TWI499623B - Composite resin composition - Google Patents

Description

Composite resin composition

The present invention relates to an alkali-soluble composite resin composition comprising an inorganic fine particle and an alkali-soluble resin having a condensed ring structure, a film obtained by hardening the composition, a molded body, an optical film using the same, and a display element , semiconductor components.

In recent years, in order to realize the high functionality of organic materials, the combination of organic materials and inorganic materials is being studied. A material having a combination of an organic material and an inorganic material and having excellent flexibility or formability of an organic material, heat resistance of an inorganic material, light resistance, and high optical characteristics (high refractive index, etc.) has been proposed. The composite material may be an organic-inorganic hybrid resin in which a metal element such as ruthenium or titanium is introduced into the organic resin skeleton by a covalent bond, or a dispersion-based material in which nano-sized inorganic fine particles are uniformly dispersed in the organic resin.

The above composite material can be used for various optical films, display elements, semiconductor elements, and the like which require high level of transparency, light resistance, heat resistance, and refractive index in recent years. In particular, in the above-mentioned applications, studies have been conducted to produce a dispersion-type material in which a film having a higher degree of freedom in design and a high level of characteristics and a molded body are uniformly dispersed with nano-sized inorganic fine particles. In general, when it is desired to disperse inorganic fine particles in an organic material, a method of adding a dispersing agent or a surfactant to the blending system is employed in order to construct a uniform and stable dispersion. However, such a dispersing agent or surfactant greatly contributes to the production of a molded body having improved uniformity or stability of the dispersion and good transparency, but sometimes due to the light resistance or heat resistance of the dispersing agent or the surfactant itself. The problem is that the obtained molded body is reduced in light resistance or heat resistance. Further, when the dispersant or the surfactant is inferior in compatibility with other blending components, problems such as white turbidity of the obtained molded body may occur. Further, in such a use, it is often required to perform patterning, and a resin composition which exhibits good pattern properties is required in a resin composition in which inorganic fine particles having low solubility such as an alkali developer for patterning are dispersed.

For example, Patent Document 1 discloses a coating composition which is excellent in transparency, high in refractive index, and high in hardness, and the coating composition contains one type of organic-inorganic hybrid resin, that is, sesquiterpene oxygen. An alkane resin and a particulate metal oxide. Patent Document 2 discloses a resin composition which can form a molded body having high transparency and a refractive index, and the resin composition comprises a base resin having an anthracene skeleton and at least zirconia having an average particle diameter of 30 nm or less. The composition is composed of inorganic fine particle components. Patent Document 3 discloses a photosensitive resin composition which can be subjected to alkali development, and the resin composition contains a hydrophilic resin containing a (meth)acryl fluorenyl group and a carboxyl group, which is modified by an epoxy resin, and has a volume average. Inorganic fine particles having a particle diameter of 1 to 200 nm and a photoradical polymerization initiator. Here, by using the above hydrophilic resin having an appropriate HBL value or SP value, a resin composition having improved developability and good pattern properties can be obtained.

In view of the above circumstances, a resin composition which is excellent in stability and uniformity of dispersion, high in transparency, heat resistance, and light resistance, and which provides high optical characteristics (high refractive index) is required.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-9079

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-133379

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-133961

However, in Patent Document 1, a film or a molded article having a high transparency and a high refractive index can be formed. However, since a dispersant is added in order to improve dispersibility, there is a problem in light resistance and heat resistance. Patent Document 2 describes that the dispersion can be improved by using a resin having an anthracene skeleton. However, in order to uniformly disperse the nano-sized microparticles, it is still insufficient to introduce only the anthracene skeleton, and in particular, there is an increase in particle blending. The tendency of the amount, the stability of dispersion, and the uniformity are lowered, and it is difficult to obtain a homogeneous coating film having high transparency. Further, in Patent Document 3, the amount of the inorganic fine particles is less than 50% by weight in the resin composition, and it is difficult to maintain a stable and uniform dispersion in a composition filled at a height exceeding 50% by weight. Therefore, in a composition highly filled with inorganic fine particles, it is difficult to obtain good developability.

An object of the present invention is to provide a composite resin composition which can form a cured product which is excellent in stability and uniformity, has a high refractive index, and is excellent in transparency, heat resistance and light resistance. Further, an object of the present invention is to provide a film, a molded article, an optical film using the same, a display element, a color filter, a touch panel, an electronic paper, and a semiconductor which are excellent in transparency, heat resistance, and light resistance. element.

The present inventors have found that inorganic fine particles having an average particle diameter of from 1 to 100 nm synthesized by a vapor phase method are selected as inorganic fine particles, and have been selected from the group consisting of ruthenium, tetrahydronaphthalene, anthracene, a polyvalent carboxylic acid resin having at least one condensed ring structure in the group consisting of ruthenium and benzopyrene, and the obtained composite resin composition has high dispersion stability and uniformity, and the composite composition is cured. The molded article has high transparency, heat resistance, and light resistance, and the refractive index is easily adjusted to complete the present invention.

That is, the present invention relates to a composite resin composition which is composed of inorganic fine particles having an average particle diameter of from 1 to 100 nm synthesized by a vapor phase method, and having an anthracene selected from the group consisting of anthracene, tetrahydronaphthalene, anthracene, A polyvalent carboxylic acid resin having at least one condensed ring structure in the group consisting of hydrazine, hydrazine, and benzopyrene.

The above inorganic fine particles are preferably metal oxides.

The metal oxide is preferably at least one selected from the group consisting of titanium oxide, zirconium oxide, and cerium oxide.

The metal oxide is preferably at least one selected from the group consisting of titanium oxide doped with antimony and titanium oxide doped with antimony.

The above polycarboxylic acid resin having a condensed ring structure preferably has Any one of the condensed ring structures of 、 and 茀, and is an unsaturated base.

The above polyvalent carboxylic acid resin having a condensed ring structure preferably contains a radiation polymerizable functional group.

Further, it is preferred to contain a photopolymerization initiator.

Further, the present invention relates to a film obtained by curing the above composite resin composition.

Further, the present invention relates to a molded body obtained by curing the above composite resin composition.

Further, the present invention relates to an optical film characterized by comprising a film obtained by curing the composite resin composition.

Further, the present invention relates to a display element characterized by comprising a film obtained by curing the composite resin composition.

Furthermore, the present invention relates to a semiconductor device comprising a molded body obtained by curing the composite resin composition.

According to the present invention, a composite resin composition excellent in dispersion stability and uniformity of inorganic fine particles can be produced. Further, the film obtained by curing the composite resin composition and the molded article have high transparency and are excellent in heat resistance and light resistance. Further, since the filling amount of the inorganic fine particles can be adjusted in a wide range, the refractive index, the film hardness, and the like can be freely adjusted depending on the application. Therefore, the composite resin composition of the present invention is suitable for use as a component for optical films, display elements, color filters, touch panels, electronic paper, solar cells, and semiconductor elements.

