JP2016155998A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is used as a sealing material, a lens material, or an adhesive, can be arbitrarily adjusted in viscosity and curing shrinkage rate, and is capable of forming a cured product having a high refractive index.SOLUTION: The composition contains a compound (A) represented by formula (a), a linear polymer (B) including a monomer unit containing a carbazole skeleton, and a polymerization initiator (C). (Ris a reactive functional group; Ris a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group, a hydroxyalkyl group, an amino group, a carboxyl group, a sulfo group, an acyl group, a nitro group, or a cyano group; Ris a single bond or a linking group; m is 0-4; and n is 0-10.)SELECTED DRAWING: None

Description

  The present invention relates to a resin composition capable of adjusting a viscosity and a curing shrinkage rate according to an application and capable of forming a cured product having a high refractive index, and a cured product thereof.

  In recent years, as a member constituting electronic devices and lenses such as organic electroluminescence devices (organic EL devices), light emitting diode devices (LED devices), displays (liquid crystal display devices, touch panels, etc.), it has excellent impact resistance and flexibility. A cured product of a resin composition is often used because of its light weight. And in the said electronic device, many members (high refractive index member) with a high refractive index are used like the electrode and passivation film in an organic EL apparatus. For this reason, even if it is a case where it arrange | positions so that the sealing material used for these electronic devices may contact the said high refractive index member, it is hard to produce light reflection at the interface with this high refractive index member. Therefore, it is required to have a high refractive index. Further, as a lens material, a resin composition having a high refractive index is required in order to realize a thin lens and a light weight.

  As a resin composition forming a cured product having a high refractive index, a resin composition containing an oligomer having a monomer unit derived from bis (4-vinylthiophenyl) sulfide is known (Patent Document 1).

JP-A-8-183816

However, the resin composition containing an oligomer having a monomer unit derived from bis (4-vinylthiophenyl) sulfide has a low viscosity, and particularly when used as a fill material for dam-fill sealing, the resin composition may easily flow out of the dam. It was a problem. That is, the resin composition has been required to adjust the viscosity according to the application.
In addition, for example, in the case of molding using a mold, it is preferable that the mold shrinks appropriately at the time of curing in terms of excellent releasability. Therefore, it has been required to adjust the curing shrinkage rate according to the application.
However, it has been very difficult to control the viscosity and curing shrinkage rate depending on the application while maintaining the refractive index of the resulting cured product high.

Accordingly, an object of the present invention is a resin composition used as a sealing material, a lens material, or an adhesive, and the viscosity and the curing shrinkage can be easily adjusted according to the application, and the high refractive index. It is providing the resin composition which can form the hardened | cured material (resin hardened | cured material) which has this.
The other object of this invention is to provide the electronic device which has the structure by which the element was sealed with the hardened | cured material of the said resin composition.
Another object of the present invention is to provide a lens comprising a cured product of the resin composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that a specific compound (A) having two reactive functional groups, two or more aromatic rings, and three or more sulfur atoms in the molecule, and a carbazole skeleton. The resin composition containing the linear polymer (B) containing the monomer unit to be contained and the polymerization initiator (C) forms a cured product in which both (A) and (B) have a high refractive index. Since (A) and (B) are excellent in compatibility, the refractive index of the resulting cured product can be kept high by changing the molecular weight and blending ratio of (B). It has been found that the viscosity and cure shrinkage can be easily adjusted to values according to the application. The present invention has been completed based on these findings.

That is, the present invention includes a compound (A) represented by the following formula (a), a linear polymer (B) containing a monomer unit containing a carbazole skeleton, and a polymerization initiator (C). A resin composition for use as a material, lens material, or adhesive is provided.
(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different)

The present invention also provides the above resin composition, wherein the monomer unit containing a carbazole skeleton in the linear polymer (B) is a monomer unit represented by the following formula (b).
(In the formula, A and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom or an organic group. Y represents a single bond or a linking group)

The present invention also provides the above resin composition, wherein R ^a in the formula (a) is a vinyl group or an allyl group.

  The present invention also provides the resin composition, wherein the content of the compound (A) is 30 to 98% by weight of the total amount of the resin composition.

  The present invention also provides the above resin composition, wherein the content of the linear polymer (B) is 1 to 50% by weight of the total amount of the resin composition.

  The present invention also provides the resin composition, wherein the proportion of the compound (A) in the total polymerizable compound contained in the resin composition is 70% by weight or more.

  The present invention also provides an electronic device having a configuration in which an element is sealed with a cured product of the resin composition.

  The present invention also provides a lens comprising a cured product of the above resin composition.

Since the resin composition of this invention has the said structure, according to a use, a viscosity and a cure shrinkage rate can be adjusted easily, and the hardened | cured material (resin hardened | cured material) which has a high refractive index can be formed. For this reason, especially the curable resin film obtained by shape | molding the resin composition of this invention and the resin composition of this invention is a sealing material or seal | sticker used for electronic devices, such as an organic EL apparatus, an LED apparatus, a display. It can be preferably used as an agent or a lens material.
Moreover, since the cured product of the resin composition or curable resin film of the present invention has a high refractive index, when the resin composition of the present invention is used as a sealing material in the process of manufacturing the electronic device, the sealing material and The reflection of light at the interface with the high refractive index member can be suppressed, the light extraction efficiency can be improved, and an electronic device having high efficiency, high luminance, and long life can be obtained. In addition, since the lens formed of the resin composition or the curable resin film of the present invention has a high refractive index, it can be made thinner and lighter, and the design of an electronic device including the lens can be improved. it can.

It is a scanning electron microscope image (SEM image) of an example of electroconductive fiber covering particle | grains.

[Compound (A)]
The compound (A) constituting the resin composition of the present invention is a polymerizable compound represented by the above formula (a). Two R ^a in the formula (a) are the same or different and represent a reactive functional group (polymerizable functional group), for example, vinyl group, allyl group, acryloyl group, methacryloyl group, epoxy group, glycidyl group. And oxetanyl group. In the present invention, among these, a group selected from a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group is preferable.

R ^b in the above formula (a) is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a protecting group. May be protected with an amino group which may be protected with, a carboxyl group which may be protected with a protective group, a sulfo group which may be protected with a protective group, a nitro group, a cyano group, or a protective group An acyl group is shown. Moreover, when m is an integer of 2-4, 2-4 ^Rb couple | bonded with the same aromatic ring may couple | bond together and may form the ring with the carbon atom which comprises an aromatic ring. Further, the plurality of R ^b in the formula (a) may be the same or different.

Examples of the halogen atom for R ^b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group in R ^b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, and nonyl group. And a C _1-10 (preferably C _1-5 ) alkyl group such as a decyl group. Examples of the haloalkyl group for R ^b include C _1-10 (preferably C _1-5 ) haloalkyl groups such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. it can. Examples of the aryl group for R ^b include a phenyl group and a naphthyl group. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, and a methoxy group. C _1-4 alkoxy group, an amino group, a dialkylamino group, a carboxyl group, C _1-4 alkoxycarbonyl group such as methoxycarbonyl group, a nitro group, a cyano group, an acyl group such as an acetyl group (in particular, C _1-6 aliphatic Group (s) such as a group acyl group).

Examples of the hydroxyalkyl group for R ^b include C _1-10 (preferably C _1-5 ) in which at least one hydrogen atom of the C _1-10 alkyl group such as hydroxymethyl group is substituted with a hydroxyl group. A hydroxyalkyl group etc. can be mentioned. The protecting group for hydroxyl group and the protecting group for hydroxyalkyl group in R ^b are those commonly used in the field of organic synthesis [for example, alkyl groups (for example, C _1-4 alkyl such as methyl group, t-butyl group, etc.). Alkenyl group (for example, allyl group); cycloalkyl group (for example, cyclohexyl group); aryl group (for example, 2,4-dinitrophenyl group); aralkyl group (for example, benzyl group); Substituted methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyrani Hydroxyl groups, tetrahydrofuranyl groups, 1-hydroxyalkyl groups (for example, 1-hydroxyethyl group, etc.) Groups and acetal or hemiacetal group capable of forming group; an acyl group (e.g., formyl group, acetyl group, a propionyl group, a butyryl group, an isobutyryl group, C _1-6 aliphatic acyl group such as pivaloyl group; acetoacetyl group; An aromatic acyl group such as a benzoyl group); an alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); an aralkyloxycarbonyl group; a substituted or unsubstituted carbamoyl group; a substituted silyl group (eg, Dimethyl hydrocarbon group (for example, methylidene group, ethylidene group, isopropylidene group, cyclopropylene group) which may have a substituent when there are two or more hydroxyl groups or hydroxymethyl groups in the molecule. Pentylidene group, cyclohexylidene group, benzylidene group, etc.)] Can do.

