WO2015033878A1 - 樹脂組成物及びその硬化物 - Google Patents
樹脂組成物及びその硬化物 Download PDFInfo
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- WO2015033878A1 WO2015033878A1 PCT/JP2014/072858 JP2014072858W WO2015033878A1 WO 2015033878 A1 WO2015033878 A1 WO 2015033878A1 JP 2014072858 W JP2014072858 W JP 2014072858W WO 2015033878 A1 WO2015033878 A1 WO 2015033878A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L41/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers
Definitions
- 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.
- Patent Document 1 a resin composition containing an oligomer having a monomer unit derived from bis (4-vinylthiophenyl) sulfide is known (Patent Document 1).
- 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.
- an object of the present invention is to provide a resin composition capable of easily adjusting the viscosity and curing shrinkage rate according to the application and forming a cured product (resin cured product) having a high refractive index.
- Another object of the present invention is to provide a cured product (resin cured product) having a high refractive index.
- 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.
- 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 is provided.
- R a represents a reactive functional group.
- R b may be protected by a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected by a protecting group, or a protecting group.
- the said resin composition whose monomer unit containing the carbazole skeleton in a linear polymer (B) is a monomer unit represented by following formula (b) is provided.
- 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 said resin composition whose said compound (A) is a compound represented by a following formula (a ') is provided. (Wherein R a , R b and m are the same as above)
- the polymerization initiator (C) is a light or thermal cationic polymerization initiator or a light or thermal radical polymerization initiator.
- a resin comprising the compound (A) represented by the above formula (a), a linear polymer (B) containing a monomer unit containing a carbazole skeleton, and a polymerization initiator (C).
- Composition [2] The resin composition according to [1], wherein the monomer unit containing a carbazole skeleton in the linear polymer (B) is a monomer unit represented by the above formula (b).
- 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
- molding the resin composition of this invention and the resin composition of this invention is a sealing material or seal
- the cured product of the resin composition or curable resin film of the present invention has a high refractive index
- 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.
- 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.
- 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 above 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.
- a group selected from a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group is preferable.
- R b in the formula (a) is a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which 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.
- R b bonded to the same aromatic ring may be bonded to each other to form a ring together with carbon atoms constituting the aromatic ring.
- the plurality of R b in the formula (a) may be the same or different.
- halogen atom in said Rb a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.
- 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.
- a C 1-10 (preferably C 1-5 ) alkyl group such as a decyl group.
- haloalkyl group for R b examples 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.
- aryl group for R b examples 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.
- 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
- 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 a hydroxymethyl group is substituted with a hydroxyl group.
- a hydroxyalkyl group etc. can be mentioned.
- Examples of the protecting group for the hydroxyl group and the hydroxyalkyl group in R b include protecting groups commonly used in the field of organic synthesis [for example, alkyl groups (for example, C 1-4 alkyl such as methyl group and t-butyl group).
- 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 Group tetrahydrofuranyl group
- 1-hydroxyalkyl group for example, 1-hydroxyethyl group, etc.
- an acyl group e.g., formyl group, acetyl group, a propionyl group, a butyryl
- 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 group for the hydroxyl group). Can do.
- Examples of the protecting group for the carboxyl group and the sulfo group for R b include protecting groups commonly used in the field of organic synthesis [for example, alkoxy groups (for example, 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.
- alkoxy groups for example, 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
- 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 acyls 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).
- 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
- 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).
- 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).
- 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.
- Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, divalent alicyclic hydrocarbon groups, and the like.
- 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.
- divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.
- the molecular weight of the compound (A) is not particularly limited, but is preferably from 300 to 10,000, particularly preferably from 300 to 1,000, and most preferably from 300 to 500, from the viewpoint of excellent solubility with the linear polymer (B).
- a plurality of m are the same or different and represent an integer of 0 to 4.
- N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.
- n is preferably 0 to 3, 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.
- R is a hydrogen atom or a methyl group.
- Compound (A) can be used singly or in combination of two or more.
- 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.
- 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).
- 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.
- a compound in which R a in formula (a) is a hydrogen atom for example, 4,4′-thiobisbenzenethiol, etc.
- a compound in which R a in formula (a) is a vinyl group includes a compound in which R a in formula (a) is a hydrogen atom (for example, 4,4′-thiobisbenzenethiol, etc.) and 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).
- 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.
- 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 (an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, a cycloalkyloxycarbonyl 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.
- halogen atom examples 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.
- 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 such as a vinyl group, an allyl group, and a 1-butenyl group (preferably 2 to 10; Preferred examples include an alkenyl group having 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.
- the alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members).
- a bridged cyclic hydrocarbon group such as a 17,7 ] dodecan-3-yl group.
- aromatic hydrocarbon group examples 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, etc.).
- the hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded includes an aralkyl group (for example, a C 7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to 4).
- 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.
- 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 (alk
- the hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- 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.
- 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 ⁇ -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.
- 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
- substituents such as groups (for example, a phenyl group, a naphthyl group, etc.).
- Y represents a single bond or a linking group.
- 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.
- 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.
- 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, for example, olefins [for example, chain olefins such as ethylene, propylene, 1-butene (particularly C 2-12 alkene); cyclopentene, cyclohexene, cycloheptene, norbornene.
- olefins for example, chain olefins such as ethylene, propylene, 1-butene (particularly C 2-12 alkene); cyclopentene, cyclohexene, cycloheptene, norbornene.