The composite resin composition of the present invention is composed of inorganic fine particles having an average particle diameter of 1 to 100 nm synthesized by a vapor phase method, and having an anthracene selected from the group consisting of ruthenium, tetrahydronaphthalene, and anthracene. A polyvalent carboxylic acid resin having at least one condensed ring structure in the group consisting of hydrazine, hydrazine, and benzopyrene.

(inorganic particles)

The inorganic fine particles used in the composite resin composition of the present invention are nano-sized inorganic fine particles having an average particle diameter of 1 to 100 nm synthesized by a vapor phase method.

In general, there are three types of methods for producing inorganic fine particles, such as a solid phase method, a liquid phase method, and a gas phase method. The solid phase method is a method of obtaining fine particles by mechanically pulverizing a solid, but the micronized level of the nanometer has its limit. Therefore, a method of obtaining nano-sized fine particles is usually carried out by a liquid phase method or a gas phase method. The liquid phase method may be a sol-gel method in which a chemical reaction occurs in a solution to grow crystals to obtain fine particles, or a mechanical pulverization method in which a liquid such as water is used as a medium to mechanically pulverize crystals in a liquid medium. Examples of the gas phase method include a laser thermal decomposition method, a combustion method, a plasma-enhanced chemical vapor deposition method, a spray combustion method, a gasification combustion method, an instantaneous gas phase generation method, and the like, which are called in the gas phase. A method of synthesizing inorganic fine particles by reaction.

In the case of the liquid phase method, most of the medium used for the production is water, so in order to be used as a composite resin composition, the blendable resin must also be a water system, and there is a large limitation in blending. Therefore, it is preferable that the fine particles which are stably dispersed in the organic solvent, the surface of the fine particles synthesized by the liquid phase method, in many cases, contain a large number of functional groups having a relatively high polarity such as a hydroxyl group, so that in order to make the hydrophobic solvent higher in the organic solvent The dispersion is kept stable, and it is necessary to treat the surface of the fine particles by a large amount of the surface treatment agent, or to add a large amount of a dispersant or a surfactant (for example, Japanese Patent Laid-Open Publication No. 2008-266661). These additives may adversely affect heat resistance or light resistance, and further, since the content of organic substances in the blending increases, it is difficult to extract high characteristics of the inorganic fine particles.

On the other hand, the inorganic fine particles obtained by the vapor phase method have properties of not only being easily dispersed in water but also being easily dispersed in various organic solvents (for example, Japanese Patent Laid-Open Publication No. 2003-327432). Therefore, the dispersion containing the inorganic fine particles synthesized by the vapor phase method can maintain a relatively stable dispersion state by adding a very small amount of a surface treatment or a dispersing agent, a surfactant, or not at all, so that the dispersion can be reduced. The organic component to be obtained is excellent in light resistance or heat resistance of a film or a molded article obtained from a composite resin composition containing the components. Further, it is possible to increase the content of the inorganic fine particles themselves in the blending, and to easily extract the original characteristics of the inorganic fine particles, and is suitable as the inorganic fine particles in the composite resin composition of the present invention.

The method for producing inorganic fine particles synthesized by the vapor phase method of the present invention is preferably a laser method or an instantaneous gas phase generating method which is high in yield and suitable for mass production.

The particle diameter of the inorganic fine particles is preferably from 1 to 100 nm, more preferably from 1 to 50 nm. When it is larger than 100 nm, light scattering due to particles in a film or a formed body becomes intense, and high transparency cannot be maintained. Moreover, when it is less than 1 nm, the specific surface area of the fine particles becomes large, and the cohesive energy becomes high, and it is difficult to maintain dispersion stability. The particle diameter can be measured by a device such as a dynamic light scattering method, a laser diffraction method, or an ultracentrifugation precipitation method.

Examples of the inorganic fine particles include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and 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 ), yttrium 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 ), yttrium oxide (Bi _{2 )} Metal oxide fine particles such as O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), cerium oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), cerium oxide (GeO ₂ , GeO); tantalum nitride, nitriding Nitrogen such as boron. Further, a composite oxide composed of two or more kinds of metal elements such as titanate such as barium titanate, titanium/ruthenium composite oxide, or yttrium-stabilized zirconia may be used. Among these, titanium oxide fine particles, zirconia fine particles or cerium oxide fine particles are preferable in terms of ease of obtaining and easy adjustment of optical characteristics such as refractive index. The inorganic fine particles may be used singly or in combination of two or more.

Further, a compound in which a metal oxide is doped with a different kind of element can also be used. Examples of the compound include titanium oxide doped with antimony or titanium oxide doped with antimony. These compounds may be used singly or in combination of two or more.

The composite oxide includes not only a compound or a solid solution composed of elements of a multi-component but also a core-shell structure having a metal oxide composed of other metal elements to coat the periphery of the metal oxide fine particles as a core. And a structure having a multi-component dispersion type in which a plurality of other metal oxide fine particles are dispersed in one metal oxide fine particle.

In the present invention, the above inorganic fine particles may be surface treated. The term "surface treatment" refers to the treatment of a compound which can react with a hydroxyl group present on the surface of the microparticles, such as a coupling agent. The above surface treatment can be carried out by dispersing inorganic fine particles in a solvent, mixing the coupling agent under acidic conditions, and allowing the surface treatment. The coupling agent which can be used for the above surface treatment may, for example, be a decane coupling agent or a titanium coupling agent, and examples thereof include 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxyloxy group. (Methyl) propylene decyloxydecane such as propylmethyldimethoxydecane; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, Epoxy decanes such as 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; vinyltrimethoxydecane, vinyl a vinyl decane such as triethoxy decane, vinyl tris(β-methoxyethoxy) decane, dimethylvinyl methoxy decane, vinyl trichloro decane or dimethyl vinyl chlorodecane; N-2-(Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyl a quaternary ammonium salt such as an amino decane such as methyl dimethoxy decane or a hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxy decane; P-styryltrimethoxydecane; phenyltrimethoxydecane; Propyl dimethylallyl acyl isostearyl titanate, isopropyl diallyl acyl isostearyl titanate esters such as titanium. These may be used alone or in combination of two or more. It is preferably an epoxy decane or a (meth) propylene decyl oxyalkylene which has a reactive functional group and is cured together with the resin of the resin composition of the present invention to fix the inorganic fine particles in the cured film or the molded body.

The blending amount of the metal oxide fine particles is 0.1 to 5000 parts by weight based on 100 parts by weight of the polyvalent carboxylic acid resin having a condensed ring structure. If it is less than 0.1 part by weight, the characteristics of the fine particles cannot be sufficiently exhibited, and if it exceeds 5000 parts by weight, the film formability is lowered. It is preferably 1 to 2000 parts by weight, more preferably 5 to 1000 parts by weight. Further, a large amount of inorganic fine particles can be blended in the composite resin composition of the invention of the present application. For example, it is also possible to blend 200 parts by weight or more, and further 500 parts by weight or more, which is usually difficult to blend, with respect to 100 parts by weight of the polyvalent carboxylic acid resin.