Examples of the protecting group for the amino group in R ^b include protecting groups commonly used in the field of organic synthesis (eg, alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the protecting groups for the hydroxyl group). Can do.

Examples of the protecting group for carboxyl group and sulfo group for R ^b include protecting groups commonly used in the field of organic synthesis [eg, alkoxy groups (eg, C _1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.). Group, etc.), cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group, etc. ] Can be mentioned.

Examples of the acyl group in R ^b include C _1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group; aromatic acyl groups such as acetoacetyl group; benzoyl group and the like. Groups and the like. As the protecting group for the acyl group, a protecting group commonly used in the field of organic synthesis can be used. Examples of the form in which the acyl group is protected include acetal (including hemiacetal).

When two or more R ^b are bonded per aromatic ring (that is, when m in the formula (a) is 2 to 4), two or more R ^b are bonded to each other to form the formula ( Examples of the ring formed together with the carbon atoms constituting the aromatic ring in a) include, for example, a 5-membered alicyclic carbocycle, a 6-membered alicyclic carbocycle, and two or more alicyclic carbocycles (monocyclic). And alicyclic carbocyclic rings such as condensed rings; lactone rings such as 5-membered lactone rings and 6-membered lactone rings.

R ^c in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are linked. The linking group may have a substituent such as a hydroxyl group or a carboxyl group, and examples of such a linking group include a divalent hydrocarbon group having one or more hydroxyl groups.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. can be mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. Examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a silene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

  Although the molecular weight of a compound (A) is not specifically limited, 300-10000 are preferable at the point which is excellent in solubility with a linear polymer (B), Most preferably, it is 300-1000, Most preferably, it is 300-500.

  Several m in the said Formula (a) is the same or different, and shows the integer of 0-4. N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.

In the formula (a), n is preferably 0 to 3 and particularly preferably 0 in that the viscosity of the resin composition can be adjusted in a wide range. That is, as the compound (A), a compound represented by the following formula (a ′) is particularly preferable.
(Wherein R ^a , R ^b and m are the same as above)

Examples of the compound (A) in the resin composition of the present invention include compounds represented by the following formulas. In the following formula, R is a hydrogen atom or a methyl group.

  A compound (A) can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the compound (A) in the total amount (100% by weight) of the resin composition of the present invention is, for example, about 30 to 99% by weight, preferably 50 to 98% by weight, particularly preferably 60 to 98%. % By weight. When content of a compound (A) is less than the said range, there exists a tendency for a resin composition to become a solid at room temperature (25 degreeC). On the other hand, when the content of the compound (A) exceeds the above range, it tends to be difficult to increase the viscosity of the resin composition.

Compound (A) can be produced by a known or conventional method. For example, a compound in which R ^a in formula (a) is a hydrogen atom (for example, 4,4′-thiobisbenzenethiol, etc.) is used as a raw material, and in the presence of a base, vinyl halide, allyl halide, ( Examples thereof include a method of reacting a halide of meth) acrylic acid, epihalohydrin and the like. In addition, a compound in which R ^a in formula (a) is a vinyl group is obtained by combining a compound in which R ^a in formula (a) is a hydrogen atom (for example, 4,4′-thiobisbenzenethiol etc.) with dihaloethane. It can also be produced by a reaction followed by dehydrohalogenation.

[Linear polymer (B)]
The linear polymer (B) constituting the resin composition of the present invention is a linear polymer containing monomer units (repeating units) containing a carbazole skeleton. The monomer unit may be one type or two or more types.

Examples of the monomer unit containing the carbazole skeleton include monomer units represented by the following formula (b). In the formula (b), A and R ^{1 to} R ⁸ are the same or different and represent a hydrogen atom or an organic group. Y represents a single bond or a linking group.

Examples of the organic group for A and R ^{1 to} R ⁸ include a halogen atom, a hydrocarbon group, a heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group). Group), carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, sulfur acid group, sulfur acid ester group, acyl group (aliphatic acyl group such as acetyl group; aromatic acyl group such as benzoyl group) ), Alkoxy group (C _1-6 alkoxy group such as methoxy group, ethoxy group, etc.), N, N-disubstituted amino group (N, N-dimethylamino group, piperidino group, etc.), etc. And the like. The carboxyl group and the like may be protected with a known or commonly used protecting group in the field of organic synthesis.

  Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms.

  The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms); 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, such as a vinyl group, an allyl group, and a 1-butenyl group) An alkenyl group having preferably about 2 to 3); an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as an ethynyl group and a propynyl group.

As the alicyclic hydrocarbon group, for example, about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. A cycloalkenyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group, Norbornyl group, adamantyl group, tetracyclo [4.4.0.1 ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group.

  Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-substituted alkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, and a 2-cyclohexylethyl group (for example, a C _3-20 cyclohexane). Alkyl-substituted C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to 4 units). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

  The hydrocarbon group may be any of various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group] Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] It may be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

The heterocyclic ring constituting the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 5-membered ring such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, a γ-butyrolactone ring; 4-oxo-4H; -6-membered ring such as pyran ring, tetrahydropyran ring, morpholine ring; condensed ring such as benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring; 3-oxatricyclo [4. 3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring or other bridged ring), sulfur as a hetero atom Heterocycles containing atoms (eg, 5-membered rings such as thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring; 6-membered ring such as 4-oxo-4H-thiopyran ring; A condensed ring such as a thiophene ring), a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, etc .; a pyridine ring, a pyridazine ring, a pyrimidine ring, 6-membered rings such as pyrazine ring, piperidine ring, piperazine ring; condensed rings such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, and purine ring). In addition to the substituents that the hydrocarbon group may have, the heterocyclic group includes an alkyl group (eg, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group You may have substituents, such as groups (for example, a phenyl group, a naphthyl group, etc.).

Y represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond ( -OCOO-) and a group in which a plurality of these are linked. Examples of the divalent hydrocarbon group include the same examples as in R ^c in the formula (a).

  The linear polymer (B) of the present invention contains a polymerizable monomer corresponding to the monomer unit containing the carbazole skeleton (for example, N-vinylcarbazole, N-acryloylcarbazole, N- (vinylbenzyl) carbazole, etc.). It can be obtained by polymerizing. The polymerization method is not particularly limited, and known methods such as solution polymerization and melt polymerization can be employed.

  Further, the linear polymer (B) of the present invention is a copolymer having another monomer unit in addition to the monomer unit containing the carbazole skeleton (for example, a graft copolymer, a block copolymer, a random copolymer). And the like. The copolymer can be produced by polymerizing a polymerizable monomer corresponding to the monomer unit containing the carbazole skeleton and a polymerizable monomer corresponding to another monomer unit.

Examples of the polymerizable monomer corresponding to the other monomer unit include olefins [for example, chain olefins such as ethylene, propylene and 1-butene (particularly C _2-12 alkene); cyclopentene, cyclohexene, cycloheptene and norbornene. , Cyclic olefins such as 5-methyl-2-norbornene and tetracyclododecene], aromatic vinyl compounds (for example, styrene, vinyltoluene, α-methylstyrene, 1-propenylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene) C _6-14 aromatic vinyl compounds such as 3-vinylpyridine, 3-vinylfuran, 3-vinylthiophene, 3-vinylquinoline), (meth) acrylic acid esters (for example, ethyl acrylate, butyl acrylate, acrylic Isobutyl acid, t-butyl acrylate, acrylic acid 2 Acrylic acid C _1-10 alkyl esters of cyclohexyl, etc., to ethyl, and methacrylic acid esters corresponding to these), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl caprylate, C _1-16 vinyl caproate, etc. Fatty acid vinyl ester, etc.), maleic acid ester or fumarate ester (eg, maleic acid di-C _1-10 alkyl ester such as diethyl maleate, dibutyl maleate, dioctyl maleate, di (2-ethylhexyl) maleate), And fumaric acid esters corresponding to these), carboxyl group-containing monomers (for example, monocarboxylic acids such as (meth) acrylic acid and itaconic acid; polyvalent carboxylic acids such as maleic anhydride, maleic acid and fumaric acid, or The acid anhydride; monoalkyl ester of the polyvalent carboxylic acid (for example, methyl ester) Le, ethyl ester, propyl ester, butyl ester, hexyl ester, octyl ester, C _1-16 alkyl esters such as lauryl), indene (e.g., indene, methyl indene, ethyl indene, alkyl indene such as dimethyl indene; chloro Indene, halogenated indene such as bromoindene, etc.), etc. These can be used alone or in combination of two or more.