- Cyclic olefins such as 5-methyl-2-norbornene and tetracyclododecene
- aromatic vinyl compounds for example, styrene, vinyltoluene, ⁇ -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, a Acrylic acid C 1-10 alkyl esters such as acrylic acid 2-ethylhexyl, and methacrylic acid esters corresponding to these), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl caprylate, C 1 vinyl caproate, etc.
- maleic acid esters or fumaric acid esters eg, maleic acid di-C 1-10 alkyl esters such as diethyl maleate, dibutyl maleate, dioctyl maleate, 2-ethylhexyl maleate, and the like) Corresponding fumaric acid esters, etc.
- carboxyl group-containing monomers for example, monocarboxylic acids such as (meth) acrylic acid and itaconic acid; polyhydric carboxylic acids such as maleic anhydride, maleic acid and fumaric acid, or acid anhydrides thereof
- a monoalkyl ester of the polyvalent carboxylic acid For example, methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, octyl ester, C 1-16 alkyl esters), indenes and lauryl esters (e.g., indene, methyl indene, e
- 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).
- 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, for example, about 500 to 1,000,000, preferably 3000 to 500,000 in terms of excellent compatibility with the compound (A).
- the said weight average molecular weight is computable from the molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC), for example.
- GPC gel permeation chromatography
- 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.).
- the linear polymer (B) can be used singly or in combination of two or more.
- 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.
- 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 preferred, particularly preferably 1 to 30% by weight, most preferably 1% by weight or more and less than 30% by weight.
- the viscosity of a resin composition is moderately high, and a linear polymer (B)
- the content is preferably 30 to 70% by weight.
- 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.
- 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.
- a low-viscosity resin composition can be obtained.
- a highly viscous resin composition can be obtained.
- 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.
- 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.
- a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed.
- 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.
- 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).
- a photocationic polymerization initiator for example, 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), AsF 6 ⁇ , SbF 6 ⁇ , pentafluorohydroxyantimonate and the like.
- photocationic polymerization initiator of the present invention examples include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tetrakis (pentafluorophenyl).
- 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.
- trade names “Sun-Aid SI-45”, “Sun-Aid SI-47”, “Sun-Aid SI” are used.
- 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
- 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.
- the content is preferably 01 to 15% by weight, 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.
- the amount of the polymerizable compound contained in the resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 100 parts by weight. 5 parts by weight, most preferably 0.1 to 3 parts by weight.
- 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.
- DBU dibenzyldimethylamine
- 2,4,6-tris dimethylaminomethyl
- 2-ethyl-4 -Imidazoles such as methylimidazole and 1-cyanoethyl
- 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.
- curing accelerator examples 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. You can also.
- 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
- Photo radical polymerization initiator examples 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 Geigy Co., Ltd.
- the photo radical polymerization initiator examples 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.
- a photosensitizer can be added to the resin composition of this invention as needed.
- thermal radical polymerization initiator organic peroxides
- 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.
- organic peroxide examples 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. .
- naphthenic acid such as cobalt naphthenate, manganese naphthenate, zinc naphthenate, cobalt octenoate and the like
- metal salts such as cobalt octenoic acid, manganese, lead, zinc, vanadium, etc.
- 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% by weight is preferable, and 0.1 to 3% by weight is more preferable. Further, for example, 0.01 to 5 parts by weight is preferable with respect to 100 parts by weight of the polymerizable compound contained in the resin composition of the present invention, and more preferably 0.1 to 3 parts by weight.
- the resin composition of the present invention may further contain an inorganic filler.
- an inorganic filler it is preferable to use a filler that does not block visible light.
- silica nanonosilica etc.
- alumina alumina
- mica synthetic mica
- talc calcium oxide
- calcium carbonate zirconium oxide (nanozirconia etc.)
- oxidation Titanium nano titania, etc.
- barium titanate kaolin
- bentonite diatomaceous earth
- 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.
- nano colloidal sols of stabilized colloidal inorganic particles and the like can be used.
- Silica sol manufactured by BAYER, SnO 2 sol manufactured by Goldschmidt, TiO 2 sol manufactured by MERCK, 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, SiO 2 dispersion (trade name “Aerosil”) manufactured by DEGUSSA are available.
- An 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.
- 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.
- 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
- monocarboxylic acids such as acid and fumaric acid
- esters thereof preferably C 1-4 alkyl esters such as methyl methacrylate
- Amides acetylacetone, 2,4-hexanedione, 3,5-heptanedione, ⁇ -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 ⁇ m.
- 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. Further, the content of the inorganic filler in the total amount (100% by weight) of the resin composition is, for example, about 5 to 95% by weight.
- 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.
- silane coupling agents include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxysilane), and phenyl.
- 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.
- 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.
- a polymerizable compound excluding the compound (A)
- a polymerization inhibitor such as pigments, organic solvents, ultraviolet absorbers, ion adsorbers, phosphors, and release agents
- 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.
- 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.
- 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”).
- “cover” means a state in which the conductive fibers cover part or all of the surface of the particulate matter.
- 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.
- 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.
- 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). .
- 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.
- 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.
- 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
- thermoplastic resin examples 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.
- it is spherical (true sphere, approximately true sphere, elliptical sphere, etc.), polyhedron, rod (column, prism, etc.), flat plate, flake shape, indefinite Examples include shape.
- 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 diameter of the particulate material is not particularly limited, but is preferably 0.1 to 100 ⁇ m, particularly preferably 1 to 50 ⁇ m, and most preferably 5 to 30 ⁇ m.
- 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.
- 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.
- the average particle diameter of the particulate matter is a median diameter (d50) by a laser diffraction / scattering method.
- the particulate matter is preferably transparent.