When the above metal oxide fine particles are blended, those which are previously dispersed in various solvents can be used. Examples of the solvent include alcohols such as methanol, ethanol, 2-propanol and butanol; and esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and γ-butyrolactone; Diethyl ether, ethylene glycol monomethyl ether (methyl acesulfame), ethylene glycol monoethyl ether (ethyl sialo), ethylene glycol monobutyl ether (butyl cyanidin), diethylene glycol monomethyl Ethers, ethers such as diethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexanone; benzene, toluene, xylene, ethyl An aromatic hydrocarbon such as benzene; guanamine such as dimethylformamide, N,N-dimethylacetoacetamide or N-methylpyrrolidone. At this time, the blend ratio of the solvent to the metal oxide fine particles is preferably from 30:70 to 90:10.

Further, a dispersing agent of a type which does not affect the effects of the present invention or a dispersing agent which does not affect the effects of the present invention may be added as needed. When a dispersing agent is added, for example, a polyacrylic dispersing agent, a polycarboxylic acid dispersing agent, a phosphate dispersing agent, an oxime dispersing agent, or the like can be used. The amount of the dispersant added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the inorganic fine particles. When it is more than 5 parts by weight, the heat resistance or light resistance of the obtained cured product may be lowered. In order to disperse the inorganic fine particles in the resin, a large amount of a dispersing agent is required depending on the resin or the inorganic fine particles. However, if the polyvalent carboxylic acid resin and the inorganic filler used in the present invention are used, the dispersing agent may be omitted, and even if used, it is 5 weights. In a very small amount below, a large amount of inorganic fine particles can be uniformly dispersed.

(polycarboxylic acid resin)

The above has a color selected from the group consisting of ruthenium, tetrahydronaphthalene a polyvalent carboxylic acid resin (D) having at least one condensed ring structure of the group consisting of hydrazine, hydrazine, and benzopyrene, which is a resin obtained by reacting an epoxy ester resin (C) with a polyvalent carboxylic acid or an anhydride thereof, and the ring The oxyester resin (C) is a reaction product of the epoxy resin (A) represented by the following formula (1) and a monocarboxylic acid, or an alcohol compound (B) represented by the following formula (10) and shrinkage The reactant of the glyceride compound. Particularly, in view of excellent dispersibility or heat resistance, the above polyvalent carboxylic acid resin having a condensed ring structure preferably has And any of the ring structure of the 茀.

Here, Y _{1 to 4} are each independently selected from the group of the following general formula (2) or the following general formula (3), and p _{1 to 4} are each independently an integer of 0 to 4.

Here, Y _{5 to 6} are each independently selected from the group of the formula (2) or the following formula (3), and p _{5 to 6} are each independently an integer of 0 to 4.

Here, the Z of the above formulae (1) and (2) includes quinone (the following formula (4)), tetrahydronaphthalene (the following formula (5)), hydrazine (the following formula (6)), (a divalent group of a condensed ring structure composed of the following formula (7)), hydrazine (the following formula (8)), and benzofluorene (the following formula (9)), and R _{1 to 6} are each independently a carbon number of 1 a linear, branched or cyclic alkyl or alkenyl group of 10, an alkoxy group having 1 to 5 carbon atoms, a phenyl group which may have a substituent, or a halogen atom, and q _{1 to 6} are each independently 0. An integer of up to 4. Further, R _{7 to 14 of the} above formulas (1), (2), and (3) are each independently a hydrogen atom or a methyl group, and m _{1 to 8} and s _{1 to 2} are each independently an integer of 0 to 10, and the structural formula is It can be symmetrical or asymmetrical. Further, a plurality of R _{1 to 14} and Y _{1 to 6} may be the same or different.

Here, Z is the same as above, and R _{15 to 16} are each independently a linear, branched or cyclic alkyl or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and may have a substituent of a phenyl group or a halogen atom, wherein f _{1 to 2} are each independently an integer of 0 to 4, and R _{17 to 18} are each independently a hydrogen atom or a methyl group, and m _{9 to 10} are each independently an integer of 0 to 10, and r _1~2 are independently integers from 1 to 5, and the structural formula can be bilaterally symmetric or asymmetric. Also, a plurality of R _15~18 may be the same or different.

The polycarboxylic acid resin (D) of the present application is soluble in a base.

The monocarboxylic acid used for the preparation of the above epoxy ester resin (C) may, for example, be a compound having one carboxyl group, but is not limited thereto: (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-hydroxyl ring Hexanecarboxylic 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-oxycyclohexyl)propionic acid, 3-cyclohexene-1-carboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid hydroalkyl ester, ring Heptanecarboxylic acid, norbornenecarboxylic acid, tetracyclododecenecarboxylic acid, 1-adamantanic acid, (4-tricyclo[5.2.1.0 ^2.6 ]indol-4-yl)acetic acid, p-methylbenzoic acid, p-ethyl Benzoic acid, p-octylbenzoic acid, p-nonylbenzoic acid, p-dodecylbenzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-propoxy Benzoic 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-tert-butyl-4-hydroxybenzoic acid, o-benzhydrylbenzoic acid, o-nitrobenzoic acid, O-(acetoxybenzoyloxy)benzoic acid, monomethyl terephthalate, monomethyl isophthalate, monocyclohexyl isophthalate, benzene Oxyacetic acid, chlorophenoxyacetic acid, phenylthioacetic acid, phenylacetic acid, 2-oxy-3-phenylpropionic acid, o-bromophenylacetic acid, o-iodophenylacetic acid, methoxyphenylacetic acid, 6-phenylhexanoic acid, dibenzoic acid, α-naphthoic acid, β-naphthoic acid, indolecarboxylic acid, phenanthrenecarboxylic acid, indole-2-carboxylic acid, indancarboxylic acid, 1,4-dioxy-1,4- Dihydronaphthalene-2-carboxylic acid, 3,3-diphenylpropionic acid, nicotinic acid, isonicotinic acid, cinnamic acid, 3-methoxycinnamic acid, 4-methoxycinnamic acid, quinolinecarboxylic acid, etc. These may be used singly or in combination of two or more. In particular, as a suitable monocarboxylic acid, those containing an unsaturated polymerizable group capable of introducing a radiation polymerizable functional group are preferable, and for example, (meth)acrylic acid is preferable. Here, the radiation polymerizable functional group means a functional group having a property of generating a polymerization reaction by various kinds of radiation. The "radiation" includes visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, molecular beams, gamma rays, synchrotron radiation, proton beam rays, and the like.

The glycidyl ester compound used for the preparation of the above epoxy ester resin (C) may, for example, be the following compounds, but is not limited thereto: glycidyl (meth)acrylate, glycidyl acetate, glycidyl butyrate, Glycidyl benzoate, glycidyl p-ethylbenzoate, glycidyl (p-) phthalate, etc. may be used alone or in combination of two or more. A monocarboxylic acid glycidyl ester is particularly preferable, and among them, an unsaturated group which can introduce a radiation polymerizable functional group is preferable, and for example, glycidyl (meth)acrylate is preferable.