  In the present invention, at least one polymerizable monomer selected from aromatic vinyl compounds (particularly styrenes) and indenes is particularly preferable in that a cured product having a high refractive index can be formed at low cost. It is preferable to have monomer units derived from the body.

  The proportion of monomer units containing a carbazole skeleton in the total monomer units constituting the linear polymer (B) is, for example, 30% by weight or more, preferably 30 to 95% by weight, particularly preferably 50 to 90% by weight. is there. A linear polymer containing a monomer unit containing a carbazole skeleton in the above range is preferable in that it has excellent solubility in the compound (A). On the other hand, when the ratio of the monomer unit containing a carbazole skeleton is less than the above range, the obtained cured product tends to become cloudy.

  The weight average molecular weight of the linear polymer (B) is preferably about 500 to 1,000,000, particularly preferably 3,000 to 500,000, from the viewpoint of excellent compatibility with the compound (A). In addition, the said weight average molecular weight is computable from the molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC), for example. When the weight average molecular weight of the linear polymer (B) is out of the above range, it is difficult to form a resin composition having a desired viscosity and curing shrinkage rate while maintaining a high refractive index of the obtained cured product. Tend to be.

  As the linear polymer (B) of the present invention, trade names “PVCZ 8K”, “PVCZ” (above, poly-N-vinylcarbazole, manufactured by Maruzen Petrochemical Co., Ltd.), “P0656” (poly-N -You may use commercial items, such as vinyl carbazole and Tokyo Chemical Industry Co., Ltd.).

  A linear polymer (B) can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the linear polymer (B) in the total amount (100% by weight) of the resin composition of the present invention is, for example, about 1 to 70% by weight. Can do. For example, when the resin composition of the present invention is used as a lens material or a liquid sealing material, the viscosity of the resin composition is preferably moderately low, and the content of the linear polymer (B) is 1 to 50. % By weight is preferable, particularly preferably 1 to 30% by weight, most preferably 1% by weight or more and less than 30% by weight. Moreover, when forming the curable resin film which can be used as a film-form sealing material from the resin composition of this invention, it is preferable that the viscosity of a resin composition is moderately high, and a linear polymer (B) The content is preferably 30 to 70% by weight. When the content of the linear polymer (B) is out of the above range, it becomes difficult to form a resin composition having a desired viscosity and curing shrinkage rate while maintaining a high refractive index of the obtained cured product. Tend.

  By adjusting the weight average molecular weight and content of the linear polymer (B) within the above range, a resin composition having a desired viscosity and curing shrinkage is formed while maintaining the refractive index of the resulting cured product high. can do. For example, when a small amount of the linear polymer (B) having a small weight average molecular weight is contained, a low-viscosity resin composition can be obtained. On the other hand, when a large amount of the linear polymer (B) having a large weight average molecular weight is contained, a highly viscous resin composition can be obtained.

  Since the resin composition of the present invention contains the linear polymer (B) as an essential component in addition to the compound (A), the desired viscosity and curing shrinkage can be maintained while maintaining a high refractive index of the resulting cured product. Rate can be granted.

[Polymerization initiator (C)]
It does not specifically limit as a polymerization initiator (C) which comprises the resin composition of this invention, A well-known and usual polymerization initiator can be used. Specifically, as the polymerization initiator (C), a photocationic polymerization initiator or a thermal cationic polymerization initiator, or a photoradical polymerization initiator or a thermal radical polymerization initiator can be preferably used. In addition, a polymerization initiator (C) can be used individually by 1 type or in combination of 2 or more types.

(Photocationic polymerization initiator)
The cationic photopolymerization initiator is a cationic photopolymerization initiator that generates a cationic species by light irradiation and initiates a curing reaction of the cationically curable compound. The cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.

  Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.

  Among these, the use of a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed. Examples of the cation moiety of the sulfonium salt compound include aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion. Examples include sulfonium ions (particularly triarylsulfonium ions).

Examples of the anion part of the cationic photopolymerization initiator include BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , [(Rf) _k PF _6−k ] ⁻ (Rf: 80% of hydrogen atoms) The above is an alkyl group substituted with a fluorine atom, k: an integer of 1 to 5, and AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ^{− and the} like.

  Examples of the photocationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4 -Biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, trade names "Syracure UVI-6970", "Syracure UVI-6974", "Syracure U “I-6990”, “Syracure UVI-950” (manufactured by Union Carbide, USA), “Irgacure 250”, “Irgacure 261”, “Irgacure 264” (above, BASF), “Adekaoptomer SP-150” "Adekaoptomer SP-151", "Adekaoptomer SP-170", "Adekaoptomer SP-171" (manufactured by ADEKA Corporation), "CG-24-61" (manufactured by BASF) “DAICAT II” (manufactured by Daicel Corporation), “UVAC1590”, “UVAC1591” (manufactured by Daicel-Cytec Inc.), “CI-2064”, “CI-2623”, “CI-2624”, “CI-2481”, “CI-2734”, “CI-2855”, “CI-2823”, “CI-2758”, “ “IT-1682” (manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, tetrakis (pentafluorophenylborate) tolylcumyl iodonium salt), “FFC509” (manufactured by 3M), “BBI” -102 "," BBI-101 "," BBI-103 "," MPI-103 "," TPS-103 "," MDS-103 "," DTS-103 "," NAT-103 "," NDS-103 " (Above, manufactured by Midori Chemical Co., Ltd.), “CD-1010”, “CD-1011”, “CD-1012” (manufactured by Sartomer, USA), “CPI-100P”, “CPI-101A” (above Commercial products such as San Apro Co., Ltd.) can be used.

(Thermal cationic polymerization initiator)
The thermal cationic polymerization initiator is a compound that generates a cationic species by heating and initiates the curing reaction of the cationic polymerizable compound. For example, trade names “Sun-Aid SI-45”, “Sun-Aid SI-47”, “Sun-Aid SI” are used. -60 "," Sun-Aid SI-60L "," Sun-Aid SI-80 "," Sun-Aid SI-80L "," Sun-Aid SI-100 "," Sun-Aid SI-100L "," Sun-Aid SI-110L "," Sun-Aid SI- " 145 "," Sun-Aid SI-150 "," Sun-Aid SI-160 "," Sun-Aid SI-180L "(product of Sanshin Chemical Industry Co., Ltd.)," CI-2921 "," CI-2920 "," CI " -2946 "," CI-3128 "," CI-2624 "," CI-2039 "," CI-2064 "( (Manufactured by Soda Co., Ltd.), “PP-33”, “CP-66”, “CP-77” (above, manufactured by ADEKA Corporation), “FC-509”, “FC-520” (above, Diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts and the like typified by 3M) can be used. Furthermore, a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S The compound with phenols, such as these, may be sufficient.

  The light or thermal cationic polymerization initiator can be used alone or in combination of two or more, and the amount used (blending amount) is 0. 0% in the resin composition (100% by weight) of the present invention. 01 to 15% by weight is preferable, more preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, and most preferably 0.1 to 3% by weight. Moreover, 0.01-15 weight part is preferable with respect to 100 weight part of polymeric compounds contained in the resin composition of this invention, More preferably, it is 0.01-10 weight part, Especially preferably, 0.05- 5 parts by weight, most preferably 0.1 to 3 parts by weight.

(Curing accelerator)
The resin composition of the present invention may contain a curing accelerator. The curing accelerator is a compound having a function of accelerating the curing rate when the polymerizable compound in the resin composition of the present invention is cured by light or a thermal cationic polymerization initiator. Diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), and salts thereof (eg, phenol salt, octylate, p-toluene) Sulfonates, formates, tetraphenylborate salts); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl-4 -Imidazoles such as methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters, triphenylphosphine, etc. Phosphines; include the metal chelates; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, tin octylate, organic metal salts such as zinc octylate. These can be used alone or in combination of two or more.

  Examples of the curing accelerator include trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “12XD” (developed product) ), “TPP-K”, “TPP-MK” (above, manufactured by Hokuko Chemical Co., Ltd.), “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.), etc. be able to.