- 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.
- the total light cotton transmittance in the visible light wavelength region of the particulate matter is obtained by polymerizing the monomer, which is 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.
- the value obtained by measuring the total light transmittance in the visible light wavelength region of the flat plate in accordance with JIS K7361-1, the value obtained by measuring the glass as 100% and the value calculated as a blank It is.
- 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 spread to details, and the occurrence of a portion with poor conductivity 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 between glasses in a temperature range of 80 to 150 ° C., 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.
- 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.
- the haze of the cured product of the present invention can be measured according to JIS K7136.
- the total light transmittance (thickness: 10 ⁇ m, 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.
- 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 common method, and the production method is not particularly limited.
- 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.
- 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.
- thermosetting resin examples include, for example, trade names “Techpolymer MBX series”, “Techpolymer BMX series”, “Techpolymer ABX series”, “Techpolymer ARX series”, and “Techpolymer AFX series”.
- 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).
- fibrous in the conductive fibers includes shapes of various linear structures such as “wire” and “rod”.
- 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
- the average length of the conductive fibers is not particularly limited, but is preferably 1 to 100 ⁇ m, particularly preferably 5 to 80 ⁇ m, and most preferably 10 to 50 ⁇ m. 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).
- the material (raw material) constituting the conductive fiber may be a conductive material, and examples thereof include metals, semiconductors, carbon materials, and conductive polymers.
- the metal examples include known or commonly used metals such as gold, silver, copper, iron, nickel, cobalt, tin, and alloys thereof.
- silver is particularly preferable in terms of excellent conductivity.
- Examples of the semiconductor include known or conventional semiconductors such as cadmium sulfide and cadmium selenide.
- Examples of the carbon material include known and commonly used carbon materials such as carbon fibers and carbon nanotubes.
- the conductive polymer examples 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).
- 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.
- 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.
- the gold nanowire can be manufactured, for example, by the method described in JP-A-2006-233252.
- a copper nanowire can be manufactured by the method as described in Unexamined-Japanese-Patent No.
- cobalt nanowire can be manufactured by the method as described in Unexamined-Japanese-Patent No. 2004-148771, for example.
- 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).
- the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
- the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
- the solvent is removed as necessary to obtain conductive fiber-coated particles (or a dispersion of the conductive fiber-coated particles).
- 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.
- the resin composition is liquid, it can also be used as the solvent.
- the step of removing the solvent can be omitted.
- the viscosity of the solvent is not particularly limited, but 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 at 1 atm of the solvent 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].
- the ratio is preferably about 100/1 to 100/100, preferably 100/10 to 100/50.
- the surface area of the said particulate matter is calculated
- 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.
- 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.
- 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.
- particulate matter having an average particle diameter L [ ⁇ m] and an average length L [ ⁇ m] or more (preferably L ⁇ 0.5 [ ⁇ m] or more, particularly preferably L
- conductive fibers of ⁇ 1.0 [ ⁇ m] or more, most preferably L ⁇ 1.5 [ ⁇ m] or more By using conductive fibers of ⁇ 1.0 [ ⁇ m] or more, most preferably L ⁇ 1.5 [ ⁇ m] or more), conductive fiber-coated particles can be more efficiently produced.
- a particulate material having an average circumference M [ ⁇ m] and an average length (M ⁇ 1/6) [ ⁇ m] or more (preferably M [ ⁇ m 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.
- SEM electron microscope
- the ratio of the particulate matter and the conductive fiber constituting the conductive fiber-coated particles 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 about a level (particularly 100/10 to 100/50) in that the conductivity can be imparted more efficiently while ensuring the transparency of the cured product.
- the surface area of the particulate matter and the projected area of the conductive fiber are determined by the above-described methods.
- 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.
- grain is made into the shape which has a fine unevenness
- the conductive fiber-coated particles follow the concavo-convex structure and deform to the details, preventing the occurrence of parts with poor conductivity and forming a cured product with excellent conductive performance. can do.
- 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.
- content of the said particulate matter is less than the said range, depending on a use, the electroconductivity of the obtained hardened
- 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 to 3% by volume, and most preferably 0.4 to 2% by 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.
- the amount is more preferably 0.03 to 0.6 parts by weight, particularly preferably 0.03 to 0.4 parts by weight, and most preferably 0.03 to 0.2 parts by weight.
- content of the said conductive fiber is less than the said range, depending on a use, the electroconductivity of the obtained hardened
- 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, and most preferably 0.03 to 0.4% by volume.
- 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.
- 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 1000000 mPa ⁇ s (preferably 15 to 100000 mPa ⁇ s, particularly by adjusting the weight average molecular weight and blending amount of the linear polymer (B) as appropriate. 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.
- the resin composition of the present invention can arbitrarily adjust the curing shrinkage within a range of, for example, 3 to 8% by appropriately adjusting the weight average molecular weight and blending amount of the linear polymer (B). . Therefore, it is possible to easily produce a resin composition having a curing shrinkage rate corresponding to the application.
- 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.
- the curable resin film of the present invention is obtained by molding the above 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 to a release paper or the like and dried (for example, dried at about 50 to 150 ° C. for about 1 to 10 minutes)].
- 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.
- 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.
- 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 depending on the application.
- it is, for example, about 0.1 to 100 ⁇ m (preferably 1 to 50 ⁇ m).
- variety and length in the surface direction of the curable resin film of this invention are not restrict
- the curable resin film of the present invention may be bonded with a release liner on the surface in order to protect the surface and prevent blocking.
- the release liner is peeled off when the curable resin film of the present invention is used.
