using the bead mill is completed, it is preferable that the inorganic fine particles, the solvent, the resin containing a condensed ring structure, and the compound having one or more epoxy groups are mixed. When the composite resin composition of the present invention contains a dispersant and / or a surface treatment agent, the inorganic fine particles, the solvent, the resin containing a condensed ring structure, the compound having one or more epoxy groups, and the compound having one or more epoxy groups at the time of completion of the dispersion using the bead mill, and It is preferable that a dispersant and / or a surface treatment agent is mixed. A major feature is that the condensed ring structure-containing resin is mixed when the dispersion using the bead mill is completed. Generally, the inorganic fine particles are dispersed in a solvent with a bead mill and then mixed with a condensed ring structure-containing resin or the like, but in this method, it is necessary to add a considerable amount of a dispersant and / or a surface treatment agent. On the other hand, by mixing the condensed ring structure-containing resin when the dispersion using the bead mill is completed, the dispersant and / or the surface treatment agent is not contained at all, or the blending amount of the dispersant and / or the surface treatment agent is reduced to the utmost limit. can do. As a result, the decrease in the refractive index can be suppressed, and the decrease in the light resistance and the heat resistance of the cured product can also be suppressed.

The order of addition of the inorganic fine particles, the solvent, the condensed ring structure-containing resin, and the compound having one or more epoxy groups before dispersion using a bead mill is not limited, and for example, all the components may be mixed at once. Each component may be added one by one in order and mixed. This also applies when the composite resin composition contains a dispersant and / or a surface treatment agent. When the composite resin composition contains a dispersant and / or a surface treatment agent and a continuous bead mill is used, for example, inorganic fine particles, a solvent, a condensed ring structure-containing resin, and an epoxy group are used in advance. After mixing the compounds having one or more of the above, dispersion using a bead mill may be started, and a dispersant and / or a surface treatment agent may be added during the dispersion using the bead mill, or inorganic fine particles, a solvent, and an epoxy may be added in advance. A compound having one or more groups and a dispersant and / or a surface treatment agent may be mixed, and then dispersion using a bead mill may be started, and a condensed ring structure-containing resin may be added during the dispersion using the bead mill. .. Further, as long as the inorganic fine particles, the solvent, the resin containing a condensed ring structure, and the compound having one or more epoxy groups are mixed at the completion of the dispersion using the bead mill, the solvent and the condensed ring structure are completed after the completion of the dispersion using the bead mill. The containing resin may be further added, and this is also the case when the composite resin composition contains a dispersant and / or a surface treatment agent.
Any component such as a curing agent may be added at any time before dispersion using a bead mill, during dispersion, or after the completion of dispersion.

Since the composite resin composition of the present invention contains a condensed ring structure-containing resin that is soluble in alkali and curable by irradiation, it can be molded into a desired shape and cured by heat and radiation for various purposes. Used for. The composite resin composition of the present invention is particularly used for the purpose of forming a thin film on a substrate, heating and irradiating the substrate, and then developing the thin film to form a thin film having a predetermined pattern.

For example, as described above, when a thin film is formed on a substrate and thermosetting, radiation curing and development are performed, usually, each component is first mixed to obtain the composite resin composition of the present invention. It is more preferable to filter this with, for example, a millipore filter having a pore size of about 1.0 to 0.2 μm to obtain a uniform liquid substance. Next, the composite resin composition of the present invention is applied onto a substrate to obtain a coating film. The coating method is not particularly limited, and examples thereof include a dipping method, a spray method, a roller coating method, a slit coating method, a bar coating method, and a spin coating method. By these methods, the composite resin composition of the present invention is applied to a thickness of about 1 to 30 μm, and then the solvent is removed to form a thin film. Usually, a prebaking treatment is performed to sufficiently remove the solvent.

After placing a mask having a desired pattern on the thin film of this substrate, irradiation with radiation is performed.

By irradiation with radiation, the exposed part is cured by a polymerization reaction. The unexposed area is developed with a developer. As a result, the unexposed portion is removed, and a thin film having a desired pattern is obtained. The developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a rocking dipping method.

Examples of the developing solution include an alkaline aqueous solution, a mixed solution of the alkaline aqueous solution and a water-soluble organic solvent and / or a surfactant, and an organic solvent in which the composite resin composition of the present invention can be dissolved, and an alkaline aqueous solution is preferable. It is a mixed solution with a surfactant.