  The content (blending amount) of the curing accelerator in the resin composition (100% by weight) of the present invention is not particularly limited, but is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, Particularly preferred is 0.2 to 3% by weight, and most preferred is 0.25 to 2.5% by weight. If the content of the curing accelerator is below the above range, the curing acceleration effect may be insufficient. On the other hand, when content of a hardening accelerator exceeds the said range, hardened | cured material may color and a hue may deteriorate.

(Photo radical polymerization initiator)
Examples of the photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, Orthobenzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name) “Kayacure DETX”, etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Gaigi Co., Ltd., trade name “Irgacure 907”, etc.), 2-dimethylamino -2 2-Amino-2-benzoyl-1-phenylalkane compounds such as (4-morpholino) benzoyl-1-phenylpropane, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1- Aminobenzene derivatives such as phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2 ′ -Imidazole compounds such as biimidazole (trade name "B-CIM" manufactured by Hodogaya Chemical Co., Ltd.), 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl)- Halomethylated triazine compounds such as 1,3,5-triazine, 2-trichloromethyl-5- (2-benzofuran-2-yl-ethenyl)- , It may be mentioned 3,4-oxadiazol-halomethyl oxadiazole compounds such like. These can be used alone or in combination of two or more. Examples of the photo radical polymerization initiator include a combination of an imidazole compound and an aminobenzene derivative, a 2-amino-2-benzoyl-1-phenylalkane compound, a halomethylated triazine compound, a halomethyl oxa compound from the viewpoints of sensitivity and chemical resistance. Diazole compounds are preferred. Moreover, a photosensitizer can be added to the resin composition of this invention as needed.

(Thermal radical polymerization initiator)
As said thermal radical polymerization initiator, organic peroxides can be mentioned, for example. Examples of the organic peroxides that can be used include dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, and peroxyesters. Specific examples of the organic peroxide include benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t -Butyl peroxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichloro Benzoyl peroxide, di-t-butylperoxydi-isopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate, etc. .

  Furthermore, together with the thermal radical polymerization initiator, naphthenic acid such as cobalt naphthenate, manganese naphthenate, zinc naphthenate, cobalt octenoate and the like, and metal salts such as cobalt octenoic acid, manganese, lead, zinc, vanadium, etc. Can do. Similarly, tertiary amines such as dimethylaniline can be used.

  The above-mentioned light or thermal radical polymerization initiator can be used alone or in combination of two or more, and the amount used (blending amount) is the resin composition (100% by weight) of the present invention. 0.01 to 5 wt% is preferable, and 0.1 to 3 wt% is more preferable. Moreover, 0.01-5 weight part is preferable with respect to 100 weight part of polymeric compounds contained in the resin composition of this invention, More preferably, it is 0.1-3 weight part.

[Inorganic filler]
The resin composition of the present invention may further contain an inorganic filler. As the inorganic filler, it is preferable to use a filler that does not block visible light. For example, silica (nanosilica etc.), alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide (nanozirconia etc.), oxidation Titanium (nano titania, etc.), barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fiber, graphite, carbon nanotube, hydroxylation Calcium, magnesium hydroxide, aluminum hydroxide, cellulose and the like can be mentioned. These can be used alone or in combination of two or more.

The said inorganic filler can be manufactured by well-known methods, such as the flame hydrolysis method described in the international publication 96/31572, a flame pyrolysis method, a plasma method, for example. As a preferred inorganic filler, nano colloidal sols of stabilized colloidal inorganic particles can be used, such as a silica sol manufactured by BAYER, SnO ₂ sol manufactured by Goldschmidt, a TiO ₂ sol manufactured by MERCK, and Nissan Chemicals. Commercially available products such as SiO ₂ sol, ZrO ₂ sol, Al ₂ O ₃ sol, and Sb ₂ O ₃ sol manufactured by the company, and SiO ₂ dispersion (trade name “Aerosil”) manufactured by DEGUSSA are available.

  The inorganic filler can change its viscosity behavior by modifying its surface. The surface modification of the inorganic filler can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the inorganic filler such as a covalent bond or complex formation, or a compound capable of interacting with a polymer matrix may be used. it can. Examples of such surface modifiers include carboxyl groups, (primary, secondary, and tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, ( A compound having a functional group such as a (meth) acryloxy group or a mercapto group can be used. As such a surface modifier, it is usually a liquid under standard temperature and pressure conditions, and a low molecular weight molecule having a carbon number in the molecule of 15 or less (more preferably 10 or less, more preferably 8 or less). Surface modifiers composed of organic compounds are preferred. The molecular weight of the low molecular weight organic compound is not particularly limited, but is preferably 500 or less, more preferably 350 or less, and still more preferably 200 or less.

Examples of the surface modifier include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid and maleic acid. C _1-12 saturated or unsaturated mono- and polycarboxylic acids (preferably monocarboxylic acids) such as acids and fumaric acids; and esters thereof (preferably C _1-4 alkyl esters such as methyl methacrylate); Amides; acetylacetone, 2,4-hexanedione, 3,5-heptanedione, β-dicarbonyl compounds such as acetoacetic acid and C _1-4 alkylacetoacetic acids, silane coupling agents, and the like.

  The particle size of the inorganic filler is, for example, about 0.01 nm to 1 μm.

  The content (blending amount) of the inorganic filler is, for example, about 1 to 2000 parts by weight with respect to 100 parts by weight of the total amount (total content) of the compound (A) and the linear polymer (B) in the resin composition. is there. Moreover, content of the inorganic filler in resin composition whole quantity (100 weight%) is about 5-95 weight%, for example.

[Silane coupling agent]
The resin composition of the present invention may further contain a silane coupling agent in order to improve adhesion to an adherend such as a substrate. Examples of silane coupling agents include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxysilane), and phenyl. Trimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ -(Meth) acryloxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Liethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N- (β -Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxy Silane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3, such as isocyanate propyl triethoxysilane, can be suitably selected from relatively stable ones in aqueous solution.

  The content (blending amount) of the silane coupling agent in the resin composition (100% by weight) of the present invention is, for example, about 0.1 to 20% by weight.

[Other additives]
The resin composition of the present invention may further include, for example, a polymerizable compound (excluding the compound (A)), a polymerization inhibitor, an antioxidant, a light stabilizer, a plasticizer, a leveling agent, and an antifoaming agent as necessary. In addition, conventional additives such as pigments, organic solvents, ultraviolet absorbers, ion adsorbers, phosphors, and release agents may be contained. The resin composition of the present invention may contain other polymerizable compounds (for example, epoxy compounds, acrylic compounds, olefin compounds, etc.) in addition to the compound (A). The proportion of the compound (A) in the total polymerizable compound contained in is, for example, 50% by weight or more, preferably 70% by weight or more.

  In addition, when the cured product obtained by curing the resin composition of the present invention is required to have conductivity, the resin composition of the present invention preferably contains a conductive material in addition to the above components. It is preferable that the following conductive fiber-coated particles are contained in that a cured product having both conductivity and transparency can be obtained.

(Conductive fiber coated particles)
The conductive fiber-coated particles include a particulate material and a fibrous conductive material that covers the particulate material (sometimes referred to herein as “conductive fibers”). In the conductive fiber-coated particles, “cover” means a state in which the conductive fibers cover part or all of the surface of the particulate matter. In the conductive fiber-coated particles, it is only necessary that the conductive fibers cover at least a part of the surface of the particulate matter. For example, even if there are more uncoated portions than coated portions. Good. In the conductive fiber-coated particles, the particulate matter and the conductive fiber are not necessarily in contact with each other, but usually a part of the conductive fiber is in contact with the surface of the particulate matter.

  FIG. 1 is an example of a scanning electron microscope image of conductive fiber-coated particles. As shown in FIG. 1, the conductive fiber-coated particles have a configuration in which at least a part of the particulate matter (the true spherical substance in FIG. 1) is covered with the conductive fiber (the fibrous substance in FIG. 1). .

(Particulate matter)
The particulate matter constituting the conductive fiber-coated particles is a particulate structure.

  The material (raw material) constituting the particulate matter is not particularly limited, and examples thereof include known or commonly used materials such as metal, plastic, rubber, ceramic, glass, and silica. In the present invention, it is particularly preferable to use a transparent material such as transparent plastic, glass, and silica, and it is particularly preferable to use a transparent plastic.

