JP2018111777A - Composite resin composition and composite resin cured article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin composition excellent in dispersion stability and uniformity of inorganic fine particles and providing a composite resin cured article excellent in optical property (high refractive index), developability and resistance to a developer.SOLUTION: There is provided a composite resin composition containing inorganic fine particles, a solvent and a condensed ring structure-containing resin in which a condensed ring structure derived from at least one kind selected from a group consisting of indene, tetralin, fluorene, xanthene, anthracene and benzanthracene is connected by a structure represented by the following general formula (I), and having average particle diameter after dispersion of the inorganic fine particles of 10 to 70 nm. In the general formula (I), Rand Rrepresent each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, l and m represent each independently an integer of 0 to 10.SELECTED DRAWING: None

Description

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

2. Description of the Related Art In recent years, with the increase in functionality and diversification of electronic devices, display devices in which a touch panel / touch sensor function is added to a display element such as a liquid crystal are rapidly spreading. In these devices, functional layers such as an insulating film and a protective film are provided in order to accurately recognize the contact position. In addition to transparency, light resistance, heat resistance, adhesion to the base material and other adjacent layers, the functional layer must have characteristics such as moldability and flexibility to ensure design flexibility. Is growing year by year. Furthermore, there is a case where the functional layer itself needs to be subjected to a patterning process, and there is a demand for a material that dissolves rapidly in a developing solution or the like and exhibits good patterning properties that do not generate a development residue. In addition, since the transparent electrode may be patterned using ITO or the like after forming the functional layer, it may be exposed to a chemical solution (resist developing solution, ITO etching solution, resist stripping solution, etc.) necessary for ITO pattern formation. It may be preferable to have resistance (chemical resistance) that does not cause film slippage. Furthermore, when the ITO pattern is formed, a difference in refractive index occurs, and the pattern becomes easy to see, resulting in inconvenience that 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 made of a composite resin composition in which an organic material and an inorganic material are combined in a functional layer. For example, as disclosed in Patent Document 1, a dispersion material in which nano-sized inorganic fine particles are uniformly dispersed has been studied, and an inorganic fine particle is finely dispersed on the order of several tens of nanometers in an organic material. In order to construct a composite resin composition in which a dispersant and a surface treatment agent are added in a large amount to a compounding system.

However, if a large amount of the dispersant or surface treatment agent is blended, the particles can be dispersed uniformly, but the light resistance and heat resistance of the resulting dispersant and surface treatment agent itself can cause the light resistance of the resulting cured composite resin. And heat resistance may be reduced. Moreover, when compatibility with a dispersing agent or a surface treating agent and another compounding component is bad, the composite resin hardened | cured material obtained may become cloudy and transparency may not be ensured. Furthermore, since the dispersing agent and the surface treatment agent present in a large amount cause a decrease in the refractive index, there arises a problem that the visibility of the display screen is lowered.

On the other hand, Patent Document 2 proposes a composite resin composition that does not contain any dispersant and / or surface treatment agent and has a high refractive index. However, the cured product obtained from the composite resin composition described in Patent Document 2 may be slipped during development depending on the use conditions, and there is room for further improvement in terms of resistance to the developer.

JP 2011-116943 A International Publication No. 2015/088794

The present invention is a composite resin composition excellent in dispersion stability and uniformity of inorganic fine particles, and having excellent optical properties (high refractive index), developability (less development residue), and resistance to developer It aims at providing the composite resin composition which gives hardened | cured material.

As a result of intensive studies, the inventor of the composite resin composition described in Patent Document 2 uses a condensed ring structure-containing resin having a specific structure, so that the resulting composite resin cured product has resistance to a developer. As a result, the present invention has been completed.

That is, the composite resin composition of the present invention has an inorganic fine particle, a solvent, and a condensed ring structure derived from at least one selected from the group consisting of indene, tetralin, fluorene, xanthene, anthracene, and benzanthracene. It includes a condensed ring structure-containing resin linked by a structure represented by the general formula (I), and the average particle size after dispersion of inorganic fine particles is 10 to 70 nm.

[In General Formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and l and m each independently represents an integer of 0 to 10; Represent].

The composite resin composition of the present invention further contains a dispersing agent and / or a surface treating agent, and the total content of the dispersing agent and the surface treating agent is 5 parts by weight as an active ingredient based on 100 parts by weight of the inorganic fine particles. The following is preferable.

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, the condensed ring structure-containing resin preferably has a condensed ring structure derived from fluorene and a (meth) acryloyl group.

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 inorganic fine particles is preferably 30 to 80% by weight in the total solid content.

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

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

The optical film of the present invention comprises the cured composite resin of the present invention.

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

Since the composite resin composition of the present invention contains a condensed ring structure-containing resin having a specific structure, it is excellent in dispersion stability and uniformity of inorganic fine particles, and has optical properties (high refractive index), developability, and developer. It is possible to give a composite resin cured product having excellent resistance.

<< Composite resin composition >>
The composite resin composition of the present invention has an inorganic fine particle, a solvent, and a condensed ring structure derived from at least one selected from the group consisting of indene, tetralin, fluorene, xanthene, anthracene, and benzanthracene. Including the condensed ring-containing resin linked by the structure represented by (I), the average particle diameter after dispersion of the inorganic fine particles is 10 to 70 nm.

