TW201529664A - Resin composition, thermally-conductive cured product, silicon compound, silane coupling agent composition and carrier - Google Patents

Abstract

Provided is a resin composition that enables a thermally-conductive cured product having excellent thermal conductivity to be produced. This resin composition contains a carrier that supports a silane coupling agent composition, said silane coupling agent composition containing a silicon compound represented by general formula (1). (In general formula (1), each R1 represents, independently, a straight or branched C1-C3 alkyl group, A1 represents a single bond or a C1-C4 alkanediyl group, and Y represents a hydrogen atom, a C1-C12 straight or branched alkyl group, or the like).

Description

Resin composition, thermally conductive cured product, bismuth compound, decane coupling agent composition and carrier

The present invention relates to a resin composition, a thermally conductive cured product obtained by curing the resin composition, a novel hydrazine compound having a specific structure, a decane coupling agent composition containing the hydrazine compound, and a decane coupling agent supported thereon. The carrier of the composition.

In recent years, with the increase in speed and high performance of electrical equipment and electronic equipment, electronic components such as semiconductor elements and power transistors tend to be highly integrated and have a high density. However, when electronic components are highly integrated and high in density, there is a problem that power consumption increases and heat generation increases. The heat generated inside the electronic parts sometimes causes defects such as deterioration or malfunction of the electronic parts.

As a method of suppressing such an inconvenience, various reports have been made. For example, as a method of removing heat from an electronic component, a method of forcibly cooling using a cooling member typified by a cooling fan is known. Further, a method of applying heat by coating a polyfluorene grease or a method of transferring heat from an electronic component to a cooling component using a thermally conductive sheet is known.

There have been various reports as thermal conductive sheets for use in a method for transferring thermal components from electronic components to cooling components. For example, Patent Document 1 discloses a thermally conductive epoxy resin sheet formed using a resin composition containing an epoxy resin, a curing agent, a filler, a surface treatment agent, and a solvent. Further, Patent Document 2 discloses a thermally conductive sheet containing a polyfluorene-based copolymer and a thermally conductive filler, and is used as a heat conductive filler. The filler is preferably aluminum nitride, aluminum oxide, and boron nitride. Further, Patent Document 2 discloses that when a decane coupling agent is contained, the dispersibility of the thermally conductive filler or the adhesion between the polyoxymethylene-based copolymer and the thermally conductive filler is improved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-007039

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-229269

When a sheet-shaped thermally conductive cured product is used as the thermally conductive sheet for transferring the electronic component to the cooling component with high thermal efficiency, the thermally conductive cured product is required to have high thermal conductivity. Conventionally, in order to improve the thermal conductivity of a thermally conductive cured product, the type of the filler or the content thereof has been examined, but a thermally conductive cured product having a desired thermal conductivity has not been obtained. Therefore, it has been desired to develop an additive or the like which effectively enhances the thermal conductivity of the thermally conductive cured product.

As a result of intensive studies, the inventors of the present invention have found that a cured product obtained by curing a resin composition containing a carrier of a decane coupling agent having a specific structure of a ruthenium compound exhibits particularly excellent thermal conductivity. , 遂 completed the present invention.

That is, the present invention provides a resin composition comprising a carrier carrying a composition of a decane coupling agent, wherein the decane coupling agent composition contains the oxime compound represented by the following general formula (1). Furthermore, the present invention provides a thermally conductive cured product obtained by curing the resin composition.

(In the above general formula (1), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and A ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched oxyalkyl group having 1 to 12 carbon atoms, a dimethylamino group, a diethylamino group or an ethyl group. Methylamino group; X represents a group represented by any one of the following formulas (X-1) to (X-6), and when Z is a group represented by the following formula (X-1), Z is -NHCO -, when X is a group represented by any one of the following formulas (X-2) to (X-6), Z is a single bond or -NHCO-.)

Further, the present invention provides a hydrazine compound represented by the following general formula (2), a decane coupling agent composition containing the hydrazine compound, and a carrier carrying the decane coupling agent composition.

(In the above general formula (2), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, A ² represents an alkanediyl group having 1 to 4 carbon atoms, and X represents the following a group represented by any one of the formulae (X-1) to (X-6), wherein Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and a carbon number of 1 to 12; Linear or branched oxyalkyl, dimethylamino, diethylamino or ethylmethylamino.)

According to the present invention, it is possible to provide a resin composition capable of producing a thermally conductive cured product having superior thermal conductivity. Further, according to the present invention, it is possible to provide a thermally conductive cured product having superior thermal conductivity. Further, according to the present invention, novel anthraquinone compounds can be provided. When this novel ruthenium compound is used, a carrier for a resin composition capable of producing a thermally conductive cured product having particularly excellent thermal conductivity can be provided.