  The transparent plastic includes a thermosetting resin and a thermoplastic resin. Examples of the thermosetting resin include poly (meth) acrylate resin; polystyrene resin; polycarbonate resin; polyester resin; polyurethane resin; epoxy resin; polysulfone resin; amorphous polyolefin resin; divinylbenzene, hexatriene, divinyl ether, Divinyl sulfone, diallyl carbinol, alkylene diacrylate, oligo or polyalkylene glycol diacrylate, oligo or polyalkylene glycol dimethacrylate, alkylene triacrylate, alkylene tetraacrylate, alkylene trimethacrylate, alkylene tetramethacrylate, alkylene bisacrylamide, alkylene bismethacryl Multifunctional monomers such as amide and polybutadiene oligomer modified with both ends Polymerized in Germany, or other monomers copolymerized allowed to network polymer obtained; phenol formaldehyde resins, melamine formaldehyde resins, benzoguanamine-formaldehyde resins, and urea-formaldehyde resins. Examples of the thermoplastic resin include ethylene / vinyl acetate copolymer, ethylene / vinyl acetate / unsaturated carboxylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, and ethylene / acrylic acid. Copolymer, ethylene / methacrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / aminoalkyl methacrylate copolymer, ethylene / vinyl silane copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / hydroxyethyl methacrylate Examples include copolymers, methyl (meth) acrylate / styrene copolymers, acrylonitrile / styrene copolymers, and the like.

  The shape of the particulate material is not particularly limited. For example, it is spherical (true sphere, approximately true sphere, elliptical sphere, etc.), polyhedron, rod (column, prism, etc.), flat plate, flake shape, indefinite Examples include shape. In the present invention, in particular, the conductive fiber-coated particles can be produced with high productivity, can be easily dispersed uniformly in the resin composition, and can easily impart conductivity to the entire cured product. Is preferable, and a spherical shape is particularly preferable.

  The average particle size of the particulate material is not particularly limited, but is preferably 0.1 to 100 μm, particularly preferably 1 to 50 μm, and most preferably 5 to 30 μm. When the average particle diameter is below the above range, it may be difficult to develop excellent conductivity by blending a small amount of conductive fiber-coated particles. When the average particle diameter exceeds the above range, the average particle diameter becomes larger than the thickness of the sealing layer of the organic EL element, and it tends to be difficult to form a coating film having a uniform thickness. In addition, the average particle diameter of the particulate matter is a median diameter (d50) by a laser diffraction / scattering method.

  The particulate material is preferably transparent. Specifically, the total light transmittance (wavelength: 450 nm) in the visible light wavelength region of the particulate matter is not particularly limited, but is preferably 70% or more, and particularly preferably 75% or more. When the total light transmittance is below the above range, the transparency of the cured product containing the conductive fiber-coated particles may be lowered. In addition, the total light transmittance in the visible light wavelength region of the particulate matter is obtained by polymerizing the monomer as a raw material of the particulate matter in a temperature region of 80 to 150 ° C. between glasses to obtain a flat plate having a thickness of 1 mm, It is a value obtained by measuring the total light transmittance in the visible light wavelength region of the flat plate in accordance with JIS K7361-1, wherein the value obtained by measuring the glass is 100% and is calculated as a blank. is there.

The particulate matter preferably has flexibility, and the 10% compressive strength of each particle is, for example, 10 kgf / mm ² or less, preferably 5 kgf / mm ² or less, particularly preferably 3 kgf / mm ² or less. The conductive fiber-coated particles containing particulate matter having a 10% compressive strength in the above range can be deformed following a fine concavo-convex structure by applying pressure. Therefore, when the resin composition containing the conductive fiber-coated particles is cured into a shape having a fine concavo-convex structure, the particulate matter can be distributed in detail, and a portion where the conductivity is poor is generated. Can be prevented.

  The refractive index of the particulate material is not particularly limited, but is preferably 1.4 to 2.7, and particularly preferably 1.5 to 1.8. The refractive index of the particulate matter is such that when the particulate matter is a plastic particle, the monomer that is the raw material of the particulate matter is polymerized in a temperature range of 80 to 150 ° C. between glasses, and the length is 20 mm × width A 6 mm test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. Can be obtained by measuring the refractive index at 25 ° C. and sodium D line.

The particulate matter preferably has a small difference in refractive index (at 25 ° C., wavelength 589.3 nm) from the cured product of the resin composition, and the particulate matter and the resin composition constituting the conductive fiber-coated particles The absolute value of the refractive index difference of the cured product is, for example, 0.1 or less (preferably 0.05 or less, particularly preferably 0.02 or less).
That is, it is preferable that the resin composition of the present invention and the particulate matter constituting the conductive fiber-coated particles satisfy the following formula.
| Refractive index of particulate matter-refractive index of cured product of resin composition | ≦ 0.1

  By making the refractive index difference between the particulate matter constituting the conductive fiber-coated particles and the cured product of the resin composition in the above range, the transparency is excellent and the haze is, for example, 10% or less (preferably 6% or less, more preferably 3% or less), and a cured product having a total light transmittance of 90% or more (preferably 93% or more) can be obtained. In addition, the haze of the hardened | cured material of this invention can be measured based on JISK7136. Further, the total light transmittance (thickness: 10 μm, wavelength: 450 nm) in the visible light wavelength region of the cured product of the present invention is in accordance with JIS K7361-1, as in the method for measuring the total light transmittance of the particulate matter. It can be measured in compliance.

  Furthermore, the particulate matter constituting the conductive fiber-coated particles has a sharp particle size distribution (= small variation in particle diameter), and can provide excellent conductivity with a smaller amount of use. The coefficient of variation (CV value) is preferably 50 or less. The coefficient of variation is a value obtained by dividing the standard deviation by the average particle diameter, and is a value that serves as an index of particle size uniformity.

  The particulate matter can be produced by a known or conventional method, and the production method is not particularly limited. For example, in the case of metal particles, it can be produced by a vapor phase method such as a CVD method or a spray pyrolysis method, or a wet method using a chemical reduction reaction. In the case of plastic particles, for example, the monomer constituting the resin (polymer) exemplified above is polymerized by a known method such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. Can be manufactured.

  In the present invention, commercially available products can also be used. Examples of particulate substances made of thermosetting resins include trade names “Techpolymer MBX series”, “Techpolymer BMX series”, “Techpolymer ABX series”, “Techpolymer ARX series”, and “Techpolymer AFX series”. (Sekisui Plastics Industry Co., Ltd.), trade names "Micropearl SP", "Micropearl SI" (Sekisui Chemical Co., Ltd.); The trade name “Soft Bead” (manufactured by Sumitomo Seika Co., Ltd.), the trade name “Duo Master” (manufactured by Sekisui Plastics Co., Ltd.), and the like can be used.

(Fibrous conductive material (conductive fiber))
The conductive fibers constituting the conductive fiber-coated particles are conductive fibrous structures (linear structures). The shape of the conductive fiber is not particularly limited as long as it is fibrous (fibrous), but the average aspect ratio is preferably 10 or more (for example, 20 to 5000), particularly preferably 50 to 3000, and most preferably. Is 100-1000. When the average aspect ratio is less than the above range, it may be difficult to develop excellent conductivity by blending a small amount of conductive fiber-coated particles. The average aspect ratio of the conductive fibers is a sufficient number (for example, 100 or more, preferably 300 or more; in particular, 100 or 300) of conductive fibers using an electron microscope (SEM, TEM). It is calculated | required by image | photographing an electron microscope image, measuring the aspect-ratio of these conductive fibers, and carrying out arithmetic average. Note that the concept of “fibrous” in the conductive fibers includes shapes of various linear structures such as “wire” and “rod”. In the present specification, fibers having an average thickness of 1000 nm or less may be referred to as “nanowires”.

  The average thickness (average diameter) of the conductive fibers is not particularly limited, but is preferably 1 to 400 nm, particularly preferably 10 to 200 nm, and most preferably 50 to 150 nm. When the average thickness is less than the above range, the conductive fibers are likely to aggregate and it may be difficult to produce the conductive fiber-coated particles. On the other hand, if the average thickness exceeds the above range, it may be difficult to coat the particulate matter, and it may be difficult to obtain conductive fiber-coated particles efficiently. The average thickness of the conductive fibers is about a sufficient number (for example, 100 or more, preferably 300 or more; in particular, 100 or 300) of conductive fibers using an electron microscope (SEM, TEM). It is calculated | required by image | photographing an electron microscope image, measuring the thickness (diameter) of these conductive fibers, and carrying out arithmetic average.