The reaction of the above epoxy resin (A) with a monocarboxylic acid and the reaction of the alcohol compound (B) with a glycidyl ester compound are carried out in a temperature range of 50 to 120 ° C for 5 to 30 hours, if necessary, using a suitable solvent. The solvent which can be used, for example, is methyl cyproterone acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol. An alkylene monoalkyl ether acetate such as diethyl ether acetate, diethylene glycol monobutyl ether acetate or 3-methoxybutyl-1-acetate; Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether, etc. alkylene monoalkyl ether; methyl ethyl ketone, methyl amyl ketone and other ketones An ester such as dimethyl succinate, diethyl succinate, diethyl adipate, diethyl malonate or dibutyl oxalate. Among these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred. Further, a catalyst and a polymerization inhibitor can be used as needed. Examples of the catalyst to be used include an onium salt, a quaternary ammonium salt, a phosphine compound, a tertiary amine compound, and an imidazole compound, and it is usually preferably in the range of 0.01 to 10% by weight based on the entire reactant. use. Further, examples of the polymerization inhibitor to be used include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, and thiophene. Further, 2,6-diisobutylphenol or 2,6-di-tert-butyl-4-methylphenol is usually added in an amount of 5% by weight or less based on the total amount of the reactant.

The polyvalent carboxylic acid used for the preparation of the polyvalent carboxylic acid resin (D) having a condensed ring structure is a carboxylic acid having a plurality of carboxyl groups such as a dicarboxylic acid or a tetracarboxylic acid, and examples of such a polycarboxylic acid or an anhydride thereof include the following compounds; : maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methyl endomethylenetetrahydrogen a dicarboxylic acid such as phthalic acid, chlorendic acid, methyltetrahydrophthalic acid or glutaric acid, and the like; a trimellitic acid or an anhydride thereof; pyromellitic acid or diphenyl A tetracarboxylic acid such as benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid or biphenyl ether tetracarboxylic acid; and an acid dianhydride such as benzophenone tetracarboxylic acid.

In one example of the polyvalent carboxylic acid resin (D) having a condensed ring structure, for example, a resin represented by the following formula (11) or formula (12) can be mentioned.

Here, Z is a ruthenium, tetrahydronaphthalene, anthracene, A divalent group of any condensed ring structure of hydrazine, benzopyrene, A ₁ and A ₃ are residues of a tetracarboxylic dianhydride, and A ₂ and A ₄ are residues of a dicarboxylic anhydride. Here, u and u _{2 are on} average from 0 to 130.

In the above formulas (11) and (12), it is preferred that Z is contained. Or the divalent group of the condensed ring structure of the skeleton.

In Z is included When the divalent group of the condensed ring structure of the fluorene skeleton is used, the refractive index of the polyvalent carboxylic acid resin (D) is high, which is advantageous in that the refractive index difference from the inorganic fine particles can be reduced.

The polyvalent carboxylic acid resin (D) having a condensed ring structure can be obtained by reacting the above-described epoxy resin (C) having a condensed ring structure with a polyvalent carboxylic acid or an anhydride thereof. Further, in the reaction, in order to increase the heat resistance or heat yellowing resistance of the obtained resin, the polyol may be allowed to coexist and react.

Examples of the above polyols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, and neopentyl Glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol, 1,9-nonanediol Aliphatic diol; alicyclic diol such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A; ethylene oxide of bisphenol A, propylene oxide adduct, etc. An aromatic diol; a trihydric or higher alcohol such as glycerin, trimethylolpropane, trimethylolethane, di-trimethylolpropane, pentaerythritol, sorbitol or dipentaerythritol.

In this reaction, the order of addition of the epoxy ester resin (C), the polyol, and the polycarboxylic acid or its anhydride is not limited. For example, there is a method in which the reaction is carried out at the same time, and a method in which the epoxy ester resin (C) is mixed with a polyhydric alcohol, followed by addition of a polyvalent carboxylic acid or an anhydride thereof, and mixing and reaction. Further, a polyvalent carboxylic acid may be further added to the reaction products to carry out the reaction.

By appropriately selecting the type of the polyvalent carboxylic acid or its anhydride, it is possible to produce a polyvalent carboxylic acid resin (D-b) having a condensed ring structure and a structure different from each other, and further reacting with a polyhydric alcohol to form a polyvalent carboxylic acid resin (D-b). Specifically, for example, the first to sixth polycarboxylic acid resins (D) represented by the following (D-a-i) to (D-a-iii) and (D-b-i) to (D-b-iii) can be prepared, and these are exemplified.

(Dai) The first polycarboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (C) with one polyvalent carboxylic acid or an anhydride thereof; (Da-ii) a second polycarboxylic acid resin a resin obtained by mixing and reacting an epoxy ester resin (C) with a mixture of two or more kinds of polycarboxylic acids or anhydrides thereof (for example, a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride); (Da-iii) The third polycarboxylic acid resin: a resin obtained by reacting an epoxy ester resin (C) with a tetracarboxylic acid or a dianhydride thereof, and reacting the obtained reaction product with a dicarboxylic acid or an anhydride thereof.

(Dbi) The fourth polycarboxylic acid resin: a resin obtained by mixing and reacting an epoxy ester resin (C), a polyhydric alcohol, and a polyvalent carboxylic acid or an anhydride thereof; (Db-ii) Carboxylic acid resin: a mixture of an epoxy ester resin (C), a polyhydric alcohol, and a mixture of two or more kinds of polycarboxylic acids or anhydrides thereof (for example, a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride) And the obtained resin; and (Db-iii) the sixth polycarboxylic acid resin: epoxy ester resin (C), polyol, and tetracarboxylic acid or its dianhydride are reacted, and the obtained reaction product is further reacted with dicarboxylic acid A resin obtained by reacting its anhydride.

The polycarboxylic acid resins (D-a) or (D-b) having different structures obtained in the above manner are utilized depending on the intended use.

In addition, the "polycarboxylic acid or its anhydride" means "at least one of a specific polycarboxylic acid and an anhydride corresponding thereto". For example, if the polycarboxylic acid is phthalic acid, it means phthalic acid. At least one of formic acid and phthalic anhydride.

Further, the phrase "a mixture of two or more polycarboxylic acids or anhydrides thereof" means that at least two kinds of polycarboxylic acids or anhydrides thereof are present at the same time. Therefore, in the above methods (D-a-ii) and (D-b-ii), at least two kinds of polycarboxylic acids or anhydrides thereof participate in the reaction.

In any of the above methods, the polyhydric carboxylic acid resin is produced by dissolving (suspending) the epoxy ester resin (C), the polyhydric alcohol, and the polycarboxylic acid or its anhydride in the above-exemplified method (sequence). For example, a cellophane solvent such as ethyl cyproterone acetate or butyl cyanoacetate, an alkanediol monoalcohol such as propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate. An ester solvent of an ether and acetic acid, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, and the like are heated and reacted. Further, a catalyst can be added as needed. Examples of the catalyst to be used include an onium salt, a quaternary ammonium salt, a phosphine compound, a tertiary amine compound, and an imidazole compound, and it is usually preferably in the range of 0.01 to 10% by weight based on the entire reactant. use.