[In General Formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and l and m each independently represents an integer of 0 to 10; Represent].

<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. 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 ) , bismuth 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 ( eO _2, GeO), and the like.

The metal oxide fine particles may be previously dispersed in various solvents. Examples of the solvent include, but are not limited to, 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), ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone , Ketones such as cyclohexanone, benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons, dimethylformamide, N, N- dimethylacetamide, etc. amides such as 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.

Although it does not specifically limit as nitride, For example, silicon nitride, boron nitride, etc. are mentioned.

Although it does not specifically limit as complex oxide comprised from 2 or more types of metal elements, For example, titanates, such as barium titanate, titanium / silicon complex oxide, yttrium stabilization zirconia, etc. are mentioned. Such composite oxides have a core-shell structure in which not only compounds and solid solutions composed of multi-component elements but also metal oxide fine particles around the core are covered with metal oxides composed of other metal elements. 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 is included.

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

These inorganic fine particles may be used alone or in combination of two or more. Also, 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 of easy availability and easy adjustment of optical properties such as refractive index.

The primary particle diameter of the inorganic fine particles is not particularly limited, but is preferably 1 to 70 nm, and 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 cohesive energy is high, so that it may be difficult to maintain dispersion stability. On the other hand, if it exceeds 70 nm, light scattering by the inorganic fine particles in the thin film or the molded product becomes intense, and the transparency may not be maintained high. The primary particle diameter can be measured with an apparatus 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 10 to 50 nm is preferable. In order to make it less than 10 nm, it is necessary to use particles having a small primary particle size, which may make dispersion difficult. On the other hand, when it exceeds 70 nm, it may become cloudy when it is used as a cured product such as a thin film or molded product.

In the composite resin composition of the present invention, a large amount of inorganic fine particles can be blended. For example, with respect to 100 parts by weight of the condensed ring structure-containing resin described later, it is possible to add 200 parts by weight or more, or even 500 parts by weight or more, which is usually difficult to add. 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, and still more preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the condensed ring structure-containing resin. . When the content is less than 0.1 parts by weight, the characteristics of the inorganic fine particles are not sufficiently exhibited, and when 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 and more preferably 45 to 75% by weight based on the total solid content. When 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 when it exceeds 80% by weight, the film forming property may be deteriorated.

<Solvent>
Examples of the solvent include, but are not limited to, 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. 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 Diethylene glycol monoalkyl ethers such as no ethyl ether and diethylene glycol 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 mono Alkylene glycol monoalkyl ether acetates such as butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclo Ketones such as xanone and 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, lactic acid Examples include esters such as methyl, ethyl lactate, dimethyl succinate, 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, diethylene glycol monoethyl 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 parts by weight to 2000 parts by weight with respect to 100 parts by weight of the inorganic fine particles, and 80 to 2000 parts by weight. More preferably. When 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 be lowered, and when it exceeds 2000 parts by weight, it may be difficult to increase the film thickness. is there.

<Condensed ring structure-containing resin>
In the composite resin composition of the present invention, a condensed ring structure derived from at least one selected from the group consisting of indene, tetralin, fluorene, xanthene, anthracene, and benzanthracene is represented by the following general formula (I). Containing a condensed ring structure-containing resin linked by a structure. Here, the condensed ring structure does not necessarily have to be a structure represented by the general formula (I), and may include a part of the structure, but the resistance to the developer is improved. Therefore, it is preferable that all have this structure.

In general formula (I), R < ¹ > and R < ² > represent a hydrogen atom or a C1-C5 alkyl group each independently. Although it does not specifically limit as a C1-C5 alkyl group, A methyl group etc. are mentioned. The number of carbon atoms of the alkyl group is preferably 1. If the alkyl group has more than 5 carbon atoms, the dispersibility may be lowered.

In general formula (I), l and m each independently represent an integer of 0 to 10, and preferably an integer of 0 to 2. When l or m exceeds 10, dispersibility may be lowered.

As such a condensed ring structure-containing resin, an epoxy ester resin (E), a polyvalent carboxylic acid resin (G), or the like can be used.
The epoxy ester resin (E) is represented by reacting an epoxy resin (A) represented by the following general formula (1) with a monobasic carboxylic acid (B) or represented by the following general formula (10). This can be obtained by reacting the alcohol compound (C) with the glycidyl ester compound (D). As the epoxy ester resin (E), those having a condensed ring structure derived from xanthene or fluorene are preferable because of excellent dispersibility and heat resistance.

In the general formula (1), Y _1-4 are each independently a group represented by the following general formula (2) or the following general formula (3), and p _1-4 are each independently 0 to 0. It is an integer of 4.

In General Formula (2), Y _5-6 are groups independently represented by General Formula (2) or the following General Formula (3), and p _5-6 are each independently _0-4. Is an integer. In the general formula (1), Y _1-4 is a group represented by the general formula (2), and in the general formula (2), Y _5-6 is a group represented by the general formula (2). Y _1-4 in the general formula (1) form an oligomer having the group represented by the general formula (2) as a structural unit.