Although the average length of the said conductive fiber is not specifically limited, 1-100 micrometers is preferable, Especially preferably, it is 5-80 micrometers, Most preferably, it is 10-50 micrometers. If the average length is less than the above range, it may be difficult to coat the particulate matter, and it may not be possible to obtain conductive fiber-coated particles efficiently. On the other hand, when the average length exceeds the above range, the conductive fibers are easily entangled. The average length of the conductive fibers is about a sufficient number (for example, 100 or more, preferably 300 or more; in particular, 100 or 300) of conductive fibers using an electron microscope (SEM, TEM). It is calculated | required by image | photographing an electron microscope image, measuring the length of these electroconductive fibers, and carrying out arithmetic average. Note that the length of the conductive fiber should be measured in a linearly stretched state, but in reality it is often bent so that the conductive fiber can be measured using an image analyzer from an electron microscope image. The projected diameter and projected area are calculated and calculated from the following equation assuming a cylindrical body.
Length = projected area / projected diameter

  The material (raw material) constituting the conductive fiber may be a conductive material, and examples thereof include metals, semiconductors, carbon materials, and conductive polymers.

  Examples of the metal include known or commonly used metals such as gold, silver, copper, iron, nickel, cobalt, tin, and alloys thereof. In the present invention, silver is particularly preferable in terms of excellent conductivity.

  Examples of the semiconductor include known or commonly used semiconductors such as cadmium sulfide and cadmium selenide.

  Examples of the carbon material include known or conventional carbon materials such as carbon fibers and carbon nanotubes.

  Examples of the conductive polymer include polyacetylene, polyacene, polyparaphenylene, polyparaphenylene vinylene, polypyrrole, polyaniline, polythiophene, and derivatives thereof (for example, an alkyl group, a hydroxyl group, a carboxyl group, a common polymer skeleton, And those having a substituent such as ethylenedioxy group; specifically, polyethylenedioxythiophene and the like). In the present invention, polyacetylene, polyaniline and derivatives thereof, polypyrrole and derivatives thereof, polythiophene and derivatives thereof are particularly preferable. The conductive polymer may contain a known or commonly used dopant (for example, an acceptor such as a halogen, a halide or a Lewis acid; a donor such as an alkali metal or an alkaline earth metal).

  The conductive fiber of the present invention is preferably a conductive nanowire, in particular, at least one conductive nanowire selected from the group consisting of metal nanowires, semiconductor nanowires, carbon fibers, carbon nanotubes, and conductive polymer nanowires, In particular, silver nanowires are most preferable in terms of excellent conductivity.

  The conductive fiber can be produced by a known or conventional production method. For example, the metal nanowire can be manufactured by a liquid phase method, a gas phase method, or the like. More specifically, silver nanowires are described in, for example, Mater. Chem. Phys. 2009, 114, p333-338, Adv. Mater. 2002, 14, p833-837, Chem. Mater. 2002, 14, p4736-4745, and the method described in JP-T-2009-505358. In addition, the gold nanowire can be manufactured, for example, by the method described in JP-A-2006-233252. Moreover, a copper nanowire can be manufactured by the method as described in Unexamined-Japanese-Patent No. 2002-266007, for example. Moreover, cobalt nanowire can be manufactured by the method as described in Unexamined-Japanese-Patent No. 2004-148771, for example. Furthermore, a semiconductor nanowire can be manufactured by the method as described in Unexamined-Japanese-Patent No. 2010-208925, for example. The carbon fiber can be produced, for example, by the method described in JP-A-06-081223. The carbon nanotube can be produced, for example, by the method described in JP-A-06-157016. The said conductive polymer nanowire can be manufactured by the method of Unexamined-Japanese-Patent No. 2006-241334, Unexamined-Japanese-Patent No. 2010-76044, for example. A commercial item can also be used as the conductive fiber.

The conductive fiber-coated particles can be produced by mixing the above-mentioned particulate material and conductive fibers in a solvent. Specific examples of the method for producing conductive fiber-coated particles include the following methods (1) to (4).
(1) Mixing a dispersion in which the particulate matter is dispersed in a solvent (referred to as “particle dispersion”) and a dispersion in which the conductive fibers are dispersed in a solvent (referred to as “fiber dispersion”). Then, if necessary, the solvent is removed to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
(2) After blending and mixing the conductive fibers in the particle dispersion, the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
(3) After mixing and mixing the particulate matter in the fiber dispersion, the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
(4) After mixing and mixing the particulate matter and the conductive fibers in a solvent, the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles). obtain.

  Examples of the solvent used in producing the conductive fiber-coated particles include water; alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; benzene, toluene, and xylene. Aromatic ethers such as ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide And nitriles such as acetonitrile, propionitrile, and benzonitrile. These can be used individually by 1 type or in combination of 2 or more types (that is, as a mixed solvent). In the present invention, alcohol and ketone are particularly preferable.

  Moreover, if the said resin composition is liquid, this can also be used as said solvent. By using a liquid resin composition as a solvent, the step of removing the solvent can be omitted.

  Although the viscosity of the solvent is not particularly limited, the viscosity at 25 ° C. is preferably 10 cP or less (for example, 0.1 to 10 cP) in that the conductive fiber-coated particles can be efficiently produced, Particularly preferred is 0.5 to 5 cP. The viscosity of the solvent at 25 ° C. can be measured using, for example, an E-type viscometer (trade name “VISCONIC”, manufactured by Tokimec Co., Ltd.) (rotor: 1 ° 34 ′ × R24, rotation speed: 0.5 rpm, measurement temperature: 25 ° C.).

  The boiling point of the solvent at 1 atm is preferably 200 ° C. or less, particularly preferably 150 ° C. or less, and most preferably 120 ° C. or less, from the viewpoint that the conductive fiber-coated particles can be efficiently produced.

  The content of the particulate matter when mixing the particulate matter and the conductive fiber in the solvent is, for example, about 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solvent. It is. By controlling the content of the particulate matter within the above range, the conductive fiber-coated particles can be generated more efficiently.

  The content of the conductive fiber when mixing the particulate matter and the conductive fiber in the solvent is, for example, about 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solvent. It is. By controlling the content of the conductive fiber within the above range, the conductive fiber-coated particles can be generated more efficiently.

  The ratio of the particulate matter and the conductive fiber when mixing the particulate matter and the conductive fiber in the solvent is the ratio of the surface area of the particulate matter to the projected area of the conductive fiber [surface area / projected area]. However, it is preferable that the ratio is, for example, about 100/1 to 100/100, preferably 100/10 to 100/50. By mixing in the above range, the conductive fiber-coated particles can be generated more efficiently. In addition, the surface area of the said particulate matter is calculated | required by the method of multiplying the specific surface area calculated | required by BET method (based on JISZ8830) by the mass (usage amount) of a particulate matter. Further, as described above, the projected area of the conductive fibers is a sufficient number (for example, 100 or more, preferably 300 or more; particularly 100 or 300, using an electron microscope (SEM, TEM)). ) Is taken by taking an electron microscope image, calculating the projected area of these conductive fibers using an image analyzer, and calculating the arithmetic mean.

  After mixing the particulate matter and the conductive fibers, the conductive fiber-coated particles can be obtained as a solid by removing the solvent. The removal of the solvent is not particularly limited, and can be performed by a known or conventional method such as heating, distillation under reduced pressure, or the like. The solvent is not necessarily removed, and can be used as it is, for example, as a dispersion of conductive fiber-coated particles.

  As described above, the conductive fiber-coated particles can be produced by mixing raw materials (particulate matter and conductive fibers) in a solvent, and do not require a complicated process. It is advantageous.

  In particular, as a combination of a particulate substance and conductive fibers, a particulate substance having an average particle diameter L [μm] and an average length L × 0.5 [μm] or more (preferably L × 1.0 [μm] or more, By using conductive fibers of L × 1.5 [μm] or more most preferably, conductive fiber-coated particles can be produced more efficiently. In particular, in the case of a spherical or substantially spherical particulate material, a particulate material having an average circumference M [μm] and an average length (M × 1/6) [μm] or more (preferably M [μm It is preferable to use the above-mentioned conductive fibers. The average perimeter of the particulate matter is a sufficient number of particles (for example, 100 or more, preferably 300 or more; in particular, 100 or 300, etc.) using an electron microscope (SEM, TEM). It is obtained by taking an electron microscopic image of the particulate matter, measuring the perimeter of these particulate matter, and calculating the arithmetic average.