- 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.
- 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.
- the resin composition or curable resin film of the present invention is cured by light irradiation, for example, the resin composition or curable resin film is irradiated with light of 1000 mJ / cm 2 or more with a mercury lamp or the like. Can be cured.
- the resin composition or curable resin film of the present invention is cured by heat treatment, for example, the resin composition or curable resin film is heated to 50 to 200 ° C.
- the resin composition or the curable resin film may be insufficiently cured.
- 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.
- the refractive index of the cured product can be measured by, for example, a method based on JIS K7142 or a method using a prism coupler.
- 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.
- 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.
- the resin composition or the curable resin film of the present invention when 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.
- 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.
- a thermal radical polymerization initiator trade name “Perbutyl O”, manufactured by NOF Corporation
- 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 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) were added to a self-revolving stirring deaerator (model: AR-250).
- 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 cast 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 ⁇ m).
- 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.
- 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.
- 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) were 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 a cyclic olefin copolymer (COC) is stacked 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 ⁇ m, refractive index: 1.725, property: uniform transparent solid).
- COC cyclic olefin copolymer
- the resin composition of the present invention can easily adjust the viscosity and cure shrinkage according to the application, and can form a cured product having a high refractive index.
- molding the resin composition of this invention and the resin composition of this invention is a sealing material or seal
- the cured product of the resin composition or curable resin film of the present invention has a high refractive index
- 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.
- 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.
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Abstract
Description
その他、例えば、金型を用いて成形する場合には、硬化時に適度に収縮することが離型性に優れる点で好ましい。そのため、用途に応じて硬化収縮率を調整することが求められていた。
しかし、得られる硬化物の屈折率を高く維持しつつ、用途に応じて粘度や硬化収縮率をコントロールすることは非常に困難であった。
また、本発明の他の目的は、高屈折率を有する硬化物(樹脂硬化物)を提供することにある。
[1] 上記式(a)で表される化合物(A)と、カルバゾール骨格を含有するモノマー単位を含む線状重合体(B)と、重合開始剤(C)を含むことを特徴とする樹脂組成物。
[2] 線状重合体(B)におけるカルバゾール骨格を含有するモノマー単位が上記式(b)で表されるモノマー単位である[1]に記載の樹脂組成物。