In general formulas (1) and (2), Z is at least selected from the group consisting of indene, tetralin, fluorene, xanthene, anthracene, and benzanthracene as shown in the following formulas (4) to (10). It is a divalent group containing a condensed ring structure derived from one type, and R _1-6 are each independently a linear, branched or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, carbon number 1 to 5 alkoxy groups, which may have a substituent phenyl group or a halogen atom, q _{1 to 6} is an integer from 0 to 4 each independently, s _{1 to 2,} the Each is independently an integer from 0 to 10. In general formulas (1) to (3), R _{7 to 14} are each independently a hydrogen atom or a methyl group, and m _{1 to 8} are each independently an integer from 0 to 10. Here, the plurality of R _1-14 and Y _1-6 may be the same or different. Further, in the general formula (1), the structural formula may be bilaterally symmetric or asymmetric.

In General Formula (10), Z is the same as defined above, and R _{15 to 16} are each independently a linear, branched, or cyclic alkyl group or alkenyl group having 1 to 10 carbon atoms, or 1 to C carbon atoms. 5 is an alkoxy group, an optionally substituted phenyl group, or a halogen atom, f _1-2 are each independently an integer of 0 to 4, and R _17-18 are each independently And m _{9 to 10} are each independently an integer of 0 to 10, and r ₁ and ₂ are each independently an integer of 1 to 5. Here, the plurality of R _{15 to 18} may be the same or different. Further, in the general formula (10), the structural formula may be bilaterally symmetric or asymmetric.

The monobasic carboxylic acid (B) is not particularly limited as long as it is a compound having one carboxyl group. For example, (meth) acrylic acid, cyclopropanecarboxylic acid, 2,2,3,3-tetramethyl- 1-cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenylcarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic 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- Rubonic 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, alkyl 4-cyclohexene-1,2-dicarboxylate, hydrogen, cycloheptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic acid, 1-adamantanecarboxylic acid, (4-tricyclo [5.2.1 0.0 ^2.6 ] dec-4-yl) acetic acid, p-methylbenzoic acid, p-ethylbenzoic acid, p-octylbenzoic acid, p-decylbenzoic acid, p-dodecylbenzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxybenzoic acid, p-butoxybenzoic acid, p-pentyloxybenzoic acid P-hexyloxybenzoic acid, p-fluorobenzoic acid, p-chlorobenzoic acid, p-chloromethylbenzoic 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-phenylpropionic acid, o-bromophenylacetic acid, o-iodophenylacetic acid, methoxyphenylacetic acid, 6-phenylhexanoic acid, biphenyl Carboxylic acid, α- Futheic acid, β-naphthoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, anthraquinone-2-carboxylic acid, indanecarboxylic acid, 1,4-dioxo-1,4-dihydronaphthalene-2-carboxylic acid, 3,3-diphenyl Examples include propionic acid, nicotinic acid, isonicotinic acid, cinnamic acid, 3-methoxycinnamic acid, 4-methoxycinnamic acid, and quinolinecarboxylic acid. These may be used alone or in combination of two or more. Particularly suitable monobasic carboxylic acid (B) is preferably one containing an unsaturated group capable of introducing a radiation-polymerizable functional group. For example, (meth) acrylic acid is preferred. Here, the radiation polymerizable functional group refers to a functional group having a property of causing a polymerization reaction by various kinds 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 (terephthalate). . These may be used alone or in combination of two or more. Among these, monobasic glycidyl carboxylate is particularly suitable, and among them, those containing an unsaturated group capable of introducing a radiation-polymerizable functional group are preferable. For example, glycidyl (meth) acrylate is preferred.

Reaction of epoxy resin (A) represented by general formula (1) and monobasic carboxylic acid (B), and alcohol compound (C) and glycidyl ester compound (D) represented by general formula (10) The reaction with is carried out at a temperature range of 50 to 120 ° C. for 5 to 30 hours using an appropriate solvent as necessary. Examples of the solvent include alkylene 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 and diethylene glycol dibutyl ether; ketones such as methyl ethyl ketone and methyl amyl ketone; dimethyl succinate, diethyl succinate, diethyl adipate, malonic acid Diethyl, oxalic acid Esters such as butyl and the like. Among these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferable. Furthermore, a catalyst and a polymerization inhibitor can be used as necessary. Examples of the catalyst include phosphonium salts, quaternary ammonium salts, phosphine compounds, tertiary amine compounds, imidazole compounds and the like, and the amount of the catalyst is not particularly limited. 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 is usually 5% by weight or less of the whole 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 its anhydride. 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 their anhydrides; Examples include acids or anhydrides thereof; tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and diphenyl ether tetracarboxylic acid, or dianhydrides thereof.

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

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

In the general formulas (11) and (12), Z is preferably a divalent group including a condensed 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 be present together in order to improve the heat resistance and heat yellowing of the resulting resin.

Although it does not specifically limit as polyhydric alcohol, For example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol , Neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol, 1,9-nonanediol, etc. Diols, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, alicyclic diols such as hydrogenated bisphenol A, aromatic diols such as ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, glycerin, Trimethylolpropane, trimethyl Ruetan, ditrimethylolpropane, pentaerythritol, sorbitol, trihydric or higher alcohols such as dipentaerythritol and the like. 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 alcohol, 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 are mixed, and then the polybasic carboxylic acid or its anhydride (F) is added and mixed. Also good. Further, a polybasic carboxylic acid may be further added to these reaction products for reaction.