  The ratio of the particulate matter and the conductive fiber constituting the conductive fiber-coated particle is such that the ratio of the surface area of the particulate matter to the projected area of the conductive fiber [surface area / projected area] is, for example, 100/1 to 100/100. It is preferable that the ratio is in a range (particularly 100/10 to 100/50) in that the conductivity can be imparted more efficiently while ensuring the transparency of the cured product. In addition, the surface area of the particulate matter and the projected area of the conductive fiber are determined by the above-described methods.

  Since the conductive fiber-coated particles have the above-described configuration, excellent conductivity (particularly, conductivity in the thickness direction) can be imparted by adding a small amount to the cured product, and the transparency and conductivity are excellent. A cured product can be formed.

And when conductive fiber covering particle | grains have a softness | flexibility (for example, when 10% compressive strength is 3 kgf / mm < ² > or less), the resin composition containing the said conductive fiber covering particle | grain is made into the shape which has a fine unevenness | corrugation. When molded, the conductive fiber-coated particles are deformed following the concavo-convex structure and spread to details, so that it is possible to prevent the occurrence of a portion with poor conductivity, and a cured product having excellent conductive performance. Can be formed.

  The content (mixing amount) of the particulate matter (particulate matter contained in the conductive fiber-coated fine particles) in the resin composition is, for example, about 0.09 to 6.0 parts by weight with respect to 100 parts by weight of the resin composition. , Preferably 0.1 to 4.0 parts by weight, more preferably 0.3 to 3.5 parts by weight, still more preferably 0.3 to 3.0 parts by weight, particularly preferably 0.3 to 2.5 parts by weight. Parts, most preferably 0.5 to 2.0 parts by weight. When content of the said particulate matter is less than the said range, depending on a use, the electroconductivity of the obtained hardened | cured material may become inadequate. On the other hand, if the content of the particulate matter exceeds the above range, the resulting cured product may have insufficient transparency depending on the application.

  The content of the particulate matter in the resin composition is, for example, about 0.02 to 7% by volume, preferably 0.1 to 5% by volume, particularly preferably relative to the total amount (100% by volume) of the resin composition. It is 0.3-3 volume%, Most preferably, it is 0.4-2 volume%.

  The conductive fiber content (blending amount) in the resin composition is, for example, about 0.01 to 1.0 part by weight, preferably 0.02 to 0.8 part by weight, with respect to 100 parts by weight of the resin composition. More preferably, it is 0.03-0.6 weight part, Especially preferably, it is 0.03-0.4 weight part, Most preferably, it is 0.03-0.2 weight part. When content of the said conductive fiber is less than the said range, depending on a use, the electroconductivity of the obtained hardened | cured material may become inadequate. On the other hand, when the content of the conductive fiber exceeds the above range, the transparency of the obtained cured product may be insufficient depending on the application.

  The content of the conductive fiber in the resin composition is preferably 0.01 to 1.1% by volume, more preferably 0.02 to 0.9% by volume with respect to the total amount (100% by volume) of the resin composition. %, Particularly preferably 0.03 to 0.7% by volume, most preferably 0.03 to 0.4% by volume.

<Resin composition and production method thereof>
The resin composition of the present invention comprises the above-mentioned compound (A), linear polymer (B), polymerization initiator (C), and other components as necessary (inorganic filler, silane coupling agent, conductive material). Etc.) can be produced by mixing uniformly. In obtaining the resin composition of the present invention, each component is made as uniform as possible by using generally known mixing equipment such as a revolving and stirring agitation / deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, and the like. Each component may be mixed simultaneously or sequentially.

  The resin composition of the present invention has a viscosity at 25 ° C. of, for example, 15 to 1,000,000 mPa · s (preferably 15 to 100,000 mPa · s, particularly, by appropriately adjusting the weight average molecular weight and the blending amount of the linear polymer (B). It can be arbitrarily controlled in the range of preferably 30 to 15000 mPa · s, most preferably 30 to 10000 mPa · s. Therefore, a resin composition having a viscosity corresponding to the use can be easily produced. The viscosity of the resin composition can be measured using an E-type viscometer or a rheometer.

Moreover, the resin composition of this invention can adjust a cure shrinkage arbitrarily in the range of 3-8%, for example by adjusting suitably the weight average molecular weight and compounding quantity of a linear polymer (B). . Therefore, it is possible to easily produce a resin composition having a curing shrinkage rate corresponding to the application. The cure shrinkage can be calculated from the following formula.
Curing shrinkage rate (%) = [(specific gravity of cured product−specific gravity of resin liquid before curing) / specific gravity of cured product] × 100

  Since the resin composition of the present invention contains the compound (A) having an action of trapping cations and suppressing the progress of cationic polymerization, when containing a photocationic polymerization initiator as a polymerization initiator (C), The curing reaction is not started only by generating cations by light irradiation, and then the curing can be started by performing a heat treatment to release the trapped cations. That is, it is possible to exhibit curing retardance. Therefore, when used as a sealing material for organic EL elements, a resin composition that has been pre-irradiated with light is applied to the organic EL element, and then subjected to heat treatment, whereby the organic material is exposed directly to light. The organic EL element can be sealed while preventing the deterioration of the EL element.

<Curable resin film>
The curable resin film of the present invention is obtained by molding the resin composition (particularly, a resin composition having a linear polymer (B) content of about 30 to 70% by weight) [for example, the resin composition is a solvent. And is applied onto a release paper or the like and dried (for example, dried at about 50 to 150 ° C. for about 1 to 10 minutes)]. In particular, when the resin composition contains a photocationic polymerization initiator as the polymerization initiator (C), a light irradiation step can be provided as necessary after the molding step.

  The curable resin film of the present invention is a curable resin obtained by forming a resin composition containing a photocationic polymerization initiator as a polymerization initiator (C) by performing light irradiation and / or heat treatment (for example, In the case of a film, a film-like cured product can be obtained by performing light irradiation and heat treatment.

  Since the resin composition of the present invention contains a compound (A) having an action of trapping cations and suppressing the progress of cationic polymerization, a curable resin containing a photocationic polymerization initiator as a polymerization initiator (C) The film does not start the curing reaction only by generating cations by light irradiation, and then heat-treats and releases the trapped cations to start and advance the curing, and then completely cure to form a cured film. Can be obtained. That is, it can exhibit delayed curability. Therefore, when used as a sealing material for organic EL elements, a curable resin film that has been pre-irradiated with light is applied to the organic EL elements, and then subjected to heat treatment, thereby being directly exposed to light. The organic EL element can be sealed while preventing the deterioration of the organic EL element.

  The thickness of the curable resin film of the present invention can be appropriately adjusted according to the application. For example, when used as a sealing sheet, it is, for example, about 0.1 to 100 μm (preferably 1 to 50 μm). . Moreover, the width | variety and length in the surface direction of the curable resin film of this invention are not restrict | limited in particular, It can adjust suitably according to a use.

  In the curable resin film of the present invention, a release liner may be bonded to the surface in order to protect the surface or prevent blocking. The release liner is peeled off when the curable resin film of the present invention is used.

  Examples of release liners include papers and plastic films (for example, polyesters such as polyethylene terephthalate, and olefins such as polyethylene and polypropylene) that have been surface-treated with a release agent such as silicone, long chain alkyl, fluorine, and molybdenum sulfide. Plastic film made of resin): polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer, etc. One type or two or more types of low-adhesive substrates made of a fluorine-based polymer can be used.

<Hardened product>
The resin composition or curable resin film of the present invention is subjected to light irradiation and / or heat treatment to obtain a cured product (a cured resin product or a cured resin product in the form of a film when the curable resin film is cured). Can do. When the resin composition or the curable resin film of the present invention is cured by light irradiation, for example, the resin composition or the curable resin film is irradiated with light of 1000 mJ / cm ² or more with a mercury lamp or the like. Can be cured. Moreover, when hardening the resin composition or curable resin film of this invention by heat processing, the said resin composition or curable resin film is 50-200 degreeC (preferably 50-170 degreeC, more preferably), for example. More preferably, it can be cured by heating at 50 to 150 ° C. for 10 to 600 minutes (more preferably 10 to 360 minutes, more preferably 15 to 180 minutes). When the heating temperature (curing temperature) or time (curing time) is below the above range, the resin composition or the curable resin film may be insufficiently cured. On the other hand, when the curing temperature or the curing time exceeds the above range, the resin component may be decomposed. The curing conditions of the resin composition or curable resin film of the present invention depend on various conditions, but when the curing temperature is high, the curing time is shortened, and when the curing temperature is low, the curing time is lengthened. Can be adjusted. A cured product having a high refractive index can be obtained by curing the resin composition or the curable resin film of the present invention.