[3] 前記化合物(A)が、上記式(a’)で表される化合物である[1]又は[2]に記載の樹脂組成物。
[4] 前記重合開始剤(C)が、光若しくは熱カチオン重合開始剤、又は光若しくは熱ラジカル重合開始剤である[1]~[3]の何れか1つに記載の樹脂組成物。
[5] 化合物(A)の含有量が樹脂組成物全量の30~99重量%である[1]~[4]の何れか1つに記載の樹脂組成物。
[6] 線状重合体(B)の含有量が樹脂組成物全量の1~70重量%である[1]~[5]の何れか1つに記載の樹脂組成物。
[7] 化合物(A)の分子量が300~10000である[1]~[6]の何れか1つに記載の樹脂組成物。
[8] 線状重合体(B)の重量平均分子量(GPCによる、標準ポリスチレン換算)が500~1000000である[1]~[7]の何れか1つに記載の樹脂組成物。
[9] 25℃における粘度が15~1000000mPa・sである[1]~[8]の何れか1つに記載の樹脂組成物。
[10] 硬化収縮率が3~8%である[1]~[9]の何れか1つに記載の樹脂組成物。
[11] [1]~[10]の何れか1つに記載の樹脂組成物を成形する工程を経て得られる硬化性樹脂フィルム。
[12] [1]~[10]の何れか1つに記載の樹脂組成物を硬化して得られる硬化物。
[13] 25℃、波長589.3nmの光に対する屈折率が1.70以上である[12]に記載の硬化物。
また、本発明の樹脂組成物や硬化性樹脂フィルムの硬化物は高屈折率を有するため、上記電子デバイスを製造する工程で本発明の樹脂組成物を封止材として使用すると、封止材と高屈折率部材との界面における光の反射を抑制することができ、光の取り出し効率を向上することができ、高効率、高輝度、長寿命を有する電子デバイスが得られる。また、本発明の樹脂組成物や硬化性樹脂フィルムにより形成されたレンズは高屈折率を有するため、薄膜化、軽量化が可能であり、該レンズを含む電子機器のデザイン性を向上することができる。
本発明の樹脂組成物を構成する化合物(A)は、上記式(a)で表される重合性化合物である。上記式(a)中の2つのRaは、同一又は異なって、反応性官能基(重合性官能基)を示し、例えば、ビニル基、アリル基、アクリロイル基、メタクリロイル基、エポキシ基、グリシジル基、オキセタニル基等を挙げることができる。本発明においては、なかでもビニル基、アリル基、アクリロイル基、及びメタクリロイル基から選択される基が好ましい。
本発明の樹脂組成物を構成する線状重合体(B)は、カルバゾール骨格を含有するモノマー単位(繰り返し単位)を含む線状重合体である。前記モノマー単位は1種であってもよく2種以上であってもよい。
本発明の樹脂組成物を構成する重合開始剤(C)としては、特に限定されず、周知慣用の重合開始剤を使用することができる。具体的には、重合開始剤(C)として、光カチオン重合開始剤若しくは熱カチオン重合開始剤、又は光ラジカル重合開始剤若しくは熱ラジカル重合開始剤を好ましく使用できる。尚、重合開始剤(C)は1種を単独で、又は2種以上を組み合わせて使用することができる。
光カチオン重合開始剤は、光の照射によってカチオン種を発生してカチオン硬化性化合物の硬化反応を開始させる光カチオン重合開始剤である。光カチオン重合開始剤は、光を吸収するカチオン部と酸の発生源となるアニオン部からなる。
熱カチオン重合開始剤は加熱によってカチオン種を発生して、カチオン重合性化合物の硬化反応を開始させる化合物であり、例えば、商品名「サンエイドSI−45」、「サンエイドSI−47」、「サンエイドSI−60」、「サンエイドSI−60L」、「サンエイドSI−80」、「サンエイドSI−80L」、「サンエイドSI−100」、「サンエイドSI−100L」、「サンエイドSI−110L」、「サンエイドSI−145」、「サンエイドSI−150」、「サンエイドSI−160」、「サンエイドSI−180L」(以上、三新化学工業(株)製品)、「CI−2921」、「CI−2920」、「CI−2946」、「CI−3128」、「CI−2624」、「CI−2639」、「CI−2064」(以上、日本曹達(株)社製)、「PP−33」、「CP−66」、「CP−77」(以上、(株)ADEKA製)、「FC−509」、「FC−520」(以上、3M社製)等に代表されるジアゾニウム塩、ヨードニウム塩、スルホニウム塩、ホスホニウム塩、セレニウム塩、オキソニウム塩、アンモニウム塩等を使用できる。さらに、アルミニウムやチタン等の金属とアセト酢酸若しくはジケトン類とのキレート化合物とトリフェニルシラノール等のシラノールとの化合物、又は、アルミニウムやチタン等の金属とアセト酢酸若しくはジケトン類とのキレート化合物とビスフェノールS等のフェノール類との化合物であってもよい。
本発明の樹脂組成物は、硬化促進剤を含んでいてもよい。上記硬化促進剤とは、本発明の樹脂組成物中の重合性化合物が光若しくは熱カチオン重合開始剤により硬化する際に、硬化速度を促進する機能を有する化合物であり、例えば、1,8−ジアザビシクロ[5.4.0]ウンデセン−7(DBU)、1,5−ジアザビシクロ[4.3.0]ノネン−5(DBN)、及びその塩(例えば、フェノール塩、オクチル酸塩、p−トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩);ベンジルジメチルアミン、2,4,6−トリス(ジメチルアミノメチル)フェノール、N,N−ジメチルシクロヘキシルアミン等の第3級アミン;2−エチル−4−メチルイミダゾール、1−シアノエチル−2−エチル−4−メチルイミダゾール等のイミダゾール;リン酸エステル、トリフェニルホスフィン等のホスフィン類;テトラフェニルホスホニウムテトラ(p−トリル)ボレート等のホスホニウム化合物;オクチル酸スズ、オクチル酸亜鉛等の有機金属塩;金属キレート等を挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン、アセトフェノンベンジル、ベンジルジメチルケトン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ジメトキシアセトフェノン、ジメトキシフェニルアセトフェノン、ジエトキシアセトフェノン、ジフェニルジサルファイト、オルトベンゾイル安息香酸メチル、4−ジメチルアミノ安息香酸エチル(日本化薬(株)製、商品名「カヤキュアEPA」等)、2,4−ジエチルチオキサンソン(日本化薬(株)製、商品名「カヤキュアDETX」等)、2−メチル−1−[4−(メチル)フェニル]−2−モルホリノプロパノン−1(チバガイギー