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

(Gai) First polyvalent carboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (E) with one kind of polybasic carboxylic acid or its anhydride (F). (G-a-ii) second polycarboxylic acid resin: mixture of epoxy ester resin (E) and two or more polybasic carboxylic acids or anhydrides (F) (for example, dicarboxylic anhydride) And a mixture of tetracarboxylic dianhydride) and a reaction; and (G-a-iii) third polycarboxylic acid resin: epoxy ester resin (E) and tetracarboxylic acid A resin obtained by reacting an acid or its dianhydride and further reacting the resulting reaction product with a dicarboxylic acid or its anhydride.

(Gbi) Fourth polycarboxylic acid resin: Epoxy ester resin (E), polyhydric alcohol, and one kind of polybasic carboxylic acid or anhydride (F) are mixed and reacted. (Gb-ii) Fifth polyvalent carboxylic acid resin: epoxy ester resin (E), polyhydric alcohol, two or more polybasic carboxylic acids or anhydrides thereof (F ) A mixture (for example, a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride) and a reaction; and (Gb-iii) a sixth polyvalent carboxylic acid resin: A resin obtained by reacting an epoxy ester resin (E), a polyhydric alcohol, tetracarboxylic acid or a dianhydride thereof, and further reacting the resulting reaction product with a dicarboxylic acid or an anhydride thereof.

The polyvalent carboxylic acid resin (G-a) or (G-b) having various condensed ring structures having different structures thus obtained is used according to the intended use.

The “polybasic carboxylic acid or its anhydride (F)” means “at least one of a specific polybasic carboxylic acid and its corresponding anhydride”. If the acid is phthalic acid, it refers to at least one of phthalic acid and phthalic anhydride. In addition, “a mixture of two or more polybasic carboxylic acids or anhydrides (F) thereof” means that at least two types of polybasic carboxylic acids or anhydrides thereof are simultaneously present. Therefore, in the methods (G-a-ii) and (Gb-ii), at least two types of polybasic carboxylic acids or their anhydrides (F) are involved in the reaction.

In any of the above-described methods, the polyvalent carboxylic acid resin (G) is obtained by changing the epoxy ester resin (E), the polyhydric alcohol, the polybasic carboxylic acid or the anhydride (F) by the above-exemplified method (order). It is produced by dissolving (suspending) in a solvent and reacting by heating. Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, ester 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. And ketone solvents such as cyclohexanone. Moreover, 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. The amount of the catalyst is not particularly limited, but is 0.01% of the total reaction product. It is preferably 10 to 10% by weight.

Although the reaction temperature of the said reaction is not specifically limited, It is preferable that it is 50-130 degreeC, and it is more preferable that it is 70-120 degreeC. When 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, when the temperature exceeds 130 ° C., some condensation of carboxyl groups and hydroxyl groups may occur, and the molecular weight may increase rapidly.

In the production of the polycarboxylic acid resin (G), when a polyhydric alcohol is used, the molar ratio of the hydroxyl group of the epoxy ester resin (E) to the hydroxyl group of the polyhydric alcohol (hydroxyl group / polyvalent of the epoxy ester resin (E)). 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. When the molar ratio of the hydroxyl groups of the polyhydric alcohol exceeds 50, the molecular weight of the polycarboxylic acid resin (G) increases rapidly and there is a risk of gelation. Moreover, when the molar ratio is less than 1, the heat resistance and the heat discoloration tend to be difficult to improve.

The blending amount of the polybasic carboxylic acid or its anhydride (F) is not particularly limited, but the hydroxyl groups of the epoxy ester resin (E) (when polyhydric alcohol is used, the total with the hydroxyl groups of the polyhydric alcohol) 1 It is preferably 0.1 to 1 equivalent, more preferably 0.4 to 1 equivalent, in terms of acid anhydride group with respect to the equivalent (mole). When 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. The composite resin composition may remain on the substrate even after development. On the other hand, when the blending amount exceeds 1 equivalent, unreacted polybasic carboxylic acid or its anhydride (F) remains, and 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. In addition, acid anhydride group conversion shows the quantity when all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid to be used or its anhydride (F) are converted into acid anhydride groups.

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

In the composite resin composition of the present invention, the polycarboxylic acid resin (G) preferably contains a radiation-polymerizable functional group, and specifically contains an unsaturated group such as a (meth) acryloyl group. Is preferred. 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, so that it is used as the photosensitive composite resin composition (H). I can do it. Here, the photosensitivity means a property that causes a chemical reaction by various kinds of radiation, and as such radiation, visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray in order from the longest wavelength. , And γ rays. Among these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. As the ultraviolet light, ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, or a xenon lamp can be suitably 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 with respect to 100 parts by weight of the inorganic fine particles. More preferably, it is a part. When 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 be lowered. When the content 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 viewpoints of heat resistance and dispersibility, the condensed ring structure-containing resin preferably has a condensed ring structure derived from fluorene. Further, from the viewpoint of photocurability, the condensed ring-containing resin preferably has a (meth) acryloyl group.

The composite resin composition of the present invention may optionally contain other components in addition to the inorganic fine particles, the solvent, and the condensed ring structure-containing resin. Examples of other components include compounds having one or more epoxy groups, dispersants and / or surface treatment agents, aliphatic polyfunctional acrylates, curing agents, leveling agents, resin components, thermal polymerization inhibitors, adhesion assistants, An epoxy group hardening accelerator, surfactant, an antifoamer, etc. are mentioned.