The term "carrier" as used in the present invention means chemical bonds (for example, covalent bonds, electric valence bonds, and ionic bonds), vantage, electrostatic force, adhesion, adsorption, solid adhesion, and other types of convergence. The combination of the decane coupling agent composition and all forms between the supported bodies.

The resin composition of the present invention contains a carrier in which a composition of a decane coupling agent is carried. Further, the decane coupling agent composition contains the oxime compound represented by the following general formula (1).

(In the above general formula (1), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and A ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched oxyalkyl group having 1 to 12 carbon atoms, a dimethylamino group, a diethylamino group or an ethyl group. Methylamino group; X represents a group represented by any one of the following formulas (X-1) to (X-6), and when X is a group represented by the following formula (X-1), Z is - When NHCO-, X is a group represented by any one of the following formulas (X-2) to (X-6), Z is a single bond or -NHCO-.)

In the above general formula (1), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms. Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

In the above general formula (1), A ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. Examples of the alkanediyl group having 1 to 4 carbon atoms include a methylene group, an ethylidene group, a propyl group and a butyl group.

In the above general formula (1), X represents a group represented by any one of the above formulas (X-1) to (X-6). Further, when X is a group represented by the formula (X-1), Z is -NHCO-. Further, when X is a group represented by the formula (X-2) to (X-6), Z is a single bond or -NHCO-.

In the above general formula (1), Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched oxyalkyl group having 1 to 12 carbon atoms, or a dimethyl group. Amino, diethylamino or ethylmethylamino. The linear or branched alkyl group having 1 to 12 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group or a third butyl group. , pentyl, pentylene, isopentyl, hexyl, heptyl, isoheptyl, octyl Base, isooctyl, 2-ethylhexyl, decyl, isodecyl, fluorenyl, and dodecyl. Further, examples of the linear or branched oxyalkyl group having 1 to 12 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, and a butyloxy group. Second butyloxy, tert-butoxy, isobutyloxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy, Heptyloxy, isoheptyloxy, third heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy and the like.

Z in the above general formula (1) is preferably -NHCO-. When the ruthenium compound in which Z in the general formula (1) is -NHCO- is used, the thermal conductivity of the obtained thermally conductive cured product can be greatly improved. Further, when A ¹ in the general formula (1) is a stretching propyl group, it is preferable from the economical side.

As a preferable specific example of the hydrazine compound represented by the general formula (1), for example, Compound Nos. 1 to No. 99 shown in the following chemical formulas No. 1 to No. 99. Further, in the following chemical formula, "Me" represents a methyl group, and "Et" represents an ethyl group. In the general formula (1), two kinds of geometric isomers caused by an azo group may be present. This is not to be distinguished in the present invention, and may be one geometric isomer or a mixture of two geometric isomers.

The hydrazine compound represented by the general formula (1) can be produced by a known reaction, depending on The manufacturing method is not limited. In the general formula (1), Z is a single bond ruthenium compound, for example, by a phenyl compound corresponding to the structure of the target compound and a trialkoxy decane, represented by hexachloroplatinum (IV) acid or the like. It is produced by reacting in the presence of a catalyst. Further, in the general formula (1), Z is a compound of -NHCO-, for example, an amine having a structure corresponding to the target compound and an amine represented by 3-aminopropyltrialkoxydecane a trialkoxy decane, a condensing agent represented by O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate under basic conditions Manufactured together in response.

The resin composition of the present invention usually contains a decane coupling agent The carrier of the material is 30 to 80% by mass, and the resin component is 20 to 70% by mass (wherein the carrier + resin component = 100% by mass).

The resin composition of the present invention is, for example, such that it contains a general formula (1). The decane coupling agent composition of the compound is carried on the carrier. As a method of supporting the decane coupling agent composition on the carrier, a known method can be used. For example, a method such as vapor phase adsorption or liquid phase adsorption can be used. In addition, as an example of the liquid phase adsorption, for example, a carrier obtained by dissolving a ruthenium compound represented by the general formula (1) in a solvent is immersed in a carrier, and the ruthenium compound is adsorbed to the carrier. method.

The type of the resin component is not particularly limited. The resin component may, for example, be a thermosetting resin or a thermoplastic resin. Among them, a thermosetting resin can be suitably used. Examples of the thermosetting resin include an amine resin, a cyanate resin, an isocyanate resin, a polyimide resin, an epoxy resin, an oxycyclobutane resin, a polyester resin, an allyl resin, a phenol resin, and benzene. and Resin, xylene resin, ketone resin, furan resin, COPNA resin, oxime resin, dicyclopentadiene resin, benzocyclobutene resin, episulfide resin, alkenyl-mercapto resin, polymethylenimine resin, polyvinyl benzyl Ether, terpene, etc. Among them, as the resin component, a cyanate resin, an isocyanate resin, an epoxy resin, or a phenol resin is preferable.