The base used for preparing an alkaline aqueous solution suitable for developing the composite resin composition of the present invention is not particularly limited, and is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate. , Ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, Examples thereof include 1,8-diazabicyclo (5.4.0) -7-undecene and 1,5-diazabicyclo (4.3.0) -5-nonane, preferably sodium carbonate, tetramethylammonium hydroxide and the like. Used.

If necessary, a water-soluble organic solvent such as methanol, ethanol, acetone, propanol, or ethylene glycol, a surfactant, or the like is added to the alkaline aqueous solution in an appropriate amount.

The composite resin composition of the present invention can be developed at a temperature of usually 10 to 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or ultrasonic cleaner. The developing time can be appropriately adjusted depending on the developing method, the developing solution, the temperature, the film thickness of the coating film, and the like.

After alkaline development, it is desirable to heat and cure in order to improve alkali resistance (post-baking treatment). In the composite resin composition of the present invention, various properties such as adhesion to a metal such as copper or glass, heat resistance, and surface hardness are improved by performing the heat treatment. Further, after forming a cured composite resin made of the composite resin composition of the present invention, a transparent electrode such as ITO may be formed by patterning, and the cured composite resin is a chemical solution (resist developer, etc.) necessary for forming an ITO pattern. Although it is exposed to an ITO etching solution, a resist stripping solution, etc.), the heat treatment improves the resistance (chemical resistance) that does not cause film slippage even when exposed to a chemical solution. Preferred heating temperature and heating time are 80 to 250 ° C. and 10 to 120 minutes. In this way, a cured thin film having a desired pattern can be obtained.

The pattern formation of the transparent electrode can be performed based on the conventional method described in JP-A-2008-270458 and the like. For example, when forming a transparent electrode pattern using ITO, first, an ITO film is formed on the cured product by spattering or the like. Next, the resist composition is applied and dried to form a resist film on the ITO film, and then exposed and developed to form a resist pattern having a desired pattern. Further, the substrate on which the resist pattern or the like is formed is immersed in an acidic chemical solution, and ITO is etched. Finally, the resist is removed by exposing the substrate to a resist stripping solution such as an amine solvent. After that, the transparent electrode can be formed by annealing the ITO film.

The composite resin composition of the present invention is used, for example, for the production of display devices such as touch panels and touch sensors, protective films for electronic components, interlayer insulating films and / or flattening films, binders for color resists, and printed wiring boards. Solder resist used; It is suitably used as an alkali-soluble photosensitive composition suitable for forming a columnar spacer as a substitute for a bead spacer in a liquid crystal display element. Further, the composite resin composition of the present invention is a material for various optical components (lens, LED, plastic film, substrate, optical disk, etc.); a coating agent for forming a protective film for the optical component; an adhesive for optical components (for optical fiber). Adhesives, etc.); Coating agents for manufacturing polarizing plates; Photosensitive resin compositions for hologram recording, etc. are also suitably used.

<< Composite resin cured product >>
The cured composite resin of the present invention is characterized by thermosetting and photocuring the composite resin composition of the present invention.

The method for thermosetting and photocuring the composite resin composition of the present invention is not particularly limited, and the photocuring may be performed after the heat curing, or the photocuring may be performed after the photocuring. You may go at the same time. The method of thermosetting is not particularly limited, and examples thereof include a method of heat-treating at 80 to 300 ° C. for 5 to 60 minutes. The method of photocuring is not particularly limited, and examples thereof include a method of irradiating ^{ultraviolet rays having a light intensity of 1 to 900 mW / cm 2} at a wavelength of 100 to 600 nm so as to have an exposure amount of 5 to 2000 mJ / cm ^2. Be done.

The cured composite resin of the present invention is preferably a thin film or a molded product in order to satisfy the required performance as an insulating film / protective film provided in a display device such as a touch panel or a touch sensor.

<< Optical film >>
The optical film of the present invention is characterized by comprising the cured composite resin of the present invention.