<Compound having one or more epoxy groups>
The composite resin composition of the present invention may optionally contain a compound having one or more epoxy groups. When patterning using a negative photoresist resin, the solvent component is removed by heating (pre-baking), and after irradiation with radiation such as ultraviolet rays, the unexposed portion is dissolved and removed by a developer. When the composite resin composition of the present invention is heat-cured, the composite resin cured product obtained by reacting the carboxyl group remaining in the condensed ring-containing resin with the epoxy group of the compound having one or more epoxy groups It is possible to improve the chemical resistance.

The compound having one or more epoxy groups is not particularly limited. 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.

Although the water solubility of the compound which has 1 or more of epoxy groups is not specifically limited, It is preferable that it is 0 to 70 weight%, and it is more preferable that it is 0 to 60 weight%. When the water content of the compound having one or more epoxy groups exceeds 70% by weight, film slippage may occur when exposed to a chemical solution such as a resist developer, an ITO etching solution, or a resist stripping solution.

In the present specification, the “water solubility” refers to a 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.

Although the epoxy equivalent of the compound which has 1 or more of epoxy groups is not specifically limited, It is preferable that it is 100-1000 g / eq, and it is more preferable that it is 100-250 g / eq. If the epoxy equivalent is less than 100 g / eq, film exposure may occur in the exposed area, and if it exceeds 1000 g / eq, a residue may be generated in the unexposed area during development, and developability may deteriorate.

Although the molecular weight of the compound which has one or more epoxy groups is not specifically limited, It is preferable that it is 100-3500, and it is more preferable that it is 110-1000. When the molecular weight is less than 100, chemical resistance may be lowered, and when it exceeds 3500, a residue may be generated in an unexposed portion during development, and developability may be lowered.

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

When the composite resin composition of the present invention contains a compound having one or more epoxy groups, the content of the compound having one or more epoxy groups relative to the condensed ring-containing resin is not particularly limited, but the condensed ring-containing resin The amount is preferably 0.01 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight. When 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 be lowered, and when it exceeds 100 parts by weight, Developability may be reduced.

<Dispersant and / or surface treatment agent>
The composite resin composition of the present invention shows good dispersibility even when it contains no dispersant and / or surface treatment agent, but may contain a small amount of the dispersant and / or surface treatment agent.
The dispersant is not particularly limited, and examples thereof include a polyacrylic acid dispersant, a polycarboxylic acid dispersant, a phosphoric acid dispersant, and a silicon 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 for bonding a compound capable of reacting with a hydroxyl group present on the surface of a fine particle, such as a coupling agent. The surface treatment can be performed by dispersing inorganic fine particles in a solvent, mixing a coupling agent under acidic conditions, and allowing them to act. Although it does not specifically limit as a surface treating agent, A silane coupling agent and a titanium coupling agent are mentioned, For example, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropylmethyl dimethoxysilane, etc. (Meth) acryloxysilanes; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxy silanes 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- Quaternary ammonium salts such as hydrochloride of aminoethyl-3-aminopropyltrimethoxysilane; titanates such as p-styryltrimethoxysilane; phenyltrimethoxysilane; isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate And the like. These surface treatment agents may be used alone or in combination of two or more. Among these surface treatment agents, epoxy silanes and (meth) acryloxy silanes have reactive functional groups, are cured together with a condensed ring-containing resin, and can fix inorganic fine particles in the cured product. preferable.

When the composite resin composition of the present invention includes a dispersant and / or a surface treatment agent, the total content of the dispersant and the surface treatment agent is not particularly limited. The amount 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 be reduced. When the composite resin composition of the present invention includes 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. For example, the active ingredient is 100 parts by weight of inorganic fine particles. The weight is preferably 0.1 parts by weight or more.

<Aliphatic polyfunctional acrylate>
The composite resin composition of the present invention preferably further contains an aliphatic polyfunctional acrylate from the viewpoint of photocurability. Examples of the aliphatic polyfunctional acrylate include, but are not limited to, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) (meth) acrylic acid esters such as acrylate. 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 with respect to the inorganic fine particles is not particularly limited, but is 0.1 to 40 parts by weight with respect to 100 parts by weight of the inorganic fine particles. The amount is preferably 1 to 30 parts by weight. When 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 when it exceeds 40 parts by weight, developability may be deteriorated.

Although the manufacturing method of the composite resin composition of this invention is not specifically limited, For example, the method etc. which disperse | distribute inorganic fine particles, a solvent, and condensed ring structure containing resin using a bead mill etc. are mentioned. At the completion of dispersion using the bead mill, it is preferable that the inorganic fine particles, the solvent, and the condensed ring structure-containing resin 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 condensed ring structure-containing resin, and the dispersant and / or the surface treatment agent are present at the completion of dispersion using the bead mill. It is preferable that they are mixed. A major feature is that a resin containing a condensed ring structure is mixed at the completion of dispersion using a bead mill. In general, inorganic fine particles are dispersed in a solvent by a bead mill and then mixed with a condensed ring-containing resin or the like. In this method, it is necessary to add a considerable amount of a dispersant and / or a surface treatment agent. On the other hand, a resin containing a condensed ring structure is mixed at the completion of dispersion using a bead mill, so that it does not contain any dispersant and / or surface treatment agent or the amount of the dispersant and / or surface treatment agent is reduced to the limit. can do. As a result, a reduction in refractive index can be suppressed, and a decrease in light resistance and heat resistance of the cured product can also be suppressed.