The cyanate resin is, for example, a cyanate resin obtained by reacting a halogenated cyanide compound with a phenol or a naphthol, and prepolymerizing it, if necessary, by heating or the like. Examples of the cyanate resin include a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a bisphenol such as a tetramethylbisphenol F type cyanate tree. A cyanate resin, a naphthol aralkyl type cyanate resin, or the like. More specifically, for example, 2,2'-bis(4-cyanooxyphenyl)isopropylidene, 1,1'-bis(4-cyanooxyphenyl)ethane, bis(4- Cyanoxy-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanooxyphenyl-1-(1-methylethylidene))benzene, dicyclopentadiene cyanide Acid ester, phenolic novolac type cyanate, bis(4-cyanooxyphenyl) sulfide, bis(4-cyanooxyphenyl)ether, 1,1,1-cis (4-cyanooxyl) Phenyl)ethane, ginseng (4-cyanooxyphenyl) phosphite, bis(4-cyanooxyphenyl)anthracene, 2,2-bis(4-cyanooxyphenyl)propane, 1, 3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanooxynaphthalene, 1,3,6-tricyanomethoxynaphthalene, 4,4-dicyanooxy Biphenyl, phenolic novolac type, cresol novolac type polyphenols, cyanate resin obtained by reaction with cyanogen halide; naphthol aralkyl type polyheptanol, reaction with cyanogen halide Cyanate resin and the like.

As the isocyanate resin, for example, dehalogenation by phenols and cyanogen halides The isocyanate resin obtained by hydrogen reaction. The isocyanate resin may, for example, be 4,4'-diphenylmethane diisocyanate MDI, polymethylene polyphenyl polyisocyanate, benzylidene diisocyanate or hexamethylene diisocyanate.

Examples of the epoxy resin include hydroquinone, resorcin, and catechol. Polyepoxypropyl ether compound of mononuclear polyphenol compound such as phloroglucin; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), and ethylene Bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1 , 4-bis(4-hydroxycumylbenzene), 1,1,3-glycol(4-hydroxyphenyl)butane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane , thiobisphenol, sulfonate bisphenol, oxybisphenol, phenolic novolac, o-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac Polyepoxypropyl ether compound of polynuclear polyphenol compound such as varnish or terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, thiodiethylene glycol, glycerin, trishydroxyl a polyepoxypropyl ether of a polyhydric alcohol such as propane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, pentane Acid, suberic acid, adipic acid, azelaic acid, azelaic acid, dimer acid, trimer acid, citric acid Aliphatic, aromatic or lipids of isophthalic acid, p-nonanoic acid, trimellitic acid, symmetrical trimellitic acid, pyroic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, endomethylene tetrahydrofurfuric acid, etc. Glycidyl ester of cycloaliphatic acid, and homopolymer or copolymer of glycidyl methacrylate; N,N-diepoxypropylaniline, bis(4-(N-methyl-N-epoxy) Propylamino)benzene Epoxy compound having a glycidylamino group such as methane or diglycidyl o-toluidine; vinyl cyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, Epoxide of a cyclic olefin compound such as bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene A heterocyclic compound such as an epoxidized conjugated diene polymer such as a polymer or a triepoxypropyl trimer isocyanate. Among them, a naphthalene type epoxy resin or a bisphenol A type epoxy resin is preferable.

As the phenol resin, there are phenol resins synthesized from phenols and aldehydes. As Examples of the phenols include phenol, cresol, phenol, n-propanol, propofol, butanol, tert-butylphenol, octylphenol, indophenol, dodecylphenol, cyclohexanol, chlorophenol, bromophenol , resorcinol, catechol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, indophenol, Phenylated dicyclopentadiene and the like. Further, examples of the aldehydes include formaldehyde.

In the resin composition of the present invention, various additives may be added as needed. Make Examples of the additive include a curing agent for an epoxy resin, a plasticizer for a natural wax, a synthetic wax, a metal salt of a long-chain aliphatic acid, and the like; an acid amide, an ester, a paraffin, and the like. Release agent; stress relaxation agent such as nitrile rubber, butadiene rubber; antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium methylborate, red phosphorus, aluminum hydroxide , inorganic flame retardant such as magnesium hydroxide or calcium aluminate; bromine-based flame retardant such as tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, brominated phenol novolac; phosphorus flame retardant; dye Or coloring agent such as pigment; oxidation stabilizer, light stabilizer, moisture resistance enhancer, shake imparting agent, diluent, antifoaming agent, various other resins, adhesion imparting agent, antistatic agent, slip agent, ultraviolet absorption Agents, etc. Further, alcohols, ethers, acetals, ketones, esters, alcohol esters, keto alcohols, ether alcohols, ketone ethers, ketoesters, ester ethers, aromatic solvents can also be formulated. Such as organic solvents and the like.