In the production of the above polycarboxylic acid resin, in the case of using a polyol, it is preferred to adjust the epoxy ester resin (C) and the polyol so that the hydroxyl group of the epoxy ester resin (C) and the hydroxyl group of the polyol are The ear ratio (hydroxyl group of the epoxy ester resin (C) / hydroxyl group of the polyol) is from 99/1 to 50/50, more preferably from 95/5 to 60/40. If the molar ratio of the hydroxyl group of the polyol exceeds 50%, the molecular weight of the obtained resin sharply increases to cause gelation. Moreover, if it is less than 1%, it is difficult to improve heat resistance or heat discoloration resistance.

The polyvalent carboxylic acid or its anhydride is 1 equivalent (mole) with respect to the hydroxyl group of the epoxy ester resin (C) (in the case of using a polyol, the total of the hydroxyl groups of the polyol), and preferably 0.1 in terms of an acid anhydride group. ～1 equivalent, more preferably 0.4 to 1 equivalent of the reaction. When the polyvalent carboxylic acid or its anhydride is less than 0.1 equivalent in terms of an acid anhydride group, the molecular weight of the obtained polyvalent carboxylic acid resin may not be sufficiently increased. Therefore, when exposure and development are carried out using a radiation sensitive resin composition containing such an alkali-soluble resin, the heat resistance of the obtained film may be insufficient or the film may remain on the substrate. When the polyvalent carboxylic acid or its anhydride exceeds 1 equivalent in terms of an acid anhydride group, an unreacted acid or acid anhydride remains, and the molecular weight of the obtained polyvalent carboxylic acid resin is lowered, and the developability of the radiation-sensitive resin composition containing the resin is obtained. Poor situation.

In addition, the acid anhydride group conversion means the amount of the carboxyl group and the acid anhydride group contained in the polycarboxylic acid or its anhydride used in the conversion of the acid anhydride.

In the production of the second, third, and fifth and sixth polycarboxylic acid resins (D), two or more kinds of polycarboxylic acids or anhydrides thereof are used. Dicarboxylic anhydrides and tetracarboxylic dianhydrides are generally used. The ratio of the dicarboxylic anhydride to the tetracarboxylic dianhydride (dicarboxylic anhydride/tetracarboxylic dianhydride) is preferably from 1/99 to 90/10, more preferably from 5/95 to 80/20, in terms of a molar ratio. When the ratio of the dicarboxylic anhydride is less than 1 mol% of the total acid anhydride, the resin viscosity is high and the workability is lowered. Further, since the molecular weight of the obtained resin is excessively large, when a film is formed on a substrate and exposed to light using a radiation-sensitive resin composition containing the resin, it is difficult to obtain a target pattern in the exposed portion. tendency. If the ratio of the dicarboxylic anhydride exceeds 90 mol% of the total acid anhydride, the molecular weight of the obtained resin becomes too small. Therefore, when a coating film is formed on the substrate using the composition containing the resin, it is likely to be applied after prebaking. Problems such as stickiness on the film.

In any of the above cases, when the epoxy ester resin (C) is reacted with a polyvalent carboxylic acid or an anhydride thereof and, if necessary, a reaction temperature, the reaction temperature is preferably from 50 to 130 ° C, more preferably from 70 to 120 ° C. When the reaction temperature exceeds 130 ° C, condensation of a carboxyl group and a hydroxyl group locally occurs, and the molecular weight sharply increases. On the other hand, if it is less than 50 ° C, the reaction does not proceed smoothly, and the unreacted polycarboxylic acid or its anhydride remains.

(composite resin composition)

In the composite resin composition of the present invention, the polyvalent carboxylic acid resin (D) preferably contains a radiation polymerizable functional group, and specifically, preferably contains an unsaturated group such as a (meth) acrylonitrile group. When the polyvalent carboxylic acid resin (D) is a resin containing a radiation polymerizable functional group, the composite resin composition has photocurability, and thus can be used as the photosensitive composite resin composition (E).

Here, the term "sensitivity" refers to the property of chemical reaction by various kinds of radiation, and the radiation may be in the form of visible light, ultraviolet light, electron beam, X-ray, alpha ray, beta ray, and the like from a longer wavelength. Gamma rays. Among these, in terms of economy and efficiency, ultraviolet rays are the best radiation in practical use. For ultraviolet rays, ultraviolet light emitted from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an arc lamp, a xenon lamp or the like can be preferably used. Radiation with a wavelength shorter than that of ultraviolet rays has a higher chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

In the case where the composite resin composition of the present invention is the photosensitive composite resin composition (E), it is preferred to add a photopolymerization initiator (F). Further, in order to adjust the curability or to adjust the film properties such as the hardness after hardening, a polybasic carboxylic acid having an unsaturated group may be added to the photosensitive composite resin composition (E) within a range that does not impair the effects of the present invention. Various photocurable monomers or photocurable resins (G) other than the resin (D).

The photopolymerization initiator (F) is a compound having a photopolymerization initiation function and/or a compound having a sensitizing effect. Examples of the above compound include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloro Acetophenones such as acetophenone and p-tert-butylacetophenone; dibenzophenones such as benzophenone, 2-chlorobenzophenone, and 4,4'-bisdimethylaminobenzophenone Benzophenone; benzoin; benzoin; benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; benzildimethylketal; 2-chlorosulfur 2,4-diethyl sulphide 2-methylsulfide 2-isopropylsulfur Sulfur compound; 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine and the like; azobisisobutyronitrile; benzoyl peroxide Organic peroxides such as formazan and cumene peroxide; and 2-mercaptobenzimidazole and 2-mercaptobenzoene a thiol compound such as azole or 2-mercaptobenzothiazole.

The blending amount of the photopolymerization initiator (F) is preferably 0.05 to 10.0 parts by weight, more preferably 0.1 to 5.0 parts by weight, per 100 parts by weight of the compound containing an unsaturated group.

The above-mentioned "unsaturated group-containing compound" means all of the radiation-curable unsaturated group-containing compounds contained in the photosensitive composite resin composition (E), and includes the polycarboxylic acid resin (D) of the present invention and has The photocurable resin, the photocurable monomer other than the polyvalent carboxylic acid resin (D) of the present invention, or the photocurable resin (G).

These photopolymerization initiators (F) may be used alone or in combination of two or more. Further, a compound which does not have a photopolymerization initiator itself can be added, but a compound which can increase the ability of a photopolymerization initiator can be used by using it in combination with the above compound. Examples of such a compound include a tertiary amine such as triethanolamine which is effective when used in combination with benzophenone.

In addition, when the polyvalent carboxylic acid resin (D) does not contain a radiation polymerizable functional group such as an unsaturated group, it contains various photocurable monomers or photocurable resins (G) or quinonediazide. (H) As an essential component, it functions as a photosensitive composite resin composition (E).

In the case where the above quinonediazide compound (H) is added, the photosensitive composite resin composition (E) of the present invention becomes a positive photosensitive composite resin composition. In the case of a positive resin composition, the composition itself does not harden when exposed to light. In the case of a positive type, in order to obtain a cured film after patterning, for example, a thermosetting resin such as an epoxy compound (I) is added to the photosensitive composite resin composition (E), and it is thermally hardened after irradiation with radiation and development. Thereby, a cured film can be formed. This thermosetting is mainly carried out by a crosslinking reaction of a carboxylic acid group of the polyvalent carboxylic acid resin (D) with an epoxy group of the epoxy compound (I) by heat.