<< Display element >>
The display element of the present invention is characterized by comprising the cured composite resin of the present invention.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

1. 1. Materials used In the following examples and comparative examples, the following materials were used.
1-1. Inorganic fine particles, zirconium oxide (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., UEP-50)
-Zirconium oxide (UEP-100, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.)
1-2. Solvent / Cyclohexanone (manufactured by Sinopec)
-Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation, PGMEA)
-Propylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd., PGME)
1-3. Dispersant / Polymer-type dispersant (manufactured by Big Chemie Japan, BYK-118)
1-4. Hardener 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF Japan Ltd., IRGACURE 907)
1-5. Aliphatic polyfunctional acrylate, pentaerythritol triacrylate (PETA) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMM-3LM-N)

2. Synthesis Example (Synthesis Example 1) Synthesis of epoxy compound A 100 g of pentaerythritol, 100 g of toluene, and 2.2 g of boron trifluoride ether complex are charged into a 1000 ml reactor equipped with a stirrer, a cooling tube, and a thermometer, and the internal temperature is adjusted. The temperature was adjusted to 90 to 100 ° C. Next, 407 g of epichlorohydrin was added dropwise over 3 hours, and after completion of the addition, the mixture was further stirred for 3 hours. It was confirmed by gas chromatography that epichlorohydrin was completely consumed, and the internal temperature was adjusted to 50 to 60 ° C. Next, 240 g of 49% liquid caustic soda was added dropwise over 3 hours, followed by aging for 1 hour. The obtained reaction solution is transferred to a 2000 ml container, diluted with 300 g of toluene, soft water is added so that the produced salt concentration becomes a 10% aqueous solution, and the mixture is stirred and dissolved, and the toluene layer is separated and extracted to obtain the produced salt. After removal, the organic layer was washed with soft water and concentrated under reduced pressure at 100 ° C. using an evaporator to remove epichlorohydrin from the organic layer to obtain epoxy compound A. The epoxy equivalent of this epoxy compound A was 240 g / eq.

(Synthesis Example 2) Synthesis of Epoxy Compound B Polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., NISSO-PB G-2000, number average molecular weight 2500, 1,2-butadiene skeleton / 1,4-butadiene skeleton = 90/10) 100 35 parts of epichlorohydrin, 16 parts of sodium hydroxide and 50 parts of toluene were charged and reacted at 50 ° C. for 5 hours in a nitrogen atmosphere with vigorous stirring. After the reaction, 100 parts of water was added, and the mixture was stirred for 10 minutes and washed with water. After standing, the upper layer was separated, and after filtration, excess epichlorohydrin and toluene were removed under reduced pressure to obtain epoxy compound B as a residue. The epoxy equivalent of this epoxy compound B was 1520 g / eq.

(Synthesis Example 3) Synthesis of epoxy compound C 114 g of trimethylolpropane and 700 g of epichlorohydrin are added to a 1000 ml reactor equipped with a stirrer, a cooling tube and a thermometer, and 5.4 g of tetramethylammonium chloride is further added under reduced pressure. While maintaining the liquid temperature at 55 to 65 ° C. and removing water, 200 g of 49% liquid caustic soda was added dropwise over 4 hours, followed by aging for 1 hour.
Soft water is added to the obtained reaction solution so that the produced salt concentration becomes a 10% aqueous solution, and the mixture is stirred and dissolved. The epichlorohydrin layer is separated and extracted to remove the produced salt, and then the organic layer is washed with soft water. , Epichlorohydrin was removed from the organic layer by concentration under reduced pressure at 100 ° C. using an evaporator to obtain epoxy compound C. The epoxy equivalent of this epoxy compound C was 150 g / eq.

(Synthesis Example 4) Synthesis of Epoxy Compound D In the operation of Synthesis Example 1, pentaerythritol was changed to 100 g of sorbitol, the amount of epichlorohydrin was 305 g, the amount of 49% caustic soda was 256 g, and the amount of toluene after the reaction was 500 g. Epoxy compound D was obtained by carrying out the same operation except for the above. The epoxy equivalent of this epoxy compound D was 170 g / eq.

(Synthesis Example 5) Synthesis of Epoxy Compound E In the operation of Synthesis Example 1, pentaerythritol was changed to 100 g of glycerin, the amount of epichlorohydrin was 302 g, the amount of 49% caustic soda was 253 g, and the amount of toluene after the reaction was 500 g. Epoxy compound E was obtained in the same manner except for the above. The epoxy equivalent of this epoxy compound E was 142 g / eq.