  The refractive index of the cured product obtained by curing the resin composition or curable resin film of the present invention with respect to light (sodium D line) having a wavelength of 589.3 nm at 25 ° C. is, for example, 1.70 or more, preferably 1. 70 to 1.74, particularly preferably 1.71 to 1.74. In addition, the refractive index of hardened | cured material can be measured by the method based on JISK7142, or the method using a prism coupler, for example.

  The resin composition or curable resin film of the present invention forms a cured product having a curing shrinkage rate according to the application and a high refractive index. For this reason, for example, a lens (high refractive index lens), a liquid or film-like sealing material (organic EL element sealing material, LED sealing material, solar cell sealing material), various refractive index adjustment layers, light It can be preferably used as a take-out layer, a dark part laminating adhesive (adhesive, sealing material) and the like. In particular, when the resin composition or the curable resin film of the present invention is used as a sealing material in a process of manufacturing an electronic device such as an organic EL device, an LED device, or a solar cell, the sealing material and the high refractive index member The reflection of light at the interface can be suppressed, the light extraction efficiency can be improved, and an electronic device having high efficiency, high luminance, and long life can be obtained.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Synthesis example 1
Synthesis of linear polymer (b-4) [poly (styrene-N-vinylcarbazole)] Styrene (trade name “S0095”, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-vinylcarbazole (trade name “V0021”, Tokyo) 2 g each of Kasei Chemical Co., Ltd.) was weighed and heated and stirred at 80 ° C. for 10 minutes to obtain a monomer mixed solution.
The obtained monomer mixed solution is cooled to 25 ° C., and then 0.4 g of a thermal radical polymerization initiator (trade name “Perbutyl O”, manufactured by NOF Corporation) is added to prepare a mixed solution. The total amount of the solution was dropped into distilled water (40 g) being stirred in a three-necked flask at 95 ° C. under a nitrogen atmosphere, and a polymerization reaction was performed at 95 ° C. for 2 hours to obtain a polymer.
The obtained polymer was collected by filtration, pulverized in a mortar, and the unreacted monomer was washed with methanol and then vacuum-dried to obtain 2.4 g of a linear polymer (b-4). The copolymerization ratio (% by weight) of the linear polymer (b-4) was carbazole: styrene = 86: 14 from H ¹ -NMR. Moreover, the weight average molecular weight (MW) was 56500 from GPC.

Example 1
89 parts by weight of the compound (a-1), 10 parts by weight of the linear polymer (b-1), and 1 part by weight of the polymerization initiator (c-1) The resin composition (1) (viscosity at 25 ° C .: 48 mPa · s) was obtained. The viscosity of the resin composition was measured using an E-type viscometer.
The obtained resin composition (1) was poured into a mold, irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1600 mJ / cm ² ), and then heat-treated (100 ° C., 60 minutes) to give a cured product (1) (thickness: 100 μm).

Examples 2 to 11, Reference Example, Comparative Examples 1 to 4
A resin composition and a cured product were prepared in the same manner as in Example 1 except that the composition shown in the following table was changed.
The resin compositions obtained in Examples 9 and 10 and Comparative Examples 1 and 2 were cured by heating for 1 hour in a constant temperature air oven at 100 ° C.

<Measurement of refractive index>
About the obtained hardened | cured material (thickness: 100 micrometers), the refractive index of light of 589.3 nm was measured at 25 degreeC using Model 2010 prism coupler (made by Metricon company).

<Measurement of cure shrinkage>
The cure shrinkage when the resin composition was cured to form a cured product was calculated by the specific gravity method.

  From the above table, it can be seen that the resin compositions (Examples) of the present invention can arbitrarily control the curing shrinkage and viscosity within a wide range while maintaining a high refractive index of the cured product obtained by curing. . Therefore, the resin composition of the present invention can be suitably used for various applications such as electronic devices and lenses.

The compounds used in Examples and Comparative Examples are as follows.
[Compound (A)]
a-1: Bis (4-vinylthiophenyl) sulfide, molecular weight: 302, manufactured by Sumitomo Seika Co., Ltd., trade name “MPV”
[Linear polymer (B)]
b-1: Poly-N-vinylcarbazole, weight average molecular weight: 8500, manufactured by Maruzen Petrochemical Co., Ltd., trade name “PVCZ 8K”
b-2: Poly-N-vinylcarbazole, weight average molecular weight: 45000, manufactured by Maruzen Petrochemical Co., Ltd., trade name “PVCZ”
b-3: Poly-N-vinylcarbazole, weight average molecular weight: 400000, manufactured by Tokyo Chemical Industry Co., Ltd., trade name “P0656”
b-4: Poly (styrene-N-vinylcarbazole) obtained in Synthesis Example 1, weight average molecular weight: 56500
[Other polymerizable compounds]
d-1: Petroleum resin, manufactured by JX Nippon Oil & Energy, trade name “Neopolymer 150”
d-2: Fluorene acrylate, manufactured by Osaka Gas Chemical Co., Ltd., trade name “Ogsol EA-0200”
d-3: Fluorene epoxy resin, manufactured by Osaka Gas Chemical Co., Ltd., trade name “PG-100”
d-4: Bis (4-glycidylthiophenyl) sulfide, manufactured by Sumitomo Seika Co., Ltd., trade name “MPG”
[Polymerization initiator (C)]
c-1: Photocationic polymerization initiator, diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate
c-2: Thermal cationic polymerization initiator, 4-hydroxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate, manufactured by Sanshin Chemical Industry Co., Ltd., trade name “SI-B3”
c-3: Thermal radical polymerization initiator, t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation, trade name “Perbutyl O”
c-4: Photoradical polymerization initiator, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, manufactured by BASF, trade name “Irgacure 819”

Example 12
60 parts by weight of the compound (a-1), 30 parts by weight of the linear polymer (b-3), and 1 part by weight of a polymerization initiator (c-1) are dissolved in 100 parts by weight of tetrahydrofuran to obtain a resin composition ( 12) (solution state) was obtained.
The resin composition (12) was coated on a PET film using an applicator to form a coating film, and the obtained coating film was dried at 80 ° C. for 1 hour to obtain a curable resin film.
A release film of cyclic olefin copolymer (COC) is overlaid on the obtained curable resin film, and ultraviolet rays are irradiated from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp through the release film (irradiation amount: 1600 mJ / cm ^2). Then, heat treatment (100 ° C., 60 minutes) was performed. Thereafter, the release film and the PET film were peeled off to obtain a film-like cured product (thickness: 100 μm, refractive index: 1.725, property: uniform transparent solid).

Claims (8)

A compound (A) represented by the following formula (a), a linear polymer (B) containing a monomer unit containing a carbazole skeleton, and a polymerization initiator (C), a sealing material, a lens material, or A resin composition for use as an adhesive.
(In the formula, R ^a represents a reactive functional group. R ^b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; .R ^c indicating the optionally protected acyl group .m which represents single bond or a linking group represents an integer of 0 to 4, n is an integer of 0. the two R ^a is Each may be the same or different, and when there are a plurality of R ^b and m, they may be the same or different) The resin composition according to claim 1, wherein the monomer unit containing a carbazole skeleton in the linear polymer (B) is a monomer unit represented by the following formula (b).
(In the formula, A and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom or an organic group. Y represents a single bond or a linking group) The resin composition according to claim 1 or 2, wherein R ^a in the formula (a) is a vinyl group or an allyl group.   4. The resin composition according to claim 1, wherein the content of the compound (A) is 30 to 98% by weight of the total amount of the resin composition.   The resin composition according to any one of claims 1 to 4, wherein the content of the linear polymer (B) is 1 to 50% by weight of the total amount of the resin composition.   The resin composition according to any one of claims 1 to 5, wherein a ratio of the compound (A) to all polymerizable compounds contained in the resin composition is 70% by weight or more.   The electronic device which has the structure by which the element was sealed with the hardened | cured material of the resin composition of any one of Claims 1-6.   The lens which consists of hardened | cured material of the resin composition of any one of Claims 1-6.