The photocurable monomer or the photocurable resin (G) is a monomer or oligomer which can be polymerized by radiation, and can be contained according to physical properties conforming to the purpose of use of the composition. Examples of the radiation-polymerizable monomer or oligomer include the following monomers or oligomers: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) a (meth) acrylate having a hydroxyl group such as 3-hydroxypropyl acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethyl bis(meth)acrylate Glycol ester, tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tris(methyl) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (meth)acrylates such as (meth)acrylic acid glycerides. These monomers or oligomers may be used alone or in combination of two or more.

These monomers or oligomers function as a viscosity modifier or a photocrosslinking agent, and can be contained in a range that does not impair the properties of the resin composition of the present invention. In general, at least one of the above monomers and oligomers is contained in the composition in an amount of 50 parts by weight or less based on 100 parts by weight of the polyvalent carboxylic acid resin (D). If the content of the monomer or oligomer exceeds 50 parts by weight, there is a possibility that problems occur in the dispersibility or uniformity of the inorganic fine particles.

The above quinonediazide compound (H) is preferably a compound esterified with 1,2-quinonediazidesulfonic acid, and examples thereof include trihydroxybenzophenone and 1,2-naphthoquinonediazide. Acid ester, ester of tetrahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid, ester of pentahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid, six An ester of hydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid, an ester of bis(2,4'-dihydroxyphenyl)methane with 1,2-naphthoquinonediazidesulfonic acid, An ester of bis(p-hydroxyphenyl)methane with 1,2-naphthoquinonediazidesulfonic acid, an esterified product of tris(p-hydroxyphenyl)methane with 1,2-naphthoquinonediazidesulfonic acid, 1, An ester of 1,1-tris(p-hydroxyphenyl)ethane with 1,2-naphthoquinonediazidesulfonic acid, bis(2,3,4-trihydroxyphenyl)methane and 1,2-naphthoquinone An ester of diazidosulfonic acid, an esterified product of 2,2-bis(2,3,4-trihydroxyphenyl)propane with 1,2-naphthoquinonediazidesulfonic acid, 1,1,3-three Esterified product of (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane with 1,2-naphthoquinonediazidesulfonic acid, 4,4'-[1-[4-[1 -[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazidesulfonic acid ester , an esterified product of bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane with 1,2-naphthoquinonediazidesulfonic acid, 3,3,3',3' - ester of tetramethyl-1,1'-spiro-5,6,7,5',6',7'-hexanol with 1,2-naphthoquinonediazidesulfonic acid, and 2,2 An esterified product of 4-trimethyl-7,2',4'-trihydroxyflavan and 1,2-naphthoquinonediazidesulfonic acid. Further, a quinonediazide compound other than the above may also be used.

The above epoxy compound (I) means a polymer or monomer having at least one epoxy group. A polymer having at least one epoxy group, for example, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type Epoxy resin such as epoxy resin, biphenyl type epoxy resin or alicyclic epoxy resin.

Examples of the monomer having at least one epoxy group include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, and allylic acid. Glycidyl ether, glycidyl methacrylate, and the like. These compounds may be used singly or in combination of two or more.

The epoxy compound (I) can be contained in a range that does not impair the properties of the resin composition of the present invention. Usually, the epoxy compound (I) is contained in an amount of 50 parts by weight or less per 100 parts by weight of the polyvalent carboxylic acid resin (D). When it exceeds 50 parts by weight, when the composition containing the component is cured, it is liable to cause breakage, and the adhesion is also liable to lower.

Further, various additives (J) may be added to the composite resin composition of the present invention as needed. The above additive (J) may be a thermal polymerization inhibitor, an adhesion aid, an epoxy hardening accelerator, a surfactant, an antifoaming agent, or the like, and these may be included in the composition in an amount that does not impair the object of the present invention. In.

Examples of the above thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, and thiophene (phenothiazine) and so on.

The adhesion aid is contained in order to improve the adhesion of the obtained composition. The adhesion aid is preferably a decane compound (functional decane coupling agent) having a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group. Specific examples of the functional decane coupling agent include trimethoxy decyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl triethoxy decane, and ethylene. Trimethoxy decane, γ-isocyanatopropyltriethoxy decane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy Base decane and the like.

Examples of the epoxy group hardening accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. By containing a small amount of the epoxy group hardening accelerator, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness of the cured film obtained by heating can be improved.

The surfactant is contained, for example, in order to facilitate application of the liquid composition on the substrate, whereby the flatness of the resulting film is also improved. Examples of the surfactants include BM-1000 (manufactured by BM Chemie Co., Ltd.), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Fluorad FC-135, and Fluorad FC-170C. , Fluorad FC-430 and Fluorad FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 and Surflon S-145 (made by Asahi Glass Co., Ltd.) , SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (manufactured by Toray Silicone Co., Ltd.).

Examples of the antifoaming agent include compounds such as polyfluorinated, fluorine, and acrylic.

The solvent which can be contained in the composite resin composition of the present invention is not particularly limited as long as it does not react with each component in the composition and dissolves or disperses the organic solvent. For example, the following compounds may be mentioned: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ether, and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetate such as methyl cyproterone acetate or ethyl cyproterone acetate; diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl Diethylene glycol dialkyl ethers such as ether, diethylene glycol ethyl methyl ether; diethylene glycol monoalkane such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Ethyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, two Alkylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone a ketone such as methyl amyl ketone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate Ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -ethyl ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, diethyl succinate, diethyl adipate, diethyl malonate And esters such as dibutyl oxalate.

Among these, glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and 3-ethoxypropane is preferred. Ethyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and methyl amyl ketone. These solvents may be used alone or in combination of two or more.

In the case where the above solvent is added, the blending amount thereof is preferably from 5 to 90% by weight based on the entire composition.

(film and formed body)

The polycarboxylic acid resin used in the present invention has a refractive index of approximately 1.55 to 1.65 (for light having a wavelength of 633 nm), but is insufficient for a refractive index required for a highly functional material. Further, since the refractive index of the inorganic fine particles synthesized by the vapor phase method used in the present invention differs greatly depending on the type of the inorganic fine particles, it cannot be generalized. For example, in the case of titanium oxide, it depends on the crystal structure, but It is usually 1.90 to 2.10, which is higher than the polycarboxylic acid resin.

According to the present invention, since a large amount of inorganic fine particles having a higher refractive index can be blended in the polyvalent carboxylic acid resin, a transparent film having a very high refractive index can be obtained from the composite resin composition of the present invention, and for example, a refractive index of 1.75 or more can be obtained. It is preferably 1.80 or more.