The order of addition of the inorganic fine particles, the solvent, and the condensed ring structure-containing resin before dispersion using a bead mill is not limited. For example, all the components may be mixed at once, or each component may be added one by one in order. You may mix. The same applies to the case where the composite resin composition contains a dispersant and / or a surface treatment agent. Further, 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, and a condensed ring structure-containing resin are mixed in advance. Then, dispersion using a bead mill may be started, and a dispersant and / or a surface treatment agent may be added during dispersion using the bead mill, or inorganic fine particles, a solvent, and a dispersant and / or a surface treatment agent may be added in advance. After mixing, the dispersion using the bead mill is started, and the condensed ring structure-containing resin may be added during the dispersion using the bead mill. Furthermore, as long as inorganic fine particles, a solvent, and a resin containing a condensed ring structure are mixed at the time of completion of dispersion using a bead mill, a solvent or a resin containing a condensed ring structure may be further added after completion of dispersion using a bead mill. This is the same when the composite resin composition contains a dispersant and / or a surface treatment agent.
Arbitrary components such as a curing agent may be added at any time before, during, or after dispersion using a bead mill.

The composite resin composition of the present invention contains a condensed ring structure-containing resin that is soluble in alkali and can be cured by radiation irradiation. Therefore, the composite resin composition is molded into a desired shape, cured by radiation, and used for various purposes. Is done. The composite resin composition of the present invention is particularly used for the purpose of forming a thin film having a predetermined pattern by forming a thin film on a substrate, irradiating with radiation, and developing. Moreover, you may perform hardening by thermosetting as needed.

For example, as described above, when a thin film is formed on a substrate and radiation curing and development are performed, usually, the components are first mixed to obtain the composite resin composition of the present invention. For example, it is more preferable to filter this with a Millipore filter having a pore diameter of about 1.0 to 0.2 μm to obtain a uniform liquid. Next, the composite resin composition of the present invention is applied onto a substrate to obtain a coating film. The method for applying 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 applying the composite resin composition of the present invention to a thickness of about 1 to 30 μm by these methods and then removing the solvent, a thin film is formed. Usually, a pre-bake treatment is performed to sufficiently remove the solvent.

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

By irradiation with radiation, the exposed portion is cured by a polymerization reaction. The unexposed portion is developed with a developer. Thereby, an unexposed part 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 piling method, a dipping method, and a rocking dipping method.

Examples of the developer 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. It is a mixed solution with a surfactant.

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

An appropriate amount of 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 as necessary.

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

After alkali development, in order to improve alkali resistance, it is desirable to perform a curing treatment by heating (post-baking treatment). In the composite resin composition of the present invention, by performing heat treatment, various properties such as adhesion to metal such as copper or glass, heat resistance, and surface hardness are improved. Moreover, after forming the composite resin cured product comprising the composite resin composition of the present invention, a transparent electrode such as ITO may be formed by patterning, and the composite resin cured product may be a chemical solution (resist developer, Although it is exposed to an ITO etching solution, a resist stripping solution, etc., the heat treatment improves the resistance (chemical resistance) to prevent film slippage even when exposed to a chemical solution. A preferable 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 a conventional method described in JP-A-2008-270458. For example, when patterning a transparent electrode using ITO, first, an ITO film is formed on the cured product by sputtering or the like. Next, after a resist composition is applied and dried to form a resist film on the ITO film, a resist pattern having a desired pattern is formed by performing exposure and development processes. 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. Then, a transparent electrode can be formed by annealing the ITO film.

The composite resin composition of the present invention can be used, for example, for forming a protective film, interlayer insulating film and / or planarizing film for display devices such as touch panels and touch sensors, electronic parts, color resist binders, and printed wiring boards. Solder resist to be 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 device. Furthermore, the composite resin composition of the present invention is a material for various optical components (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film for the optical components; an adhesive for optical components (for optical fibers). Adhesives, etc.]; Coating agents for producing polarizing plates; photosensitive resin compositions for hologram recording, etc. are also suitably used.

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

The method for photocuring the composite resin composition of the present invention is not particularly limited. For example, ultraviolet light having a light intensity of 1 to 900 mW / cm ² at a wavelength of 100 to 600 nm is exposed to 5 to 2000 mJ / cm ^2. And so on.

The composite resin cured product of the present invention can also be obtained by thermosetting and photocuring the composite resin composition of the present invention. The method of thermosetting and photocuring is not particularly limited, and photocuring may be performed after thermosetting, thermosetting may be performed after photocuring, or both may be performed simultaneously. Although the method of thermosetting is not specifically limited, For example, the method etc. which heat-process at 80-300 degreeC for 5 to 60 minutes are mentioned.

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

<< Optical film >>
The optical film of the present invention comprises the cured composite resin of the present invention.