(Synthesis Example 6) Synthesis of Epoxy Compound F In the operation of Synthesis Example 1, pentaerythritol was changed to 100 g of sorbitol, the amount of epichlorohydrin was 270 g, the amount of 49% caustic soda was 226 g, and the amount of toluene after the reaction was 500 g. Epoxy compound F was obtained by carrying out the same operation except for the above. The epoxy equivalent of this epoxy compound F was 175 g / eq.

(Synthesis Example 7) Synthesis of Epoxy Compound G In the operation of Synthesis Example 1, pentaerythritol was changed to 100 g of Polyglycerol 4 (manufactured by Solbay Japan Co., Ltd.), the amount of epichlorohydrin was 130 g, the amount of 49% caustic soda was 107 g, and after the reaction. The same operation was carried out except that the amount of toluene was 500 g, to obtain epoxy compound G. The epoxy equivalent of this epoxy compound G was 190 g / eq.

(Synthesis Example 8) Synthesis of fused ring structure-containing resin A 115 g (epoxy equivalent 270 g / eq) of bisphenol full orange glycidyl ether (manufactured by Osaka Gas Chemical Co., Ltd .: Ogsol PG) in a 300 ml four-necked flask, and triethylbenzyl as a catalyst. 600 mg of ammonium chloride, 30 mg of 2,6-diisobutylphenol as a polymerization inhibitor, and 36 g of acrylic acid were charged and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. The solution became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g to obtain a pale yellow transparent solid-state condensed ring structure-containing epoxy ester resin. It took 15 hours for the acid value to reach the target. To this fused ring structure-containing epoxy ester resin, 65 g of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved, and then 27 g of pyromellitic anhydride (PMDA), 7.6 g of tetrahydrophthalic anhydride (THPA) and tetraethylammonium bromide were added. 0.1 g was mixed, the temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C. for 14 hours. In this way, a PGMEA solution of the fused ring structure-containing resin A was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. Further, the condensed ring structure-containing resin A corresponds to the above-mentioned multivalent carboxylic acid resin (GA-ii).

(Synthesis Example 9) Synthesis of Fused Ring Structure-Containing Resin B In the condensed ring structure-containing epoxy ester resin obtained in the same manner as in Synthesis Example 8, 65 g of propylene glycol monomethyl ether acetate (PGMEA) and ditrimethylolpropane as a polyhydric alcohol are used. After 1.5 g was added and dissolved, 27 g of pyromellitic anhydride (PMDA) and 0.1 g of tetraethylammonium bromide were mixed, and the temperature was gradually increased and reacted at 110 to 115 ° C. for 14 hours. Further, 7.6 g of tetrahydrophthalic anhydride (THPA) was added and reacted for 10 hours to obtain a PGMEA solution of the fused ring structure-containing resin B. The disappearance of the acid anhydride was confirmed by IR spectrum. Further, the condensed ring structure-containing resin B corresponds to the above-mentioned multivalent carboxylic acid resin (G-b-iii).

(Synthesis Example 10) Synthesis of fused ring structure-containing resin C After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to an epoxy ester resin represented by the following formula (13) and dissolving it, bisphenol tetracarboxylic acid dianhydride 35 g of (BPDA) and 0.1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 14 hours to obtain a PGMEA solution of the fused ring structure-containing resin C. The disappearance of the acid anhydride was confirmed by IR spectrum. Further, the condensed ring structure-containing resin C corresponds to the above-mentioned multivalent carboxylic acid resin (GAi).
The epoxy ester resin represented by the following formula (13) was synthesized according to the method disclosed in JP-A-2009-185270.

3. 3. Examples (Examples 1 to 17, Comparative Example 1)
Inorganic fine particles, solvent, fused ring structure-containing resin, compound having one or more epoxy groups, dispersant and aliphatic polyfunctional acrylate are mixed in the weight ratio shown in Table 1 and dispersed using a media type disperser (bead mill). The mixture was further mixed with a curing agent to obtain a composite resin composition. Using the obtained composite resin composition, the average particle size, refractive index, developability, and residual film ratio after dispersion of the inorganic fine particles were evaluated by the method described later. The results are shown in Table 1.