The cured film obtained by curing the composite resin composition of the present invention and the molded body have a high refractive index and are excellent in transparency, heat resistance, light resistance, and the like. Therefore, the composition of the present invention is preferably used as, for example, a display device or a material for a protective film for an electronic component (for example, a liquid crystal display element such as a color filter, an integrated circuit element, a solid-state imaging element, or the like). a film forming material); an interlayer insulating film and/or a forming material for a planarizing film; a binder for a color photoresist; a solder resist used in the manufacture of a printed wiring board; and a bead spacer instead of the liquid crystal display element An alkali-soluble photosensitive composition or the like which is suitable for formation of a columnar spacer. Further, the composition of the present invention can be preferably used as a material for various optical parts (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film of the optical parts; and an adhesive for optical parts ( An adhesive for optical fibers, etc.; a coating agent for producing a polarizing plate; a photosensitive resin composition for hologram recording, and the like.

The film and the molded body obtained by curing the composite resin composition of the present invention are also one of the inventions.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples.

Production Example 1 (Preparation of vapor phase titanium oxide dispersion)

Super Titania F-2 (gas phase oxidation method) 100 g manufactured by Showa Denko Co., Ltd., and 3-methylpropenyl propyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) 50 g was mixed with propylene glycol monomethyl ether acetate (PGMEA) 2000 g, and dispersed in a zirconia bead using a paint shaker (manufactured by Red Devil Co., Ltd.) for 5 hours to obtain a titanium oxide dispersion. Further, the dispersion was heated at 60 to 70 ° C for 3 hours to carry out a surface treatment, and then a part of the solvent was removed by concentration under reduced pressure to obtain a titanium oxide having a solid content of 20% by weight and an average particle diameter of 33 nm. Dispersions.

Production Example 2 (Preparation of a vapor phase doped titanium oxide dispersion)

10 g of antimony-doped titanium oxide synthesized by an instant vapor phase generation method, and 3-methylpropenylpropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) 4 g and 200 g of propylene glycol monomethyl ether acetate (PGMEA) was mixed, and zirconia beads were used as a medium, and dispersed by a paint shaker (manufactured by Red Devil Co., Ltd.) for 5 hours to obtain a cerium-doped titanium oxide dispersion. Further, the dispersion was heated at 60 to 70 ° C for 3 hours to carry out a surface treatment, and then a part of the solvent was removed by concentration under reduced pressure to obtain a doping having a solid content of 20% by weight and an average particle diameter of 41 nm. A titanium oxide dispersion with ruthenium. It was confirmed by X-ray diffraction analysis that the doped titanium oxide dispersion was a solid solution in which Nb was solid-solubilized in the TiO ₂ crystal.

Production Example 3 (Synthesis of Polycarboxylic Acid Resin (1))

To a 300 ml four-necked flask, bisphenol fluorene diglycidyl ether (Osaka Gas Chemical Co., Ltd.: Ogsol PG) 115 g (epoxy equivalent: 270 g/eq) was added as a catalyst. 600 mg of ethylbenzylammonium chloride, 30 mg of 2,6-diisobutylphenol as a polymerization inhibitor, and 36 g of acrylic acid, and air was blown into it at a rate of 10 mL/min on one side at 90 ° Dissolved by heating at 100 °C. Then, it was slowly heated to 120 °C. The solution became transparent and viscous, and stirring was continued in this state. During this period, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH/g to obtain a light yellow transparent and solid condensed ring structure-containing epoxy ester resin. It takes 15 hours for the acid value to reach the target. To the epoxy ester resin, 65 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and after dissolution, 15 g of pyromellitic anhydride (PMDA), tetrahydrophthalic anhydride (THPA) 7.6 g, and bromine were mixed. 0.1 g of tetraethylammonium was gradually added to the temperature, and the reaction was carried out at 110 to 115 ° C for 14 hours. In this manner, a PGMEA solution of the polycarboxylic acid resin (1) was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy.

Further, the polyvalent carboxylic acid resin (1) corresponds to the above polyvalent carboxylic acid resin (D-a-ii).

Production Example 4 (Synthesis of Polycarboxylic Acid Resin (2))

Adding propylene glycol monomethyl ether acetate (PGMEA) 65 g and polyhydric alcohol di-trimethylolpropane 1.5 g to the epoxy resin containing a condensed ring structure obtained in the same manner as in Production Example 3, after dissolving, 15 g of pyromellitic anhydride (PMDA) and 0.1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised, and the reaction was carried out 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 polyvalent carboxylic acid resin (2). The disappearance of the acid anhydride was confirmed by IR spectroscopy.

Further, the polyvalent carboxylic acid resin (2) corresponds to the above polyvalent carboxylic acid resin (D-b-iii).

Production Example 5 (Synthesis of Polycarboxylic Acid Resin (3))

The epoxy ester resin represented by the following formula (13) is added to 65 g of propylene glycol monomethyl ether acetate (PGMEA), and after dissolution, benzophenonetetracarboxylic dianhydride (BTDA) 15 g and brominated tetra are mixed. 0.1 g of ethylammonium was gradually heated, and reacted at 110 to 115 ° C for 14 hours to obtain a PGMEA solution of a polyvalent carboxylic acid resin (3). The disappearance of the acid anhydride was confirmed by IR spectroscopy.

Further, the polyvalent carboxylic acid resin (3) corresponds to the above polyvalent carboxylic acid resin (D-a-i). Further, the epoxy ester resin represented by the following formula can be synthesized by the method disclosed in Japanese Laid-Open Patent Publication No. 2009-185270.

Comparative Production Example 1 (Synthesis of Polycarboxylic Acid Resin (4))

To a 300 ml four-necked flask, cresol novolac type epoxy resin (manufactured by DIC Co., Ltd., Epiclon N-680) 115 g (epoxy equivalent 210 g/eq), triethylbenzyl chloride as a catalyst was added. Ammonium 600 mg, 2,6-diisobutylphenol 30 mg as a polymerization inhibitor, and 36 g of acrylic acid, and air is blown at a rate of 10 mL/min while heating at 90 to 100 ° C. Dissolved. Then, it was slowly heated to 120 °C. The solution became transparent and viscous, and stirring was continued in this state. The acid value was measured during this period, and heating and stirring were continued until the acid value was less than 1.0 mgKOH/g to obtain a pale yellow transparent and solid epoxy ester resin. It takes 15 hours for the acid value to reach the target. 65 g of propylene glycol monomethyl ether acetate (PGMEA) was added to the epoxy ester resin, and after dissolving, tetrahydrophthalic anhydride (THPA) 7.6 g and tetraethylammonium bromide 0.1 g were mixed to make it slow. The temperature was raised slowly and the reaction was carried out at 110 to 115 ° C for 14 hours. In this manner, a PGMEA solution of the polycarboxylic acid resin (4) was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy.