(株)製、商品名「イルガキュア907」等)、2−ジメチルアミノ−2−(4−モルホリノ)ベンゾイル−1−フェニルプロパン等の2−アミノ−2−ベンゾイル−1−フェニルアルカン化合物、テトラ(t−ブチルパーオキシカルボニル)ベンゾフェノン、ベンジル、2−ヒドロキシ−2−メチル−1−フェニル−プロパン−1−オン、4,4−ビスジエチルアミノベンゾフェノン等のアミノベンゼン誘導体、2,2’−ビス(2−クロロフェニル)−4,5,4’,5’−テトラフェニル−1,2’−ビイミダゾール(保土谷化学(株)製、商品名「B−CIM」等)等のイミダゾール化合物、2,6−ビス(トリクロロメチル)−4−(4−メトキシナフタレン−1−イル)−1,3,5−トリアジン等のハロメチル化トリアジン化合物、2−トリクロロメチル−5−(2−ベンゾフラン2−イル−エテニル)−1,3,4−オキサジアゾール等のハロメチルオキサジアゾール化合物等を挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。上記光ラジカル重合開始剤としては、感度及び耐薬品性等の観点から、イミダゾール化合物とアミノベンゼン誘導体の組合せ、2−アミノ−2−ベンゾイル−1−フェニルアルカン化合物、ハロメチル化トリアジン化合物、ハロメチルオキサジアゾール化合物等が好ましい。また、本発明の樹脂組成物には、必要に応じて、光増感剤を加えることができる。
上記熱ラジカル重合開始剤としては、例えば、有機過酸化物類を挙げることができる。上記有機過酸化物類としては、例えば、ジアルキルパーオキサイド、アシルパーオキサイド、ハイドロパーオキサイド、ケトンパーオキサイド、パーオキシエステル等を使用することができる。有機過酸化物の具体例としては、ベンゾイルパーオキサイド、t−ブチルパーオキシ−2−エチルヘキサノエート、2,5−ジメチル−2,5−ジ(2−エチルヘキサノイル)パーオキシヘキサン、t−ブチルパーオキシベンゾエート、t−ブチルパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、2,5−ジメチル−2,5−ジブチルパーオキシヘキサン、2,4−ジクロロベンゾイルパーオキサイド、ジ−t−ブチルパーオキシジ−イソプロピルベンゼン、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、メチルエチルケトンパーオキシド、1,1,3,3−テトラメチルブチルパーオキシ−2−エチルヘキサノエート等を挙げることができる。
本発明の樹脂組成物は、さらに、無機フィラーを含んでいてもよい。無機フィラーとしては、可視光線を遮断しないフィラーを使用することが好ましく、例えば、シリカ(ナノシリカ等)、アルミナ、マイカ、合成マイカ、タルク、酸化カルシウム、炭酸カルシウム、酸化ジルコニウム(ナノジルコニア等)、酸化チタン(ナノチタニア等)、チタン酸バリウム、カオリン、ベントナイト、珪藻土、窒化ホウ素、窒化アルミ、炭化ケイ素、酸化亜鉛、酸化セリウム、酸化セシウム、酸化マグネシウム、ガラスビーズ、ガラス繊維、グラファイト、カーボンナノチューブ、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、セルロース等を挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の樹脂組成物は、基板等の被接着体に対する接着性を向上させるために、さらにシランカップリング剤を含んでいてもよい。シランカップリング剤としては、例えば、テトラメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、メチルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス(メトキシエトキシシラン)、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、ビニルトリアセトキシシラン、γ−(メタ)アクリロキシプロピルトリエトキシシラン、γ−(メタ)アクリロキシプロピルトリメトキシシラン、γ−(メタ)アクリロキシプロピルメチルジメトキシシラン、γ−(メタ)アクリロキシプロピルメチルジエトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、p−スチリルトリメトキシシラン、3−アクリロキシプロピルトリメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルメチルジエトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリエトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−メルカプトプロピルメチルジメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3−イソシアネートプロピルトリエトキシシラン等の、水溶液中で比較的安定なものの中から適宜選択して使用することができる。
本発明の樹脂組成物は、更に、必要に応じて、例えば、重合性化合物(化合物(A)を除く)、重合禁止剤、酸化防止剤、光安定剤、可塑剤、レベリング剤、消泡剤、顔料、有機溶剤、紫外線吸収剤、イオン吸着体、蛍光体、離型剤等の慣用の添加剤を含有していてもよい。尚、本発明の樹脂組成物は上記化合物(A)以外にも他の重合性化合物(例えば、エポキシ系化合物、アクリル系化合物、オレフィン系化合物等)を含有していても良いが、樹脂組成物に含まれる全重合性化合物に占める化合物(A)の割合は、例えば50重量%以上、好ましくは70重量%以上である。
導電性繊維被覆粒子は、粒子状物質と、該粒子状物質を被覆する繊維状の導電性物質(本明細書では「導電性繊維」と称する場合がある)とを含む。尚、導電性繊維被覆粒子において「被覆する」とは、導電性繊維が粒子状物質の表面の一部又は全部を覆った状態を意味する。導電性繊維被覆粒子においては、導電性繊維が粒子状物質の表面の少なくとも一部を被覆していればよく、例えば、被覆した部分よりも被覆していない部分の方が多く存在していてもよい。また、導電性繊維被覆粒子においては、必ずしも粒子状物質と導電性繊維とが接触している必要はないが、通常、導電性繊維の一部は粒子状物質の表面に接触している。
導電性繊維被覆粒子を構成する粒子状物質は、粒子状の構造体である。
すなわち、本発明の樹脂組成物と導電性繊維被覆粒子を構成する粒子状物質とは、下記式を満たすことが好ましい。
|粒子状物質の屈折率−樹脂組成物の硬化物の屈折率|≦0.1