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

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

1. Materials used The following materials were used in the following examples and comparative examples.
1-1. Inorganic fine particles / zirconium oxide (UEP-50, manufactured by Daiichi Elemental Chemical Co., Ltd.)
・ Zirconium oxide (Daiichi Rare Element Chemical Industries, Ltd., UEP-100)
1-2. Solvent, cyclohexanone (manufactured by Sinopec)
・ Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation, PGMEA)
・ Propylene glycol monomethyl ether (PGME)
1-3. Dispersant / polymer type dispersant (BYK-118, manufactured by BYK Japan)
1-4. Aliphatic polyfunctional acrylate pentaerythritol triacrylate (PETA) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMM-3LM-N)
1-5. Curing agent 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF Japan, IRGACURE 907)

2. Synthesis Example (Synthesis Example 1) Synthesis of epoxy compound A To a 1000 ml reactor equipped with a stirrer, a condenser and a thermometer, 700 g of epichlorohydrin was added to 114 g of trimethylolpropane, and 5.4 g of tetramethylammonium chloride was further added. While maintaining the liquid temperature at 55 to 65 ° C. under reduced pressure and simultaneously 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 resulting reaction solution so that the resulting salt concentration is 10% aqueous solution, and dissolved by stirring. The epichlorohydrin layer is separated and extracted to remove the produced salt, and then the organic layer is washed with soft water. Then, the resultant was concentrated under reduced pressure at 100 ° C. with an evaporator to remove epichlorohydrin from the organic layer, thereby obtaining an epoxy compound A. The epoxy content of this epoxy compound was 150 g / eq.

(Synthesis Example 2) Synthesis of condensed ring structure-containing resin A 324 g of bisphenolfluorene was dissolved in 257 g of epichlorohydrin, and 243 g of 40% aqueous sodium hydroxide solution was added dropwise at 80 ° C. over 10 hours. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, 1500 g of toluene and 300 g of water were added to the reaction solution, and the resulting salt was dissolved in water. After liquid separation, the lower aqueous layer was removed. Further, the upper toluene layer was washed with water, and then the solvent was distilled off under reduced pressure to obtain 400 g of a bisphenolfluorene type epoxy resin. A 300 ml four-necked flask was charged with 250 g of the bisphenolfluorene type epoxy resin obtained by the above method, 600 mg of triethylbenzylammonium chloride as a catalyst, 56 mg of 2,6-diisobutylphenol as a polymerization inhibitor, and 45 g of acrylic acid. It melt | dissolved by heating at 90-100 degreeC, blowing in air at the speed | rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and by continuing heating and stirring for 20 hours until the acid value was less than 1.0 mg KOH / g, a condensed ring structure-containing epoxy ester resin was obtained.

After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to this fused ring structure-containing epoxy ester resin and dissolving, 27 g of pyromellitic anhydride (PMDA), 7.6 g of tetrahydrophthalic anhydride (THPA) and tetraethylammonium bromide 0.1g was mixed, this was heated up gradually and it was made to react at 110-115 degreeC for 14 hours. In this way, a PGMEA solution of the condensed ring structure-containing resin A was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Synthesis Example 3) Synthesis of the condensed ring structure-containing resin B To the condensed ring structure-containing epoxy ester resin obtained in the same manner as in Synthesis Example 2, 65 g of propylene glycol monomethyl ether acetate (PGMEA) and ditrimethylolpropane as polyhydric alcohol After 1.5 g was added and dissolved, 27 g of pyromellitic anhydride (PMDA) and 0.1 g of tetraethylammonium bromide were mixed, and this was gradually heated 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 condensed ring structure-containing resin B. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Synthesis Example 4) Synthesis of condensed ring structure-containing resin C 340 g of bisphenolxanthene was dissolved in 257 g of epichlorohydrin, and 243 g of a 40% aqueous sodium hydroxide solution was added dropwise at 80 ° C. over 10 hours. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, 1500 g of toluene and 300 g of water were added to the reaction solution, and the resulting salt was dissolved in water. After liquid separation, the lower aqueous layer was removed. Further, the upper toluene layer was washed with water, and then the solvent was distilled off under reduced pressure to obtain 420 g of a bisphenolxanthene type epoxy resin.
A 300 ml four-necked flask was charged with 250 g of the bisphenolxanthene type epoxy resin obtained by the above method, 600 mg of triethylbenzylammonium chloride as a catalyst, 56 mg of 2,6-diisobutylphenol as a polymerization inhibitor, and 45 g of acrylic acid. It melt | dissolved by heating at 90-100 degreeC, blowing in air at the speed | rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and by continuing heating and stirring for 20 hours until the acid value was less than 1.0 mg KOH / g, a condensed ring structure-containing epoxy ester resin was obtained.

After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to this fused ring structure-containing epoxy ester resin and dissolving, 27 g of pyromellitic anhydride (PMDA), 7.6 g of tetrahydrophthalic anhydride (THPA) and tetraethylammonium bromide 0.1g was mixed, this was heated up gradually and it was made to react at 110-115 degreeC for 14 hours. In this way, a PGMEA solution of the condensed ring structure-containing resin C was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Synthesis example 5) Synthesis of condensed ring structure-containing resin D In a 300 ml four-necked flask, 115 g (epoxy equivalent 270 g / eq) of bisphenol fluorenediglycidyl ether (Osaka Gas Chemical Co., Ltd .: Ogsol PG) and triethylbenzyl as a catalyst Ammonium chloride (600 mg), 2,6-diisobutylphenol (30 mg) as a polymerization inhibitor and acrylic acid (36 g) were charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mg KOH / g, to obtain a light yellow transparent and solid condensed ring structure-containing epoxy ester resin. It took 15 hours for the acid value to reach the target.