Comparative Production Example 2 (Preparation of TiO ₂ dispersion by liquid phase method)

Titanium oxide TTO-51 (A) (primary particle size 30 nm) manufactured by Ishihara Sangyo Co., Ltd., which is a titanium oxide synthesized by a liquid phase method (hydrolysis), 100 g, and BYK Chemie Japan Limited as a dispersing agent DISPERBYK-112 (60% by weight solids) manufactured by the company, 16.7 g, 3-methylpropenylpropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) 50 g and propylene glycol monomethyl ether Acetic acid ester (PGMEA) 2000 g was mixed, and dispersed in a zirconia bead using a paint shaker (manufactured by Red Devil Co., Ltd.) for 5 hours to obtain a titanium oxide dispersion. Further, the dispersion was heated at 60 to 70 ° C for 3 hours to carry out a surface treatment, and then a part of the solvent was removed by concentration under reduced pressure to obtain a titanium oxide having a solid content of 21% by weight and an average particle diameter of 35 nm. Dispersions.

Examples 1 to 5 and Comparative Examples 1 to 2

Each component was separately mixed according to the blending of Table 1, and a composite resin composition was obtained. Here, the blending ratio of each component shown in Table 1 is described as a solid component (excluding a solvent), and PGMEA is added separately, and the solid content concentration is 20% by weight. The particle size distribution and stability were evaluated for the obtained composite resin composition. Further, the solution was applied onto a glass substrate and a ruthenium substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 120 seconds to form a coating film having a thickness of about 1 μm. The surface of the coating film of the glass substrate and the ruthenium substrate having the coating film was irradiated with a light intensity of 9.5 mW/min in a nitrogen atmosphere using a 250 W high-pressure mercury lamp at a wavelength of 405 nm and an energy of 1000 mJ/cm ² . Ultraviolet light of cm ² . Then, development treatment was carried out at 23 ° C for 120 seconds using a 0.1% by weight aqueous sodium carbonate solution to remove the unexposed portion of the coating film. Thereafter, the cleaning treatment is performed using ultrapure water. The substrate having the obtained film was placed in an oven at 200 ° C, and baked for 30 minutes to heat-harden the film (hereinafter, the film hardened in this manner is referred to as a heat-cured film).

<1> particle size distribution

The Zetasizer Nano ZS manufactured by Malvern Co., Ltd. was measured by a dynamic light scattering method, and the Z-average particle diameter of the composite resin composition was calculated from the scattering intensity distribution.

<2> Stability

The composite resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were stored in a sealed container at 40 ° C for 2 weeks, and the particle size distribution after storage was measured in the same manner as in <1> above. Further, the rate of change of the Z-average particle diameter [| (Z-average particle diameter after storage for 2 weeks at 40 ° C) - (Z-average particle diameter immediately after dispersion) | / (Z after the dispersion) - average particle size)] × 100. In this evaluation, the smaller the value, the better the dispersion stability.

<3> Total light transmittance

The heat-cured film obtained by forming the film on the glass substrate was measured using a hazemeter HZ-2 manufactured by Suga Test Instruments Co., Ltd.

<4> fog value

The heat-cured film obtained by film-forming on the glass substrate was measured using the measuring instrument HZ-2 by Suga Test Instruments Co., Ltd.

<5>Refractive index

The heat-cured film obtained above was measured for a refractive index at 632.8 nm by an optical interference type film quality measuring machine.

<6> Spectral transmittance

The spectral transmittance of the visible light region was measured for the heat-cured film obtained above using a spectrophotometer U-2000 manufactured by Hitachi, and the transmittance at 400 nm was recorded.

<7> developability

The glass substrate having the pre-baked coating film was not subjected to exposure treatment, and was immersed in a 0.1% by weight aqueous sodium carbonate solution for 120 seconds to carry out development. After the development, the substrate was washed with running water for 30 seconds, and the state of the substrate after air-drying was visually observed to confirm the presence or absence of the residue, and the developability was evaluated based on the following evaluation criteria.

◎: no residue on the substrate

○: A small amount of residue was observed on the substrate.

×: A large amount of resin or inorganic fine particles are observed on the substrate.

<8> resolution

A mask having a line-and-gap pattern having a line width of 10 to 100 μm was placed on the glass substrate having the pre-baked coating film obtained above, and after being irradiated with ultraviolet rays under the above conditions, development treatment was carried out. The obtained substrate was observed by an optical microscope, and the line width of the pattern having the smallest line width remaining on the substrate was recorded as the resolution.

<9> Lightfastness

The heat-cured film obtained above was irradiated for 1000 hours using a Sunshine wether meter. The change in the spectral transmittance before and after the irradiation [(the transmittance at a wavelength of 400 nm before the irradiation) - (the transmittance at a wavelength of 400 nm after the irradiation)] was determined. In this evaluation, the smaller the value, the better the light resistance.

<10> Heat resistance

The heat-cured film obtained above was placed in an oven at 250 ° C for 3 hours to be heated. The change in the spectral transmittance before and after heating [(the transmittance at a wavelength of 400 nm before heating) - (the transmittance at a wavelength of 400 nm after heating)] was determined. In this evaluation, the smaller the value, the better the heat resistance.

The above results are shown in Table 1.

(Note 1) Irgacure 907 manufactured by Ciba Japan Co., Ltd.

(Note 2) DISPERBYK-112 manufactured by BYK Chemie Japan Co., Ltd.

(Note 3) Kayarad DPHA (pentaerythritol dihexaacrylate) manufactured by Nippon Kayaku Co., Ltd.

(Note 4) shows the amount of the dispersant blended when preparing the TiO ₂ dispersion of Comparative Production Example 2

According to Table 1, it is understood that the composite resin composition of the present invention can form a cured film having high stability and excellent optical properties, light resistance, and heat resistance when the amount of the inorganic fine particles blended is high.

[Industrial availability]

The composite resin composition of the present invention is suitable for use as a component of an optical film, a display element, a color filter, a touch panel, an electronic paper, a solar cell, a semiconductor element, or the like.

Claims (12)

A composite resin composition comprising inorganic fine particles having an average particle diameter of 1 to 100 nm synthesized by a vapor phase method, and having an anthracene selected from the group consisting of anthracene, tetrahydronaphthalene, anthracene, A polyvalent carboxylic acid resin having at least one condensed ring structure in the group consisting of ruthenium and benzopyrene. The composite resin composition of claim 1, wherein the inorganic fine particles are metal oxides. The composite resin composition according to claim 2, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, and cerium oxide. The composite resin composition according to claim 2, wherein the metal oxide is at least one selected from the group consisting of titanium oxide doped with antimony and titanium oxide doped with antimony. The composite resin composition according to any one of claims 1 to 4, wherein the polyvalent carboxylic acid resin having a condensed ring structure has Any of the condensed ring structures of 、 and 茀, and those containing unsaturated groups. The composite resin composition according to any one of claims 1 to 4, wherein the polyvalent carboxylic acid resin having a condensed ring structure contains a radiation polymerizable functional group. A composite resin composition according to claim 6 of the patent application, which further contains a photopolymerization initiator. A film obtained by hardening a composite resin composition according to any one of claims 1 to 7. A molded body obtained by hardening a composite resin composition according to any one of claims 1 to 7. An optical film comprising a film obtained by curing a composite resin composition according to any one of claims 1 to 7. A display element comprising a film obtained by curing a composite resin composition according to any one of claims 1 to 7. A semiconductor element comprising a molded body obtained by curing a composite resin composition according to any one of claims 1 to 7.