導電性繊維被覆粒子を構成する導電性繊維は、導電性を有する繊維状の構造体(線状構造体)である。上記導電性繊維の形状は繊維状(ファイバー状)であればよく、特に限定されないが、その平均アスペクト比は、10以上(例えば、20~5000)が好ましく、特に好ましくは50~3000、最も好ましくは100~1000である。平均アスペクト比が上記範囲を下回ると、少量の導電性繊維被覆粒子の配合によって優れた導電性を発現させることが困難となる場合がある。上記導電性繊維の平均アスペクト比は、電子顕微鏡(SEM、TEM)を用いて十分な数(例えば、100個以上、好ましくは300個以上;特に、100個、又は300個)の導電性繊維について電子顕微鏡像を撮影し、これらの導電性繊維のアスペクト比を計測し、算術平均することにより求められる。尚、上記導電性繊維における「繊維状」の概念には、「ワイヤー状」、「ロッド状」等の各種の線状構造体の形状も含まれる。また、本明細書においては、平均太さが1000nm以下の繊維を「ナノワイヤ」と称する場合がある。
長さ=投影面積/投影径
(1)上記粒子状物質を溶媒に分散させた分散液(「粒子分散液」と称する)と、上記導電性繊維を溶媒に分散させた分散液(「繊維分散液」と称する)とを混合し、必要に応じて溶媒を除去して、導電性繊維被覆粒子(又は該導電性繊維被覆粒子の分散液)を得る。
(2)上記粒子分散液に上記導電性繊維を配合し、混合した後、必要に応じて溶媒を除去して、導電性繊維被覆粒子(又は該導電性繊維被覆粒子の分散液)を得る。
(3)上記繊維分散液に上記粒子状物質を配合し、混合した後、必要に応じて溶媒を除去して、導電性繊維被覆粒子(又は該導電性繊維被覆粒子の分散液)を得る。
(4)溶媒に上記粒子状物質及び上記導電性繊維を配合し、混合した後、必要に応じて溶媒を除去して、導電性繊維被覆粒子(又は該導電性繊維被覆粒子の分散液)を得る。
本発明の樹脂組成物は、上述の化合物(A)、線状重合体(B)、重合開始剤(C)、及び必要に応じてその他の成分(無機フィラー、シランカップリング剤、導電性材料等の添加剤)を、均一に混合することにより製造することができる。本発明の樹脂組成物を得るにあたっては、各成分を自公転式撹拌脱泡装置、ホモジナイザー、プラネタリーミキサー、3本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用してなるべく均一になるように、撹拌、溶解、混合、分散等を行うことが望ましい。尚、各成分は、同時に混合してもよいし、逐次混合してもよい。
硬化収縮率(%)=[(硬化物の比重−硬化前の樹脂液の比重)/硬化物の比重]×100
本発明の硬化性樹脂フィルムは、上記樹脂組成物(特に、線状重合体(B)の含有量が30~70重量%程度の樹脂組成物)を成形工程[例えば、上記樹脂組成物を溶媒に溶解し、剥離紙等の上に塗布して乾燥(例えば、50~150℃程度で1~10分程度乾燥)]に付して得られる。特に、樹脂組成物が重合開始剤(C)として光カチオン重合開始剤を含有する場合は、成形工程後に、必要に応じて光照射工程を設けることができる。
本発明の樹脂組成物又は硬化性樹脂フィルムに光照射及び/又は加熱処理を施すことにより硬化物(樹脂硬化物、硬化性樹脂フィルムを硬化させた場合はフィルム状の樹脂硬化物)を得ることができる。本発明の樹脂組成物又は硬化性樹脂フィルムを光照射により硬化させる場合には、例えば、上記樹脂組成物又は硬化性樹脂フィルムに対して、水銀ランプ等で1000mJ/cm2以上の光を照射することで硬化させることができる。また、本発明の樹脂組成物又は硬化性樹脂フィルムを加熱処理により硬化させる場合には、例えば、上記樹脂組成物又は硬化性樹脂フィルムを、温度50~200℃(より好ましくは50~170℃、さらに好ましくは50~150℃)で、10~600分間(より好ましくは10~360分間、さらに好ましくは15~180分間)加熱することで硬化させることができる。加熱する温度(硬化温度)や時間(硬化時間)が上記範囲を下回ると、樹脂組成物又は硬化性樹脂フィルムの硬化が不十分となる場合がある。一方、硬化温度や硬化時間が上記範囲を上回ると、樹脂成分の分解が起きる場合がある。本発明の樹脂組成物又は硬化性樹脂フィルムの硬化条件は、種々の条件に依存するが、硬化温度が高い場合は硬化時間を短く、硬化温度が低い場合は硬化時間を長くする等により、適宜調整することができる。本発明の樹脂組成物又は硬化性樹脂フィルムを硬化させることにより、高屈折率を有する硬化物を得ることができる。
線状重合体(b−4)[ポリ(スチレン−N−ビニルカルバゾール)]の合成
スチレン(商品名「S0095」、東京化成(株)製)及びN−ビニルカルバゾール(商品名「V0021」、東京化成(株)製)を各2g秤量し、80℃で10分加熱撹拌してモノマー混合溶液を得た。
得られたモノマー混合溶液を25℃まで冷却し、その後、熱ラジカル重合開始剤(商品名「パーブチルO」、日油(株)製)を0.4g添加して混合溶液を調製し、該混合溶液を窒素雰囲気下、95℃で三つ口フラスコにて撹拌中の蒸留水(40g)に全量滴下し、95℃で2時間重合反応させて重合物を得た。
得られた重合物を濾集し、乳鉢で粉砕し、未反応モノマーをメタノールで洗浄した後に真空乾燥して線状重合体(b−4)を2.4g得た。線状重合体(b−4)の共重合比(重量%)はH1−NMRよりカルバゾール:スチレン=86:14であった。またGPCより重量平均分子量(MW)は56500であった。
化合物(a−1)89重量部、線状重合体(b−1)10重量部、及び重合開始剤(c−1)1重量部を、自公転式撹拌脱泡装置(型式:AR−250、(株)シンキー製)内に投入して撹拌し、樹脂組成物(1)(25℃における粘度:48mPa・s)を得た。尚、樹脂組成物の粘度はE型粘度計を使用して測定した。
得られた樹脂組成物(1)を金型に注型し、200W/cmの高圧水銀灯で10cmの距離から紫外線を照射(照射量:1600mJ/cm2)し、その後、加熱処理(100℃、60分)を施して硬化物(1)(厚み:100μm)を得た。
下記表に示す組成に変更した以外は実施例1と同様にして樹脂組成物及び硬化物を作製した。
尚、実施例9、10及び比較例1、2で得られた樹脂組成物の硬化は、100℃の定温送風オーブンにて1時間加熱することにより行った。
得られた硬化物(厚み:100μm)について、Model 2010プリズムカプラ(メトリコン社製)を使用して、25℃において、589.3nmの光の屈折率を測定した。
樹脂組成物を硬化させて硬化物を形成した際の硬化収縮率を、比重法により算出した。
[化合物(A)]