After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to this fused ring structure-containing epoxy ester resin and dissolving, 27 g of pyromellitic anhydride (PMDA), 7.6 g of tetrahydrophthalic anhydride (THPA) and tetraethylammonium bromide 0.1g was mixed, this was heated up gradually and it was made to react at 110-115 degreeC for 14 hours. In this way, a PGMEA solution of the condensed ring structure-containing resin D was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Synthesis Example 6) Synthesis of Condensed Ring Structure-Containing Resin E To the condensed ring structure-containing epoxy ester resin obtained in the same manner as in Synthetic Example 5, 65 g of propylene glycol monomethyl ether acetate (PGMEA) and polyhydric alcohol were used as ditrimethylolpropane. After 1.5 g was added and dissolved, 27 g of pyromellitic anhydride (PMDA) and 0.1 g of tetraethylammonium bromide were mixed, and this was gradually heated 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 condensed ring structure-containing resin E. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Synthesis Example 7) Synthesis of condensed ring structure-containing resin F After adding 65 g of propylene glycol monomethyl ether acetate (PGMEA) to the epoxy ester resin represented by the following formula (13) and dissolving it, bisphenol tetracarboxylic dianhydride (BPDA) 35g and tetraethylammonium bromide 0.1g were mixed, this was heated up gradually, and it was made to react at 110-115 degreeC for 14 hours, and the PGMEA solution of condensed ring structure containing resin F was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.
In addition, the epoxy ester resin represented by following formula (13) was synthesize | combined according to the method disclosed by Unexamined-Japanese-Patent No. 2009-185270.

3. Examples (Examples 1 to 12, Comparative Examples 1 to 4)
Mixing inorganic fine particles, solvent, condensed ring structure-containing resin, dispersant, aliphatic polyfunctional acrylate and compound having one or more epoxy groups at a weight ratio shown in Table 1, and dispersing using a media type disperser (bead mill) And a composite resin composition was obtained by further mixing a curing agent. Using the obtained composite resin composition, the average particle diameter after dispersion of inorganic fine particles, the refractive index, the developability, and the remaining film ratio during development were evaluated by the methods described later. The results are shown in Table 1.

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

4-2. Refractive index The composite resin compositions obtained in Examples and Comparative Examples were applied on a silicon substrate using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of about 1 μm. did. A mask having a predetermined pattern is placed on the coating film surface of the silicon substrate having this coating film, and UV light having a light intensity of 18.9 mW / cm ² is applied 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 . Subsequently, the development process for 60 second was performed at 23 degreeC using 0.5 weight% potassium hydroxide aqueous solution, and the unexposed part of the coating film was removed. Then, the rinse process was performed with the ultrapure water. The substrate having the obtained coating film was placed in an oven at 200 ° C., post-baking treatment was performed for 30 minutes, and the coating film was heated and cured to obtain a cured composite resin. About the obtained composite resin hardened | cured material, the refractive index in 550 nm was measured using the optical interference type film quality measuring machine.

4-3. Development residue 4-2. The presence or absence of a residue was visually confirmed in the unexposed portion after development when the development processing described in 1 was performed.
◎: No residue ○: Slightly residual

4-4. Residual film ratio upon development 4-2. The residual film ratio ((film thickness after development / film thickness before development) × 100) was determined using the silicon substrate having the coating film described in 1).

In the composition of the comparative example, the residual ratio was 90% or less, but in the composition of the present invention, as shown in Examples 1 to 12, all were greatly improved to 100%.

Claims (10)

Inorganic fine particles,
Solvent, and
Containing a condensed ring structure in which a condensed ring structure derived from at least one selected from the group consisting of indene, tetralin, fluorene, xanthene, anthracene, and benzanthracene is linked by a structure represented by the following general formula (I) Including resin,
The composite resin composition, wherein the average particle size after dispersion of the inorganic fine particles is 10 to 70 nm:

[In General Formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and l and m each independently represents an integer of 0 to 10; Represent]. Furthermore, a dispersant and / or a surface treatment agent is included,
2. 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 active ingredient weight with respect to 100 parts by weight of the inorganic fine particles. The composite resin composition according to claim 1 or 2, wherein the inorganic fine particles are at least one selected from the group consisting of zirconium oxide, titanium oxide, and barium titanate. The composite resin composition according to any one of claims 1 to 3, wherein the condensed ring structure-containing resin has a condensed ring structure derived from fluorene and a (meth) acryloyl group. Furthermore, the composite resin composition of any one of Claims 1-4 containing aliphatic polyfunctional acrylate. The composite resin composition according to any one of claims 1 to 5, wherein the content of the inorganic fine particles is 30 to 80% by weight in the total solid content. A composite resin cured product obtained by photocuring the composite resin composition according to any one of claims 1 to 6. The composite resin cured product according to claim 7, which is a thin film or a molded body. An optical film comprising the composite resin cured product according to claim 7 or 8. A display element comprising the cured composite resin according to claim 7.