4. Evaluation method 4-1. Average particle size after dispersion of inorganic fine particles The composite resin compositions obtained in each Example and Comparative Example were based on the scattering intensity distribution measured by a dynamic light scattering method using a Zetasizer Nano ZS manufactured by Malvern. The Z-average particle size was calculated.

4-2. Refractive index The composite resin compositions obtained in each Example and Comparative Example are applied to a silicon substrate using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of about 0.1 μm. Formed. A mask having a predetermined pattern is placed on the coating film surface of a silicon substrate having this coating film, and an ultraviolet ray having a ^{light intensity of 18.9 mW / cm 2 is emitted at a wavelength of 365 nm using a 250 W high-pressure mercury lamp in a nitrogen atmosphere.} Irradiation was performed so that the energy amount was 1000 mJ / cm ^2. Next, a development treatment was carried out at 23 ° C. for 60 seconds using a 0.5% by weight potassium hydroxide aqueous solution to remove an unexposed portion of the coating film. Then, it was rinsed with ultrapure water. The substrate having the obtained coating film was placed in an oven at 200 ° C., post-baked for 30 minutes, and the coating film was heat-cured to obtain a cured composite resin. The refractive index of the obtained cured composite resin product at 550 nm was measured using a photo-interference type film quality measuring machine.

4-3. Developability 4-2. The presence or absence of residue was visually confirmed in the unexposed portion after development when the development treatment described in the above was performed.
◎: No residue ○: Slight residue

4-4. Residual film ratio 4-2. Using the silicon substrate having the coating film after the post-baking treatment described in the above, a chemical resistance test is performed under the conditions of 25 ° C. according to the following steps (i) to (iv), and the residual film thickness after the test ((test). Later film thickness / film thickness before test) × 100) was determined.
(I) After immersing the substrate in PGMEA for 180 seconds, the substrate was placed in an oven at 150 ° C. to remove the solvent remaining in the coating film.
(Ii) After immersing in a 5 wt% potassium hydroxide aqueous solution for 180 seconds, the mixture was rinsed with ultrapure water and placed in an oven at 150 ° C. to remove residual water.
(Iii) After immersing in a 3.4% by weight aqueous oxalic acid solution for 180 seconds, washing and drying were carried out in the same manner as in (ii).
(Iv) After immersing in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 180 seconds, washing and drying were carried out in the same manner as in (ii).

Claims (11)

Inorganic particles,
solvent,
Indene, tetralin, fluorene, xanthene, anthracene, and epoxy ester resins or polycarboxylic acid resins which have a condensed ring structure derived from at least one selected from the group consisting of benzanthracene, and,
Contains compounds with one or more epoxy groups
The compound having one or more epoxy groups is selected from the group consisting of polybutadiene diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. At least one species that is
The average particle size after dispersion of the inorganic fine particles Ri 10~70nm der,
Inorganic fine particles, zirconium oxide, a composite resin composition, wherein the at least one Tanedea Rukoto selected from the group consisting of titanium oxide and barium titanate. In addition, it contains a dispersant and / or a surface treatment agent.
The composite resin composition according to claim 1, wherein the total content of the dispersant and the surface treatment agent is 5 parts by weight or less in terms of the weight of the active ingredient with respect to 100 parts by weight of the inorganic fine particles. The composite resin composition according to claim 1 or 2 , wherein the epoxy ester resin or polyvalent carboxylic acid resin has a fused ring structure derived from fluorene and a (meth) acryloyl group. The composite resin composition according to any one of claims 1 to 3 , wherein the water content of the compound having one or more epoxy groups is 0 to 70% by weight. The claim that the epoxy equivalent of the compound having one or more epoxy groups is 100 to 1000 g / eq, and the content of the compound having one or more epoxy groups is 0.1 to 45% by weight in the total solid content. The composite resin composition according to any one of 1 to 4. The composite resin composition according to any one of claims 1 to 5 , further comprising an aliphatic polyfunctional acrylate. The composite resin composition according to any one of claims 1 to 6 , wherein the content of the inorganic fine particles is 30 to 80% by weight based on the total solid content. A cured composite resin obtained by thermosetting and photocuring the composite resin composition according to any one of claims 1 to 7. The cured composite resin according to claim 8 , which is a thin film or a molded product. An optical film comprising the cured composite resin according to claim 8 or 9. A display device comprising the cured composite resin according to claim 8 or 9.