a−1:ビス(4−ビニルチオフェニル)スルフィド、分子量:302、住友精化(株)製、商品名「MPV」
[線状重合体(B)]
b−1:ポリ−N−ビニルカルバゾール、重量平均分子量:8500、丸善石油化学(株)製、商品名「PVCZ 8K」
b−2:ポリ−N−ビニルカルバゾール、重量平均分子量:45000、丸善石油化学(株)製、商品名「PVCZ」
b−3:ポリ−N−ビニルカルバゾール、重量平均分子量:400000、東京化成(株)製、商品名「P0656」
b−4:合成例1で得られたポリ(スチレン−N−ビニルカルバゾール)、重量平均分子量:56500
[他の重合性化合物]
d−1:石油樹脂、JX日鉱日石エネルギー(株)製、商品名「ネオポリマー150」
d−2:フルオレンアクリレート、大阪ガスケミカル(株)製、商品名「オグソールEA−0200」
d−3:フルオレン系エポキシ樹脂、大阪ガスケミカル(株)製、商品名「PG−100」
d−4:ビス(4−グリシジルチオフェニル)スルフィド、住友精化(株)製、商品名「MPG」
[重合開始剤(C)]
c−1:光カチオン重合開始剤、ジフェニル[4−(フェニルチオ)フェニル]スルホニウム トリス(ペンタフルオロエチル)トリフルオロホスフェート
c−2:熱カチオン重合開始剤、4−ヒドロキシフェニルベンジルメチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、三新化学工業(株)製、商品名「SI−B3」
c−3:熱ラジカル重合開始剤、t−ブチルパーオキシ−2−エチルヘキサノエート、日油(株)製、商品名「パーブチルO」
c−4:光ラジカル重合開始剤、フェニルビス(2,4,6−トリメチルベンゾイル)ホスフィンオキシド、BASF社製、商品名「イルガキュア819」
上記化合物(a−1)60重量部、線状重合体(b−3)30重量部、及び重合開始剤(c−1)1重量部を、テトラヒドロフラン100重量部に溶解して樹脂組成物(12)(溶液状)を得た。
前記樹脂組成物(12)をPETフィルム上にアプリケーターを使用して塗工して塗膜を形成し、得られた塗膜を80℃で1時間乾燥して、硬化性樹脂フィルムを得た。
得られた硬化性樹脂フィルムの上に環状オレフィンコポリマー(COC)の離型フィルムを重ね、離形フィルム越しに200W/cmの高圧水銀灯で10cmの距離から紫外線を照射(照射量:1600mJ/cm2)し、その後加熱処理(100℃、60分)を施した。その後、離型フィルムとPETフィルムを剥がして、フィルム状の硬化物(厚み:100μm、屈折率:1.725、性状:均一透明固体)を得た。
また、本発明の樹脂組成物や硬化性樹脂フィルムの硬化物は高屈折率を有するため、上記電子デバイスを製造する工程で本発明の樹脂組成物を封止材として使用すると、封止材と高屈折率部材との界面における光の反射を抑制することができ、光の取り出し効率を向上することができ、高効率、高輝度、長寿命を有する電子デバイスが得られる。
また、本発明の樹脂組成物や硬化性樹脂フィルムにより形成されたレンズは高屈折率を有するため、薄膜化、軽量化が可能であり、該レンズを含む電子機器のデザイン性を向上することができる。
Claims (6)
- 下記式(a)で表される化合物(A)と、カルバゾール骨格を含有するモノマー単位を含む線状重合体(B)と、重合開始剤(C)を含むことを特徴とする樹脂組成物。
- 前記重合開始剤(C)が、光若しくは熱カチオン重合開始剤、又は光若しくは熱ラジカル重合開始剤である請求項1~3の何れか1項に記載の樹脂組成物。
- 請求項1~4の何れか1項に記載の樹脂組成物を成形する工程を経て得られる硬化性樹脂フィルム。
- 請求項1~4の何れか1項に記載の樹脂組成物を硬化して得られる硬化物。
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JP2019172873A (ja) * | 2018-03-29 | 2019-10-10 | 日産化学株式会社 | 硬化性組成物、その硬化物、及び電子デバイス |
JP2020056825A (ja) * | 2018-09-28 | 2020-04-09 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜、積層体、転写フィルム、及び、タッチパネルの製造方法 |
WO2021002379A1 (ja) * | 2019-07-04 | 2021-01-07 | 積水化学工業株式会社 | 有機el表示素子用封止剤セット及び有機el表示素子 |
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CN105745273B (zh) * | 2013-09-05 | 2019-05-07 | 株式会社大赛璐 | 树脂组合物及其固化物 |
TWI750321B (zh) * | 2017-02-21 | 2021-12-21 | 日商住友化學股份有限公司 | 樹脂組成物及硬化膜 |
CN110819141B (zh) * | 2018-08-10 | 2022-07-12 | Jsr株式会社 | 硬化性组合物及化合物 |
CN109080967B (zh) * | 2018-10-09 | 2019-12-17 | 中山市富日印刷材料有限公司 | 一种具有五层结构的油墨包装袋 |
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KR20160077232A (ko) | 2016-07-01 |
JPWO2015033878A1 (ja) | 2017-03-02 |
CN105745273B (zh) | 2019-05-07 |
JP2016155998A (ja) | 2016-09-01 |
TWI551647B (zh) | 2016-10-01 |
KR20160011229A (ko) | 2016-01-29 |
JP6074522B2 (ja) | 2017-02-01 |
CN105745273A (zh) | 2016-07-06 |
KR101838830B1 (ko) | 2018-03-14 |
TW201518378A (zh) | 2015-05-16 |
JP6336002B2 (ja) | 2018-06-06 |
JP2017057401A (ja) | 2017-03-23 |
JP5872121B2 (ja) | 2016-03-01 |
KR101635722B1 (ko) | 2016-07-01 |
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