As the hardener used for the epoxy resin, for example, latent hardening A reagent, an acid anhydride, a polyamine compound, a polyphenol compound, a cationic photoinitiator, and the like.

As the latent hardener, for example, dicyandiamide, hydrazine, and imidazole may be mentioned. A compound, an amine adduct, a phosphonium salt, a phosphonium salt, a ketimine, an acid anhydride, a tertiary amine or the like. When such a latent curing agent is used, the resin composition of the present invention can be preferably used as a one-liquid type curable composition which is easy to handle.

As the acid anhydride, for example, phthalic anhydride, trimellitic anhydride, or methic acid Anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexa Fluoropropane dianhydride and the like.

The polyamine compound may, for example, be an aliphatic polyamine such as ethylenediamine, diethylenetriamine or triethylenetetramine; Alkylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2 , an alicyclic polyamine such as 4,8,10-tetraoxaspiro[5,5]undecane; an aliphatic amine having an aromatic ring such as m-xylenediamine; m-phenylenediamine, 2, 2 - bis(4-aminophenyl)propane, diaminodiphenylmethane, diaminodiphenyl hydrazine, α,α-bis(4-aminophenyl)-p-diisopropylbenzene, 2,2-dual ( An aromatic polyamine such as 4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the polyphenol compound include a phenol novolak and an o-cresol novolac. Varnish, third butyl phenol novolac, dicyclopentadienyl cresol, quinolol, quinone catechol, 1, 1,3- gin (3-tert-butyl-4-hydroxy-6- Phenyl)butane, butylene bis(3-tert-butyl-4-hydroxy-6-methylphenyl), 2,2-bis(4-hydroxyphenyl)-1,1,1,3 , 3,3-hexafluoropropane, and the like.

The imidazole compound may, for example, be 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-deca Monomimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-three 2,4-diamino-6(2'-undecylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-ethyl, 4-methylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-s-three ‧Iso-cyanuric acid adduct, 2:3 adduct of 2-methylimidazolium isocyanuric acid, 2-phenylimidazole triisocyanate adduct, 2-phenyl-3,5 -Dimethylolidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Imidazoles; salts of such imidazoles with polycarboxylic acids such as capric acid, isodecanoic acid, p-citric acid, trimellitic acid, pyroic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, and the like.

By curing the resin composition of the present invention, a good heat can be obtained. Conductive hardened material. Further, by selecting an appropriate composition, it is possible to impart coatability, low viscosity, flexibility of the coating film before curing, flexibility of the cured product after curing, adhesion to the substrate, and the like. Therefore, the thermally conductive cured product obtained by curing the resin composition of the present invention can be widely used as a printed wiring board, a semiconductor sealing insulating material, a power semiconductor, an LED lighting, an LED backlight, a power LED, a solar battery, etc. A resin substrate for various components of the field. More specifically, it can be used as a prepreg, a sealant, a laminated substrate, a tackifier for a coating property, an adhesive sheet, and the like, and a curable component such as these, and a curable component of various coating materials.

The thermally conductive cured product of the present invention comprises the above resin composition of the present invention A hardened material obtained by hardening a substance. The shape of the thermally conductive cured product is not particularly limited, and examples thereof include a sheet shape, a film shape, and a plate shape. The sheet-like cured product can be produced by applying the resin composition of the present invention to a support such as a carrier film or a metal foil and then curing it. In the case where the resin composition to be used as the raw material contains an organic solvent, the thermally conductive cured product of the present invention includes both a cured product in a state in which a solvent remains and a cured product in a state in which a solvent is volatilized and substantially no solvent is contained.

The thermally conductive cured product of the present invention can be produced by a known method. example For example, when the shape of the thermally conductive cured product is a sheet shape, the resin composition can be applied onto the support and the formed coating film can be cured. A coating device or a spray device can be used for the coating of the resin composition on the support. Examples of the coating device include a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, a screen printing apparatus, and bristles.

When manufacturing a sheet-shaped thermally conductive cured product, it is preferred to use a volume. Easy to operate support. Moreover, in the case where the sheet-shaped thermally conductive cured product is peeled off by the support, it is preferable to use a support which is easy to peel off the thermally conductive cured product. As the support, a carrier film is suitable. As the carrier film, a polyester resin containing, for example, polyethylene terephthalate or polybutylene terephthalate, or a heat-resistant thermoplastic such as a fluorine-based resin or a polyimide resin can be appropriately selected. A film of resin.

Moreover, in the case where a metal foil is used as the support, the heat formed can be formed The conductive cured product is used by being peeled off from the metal foil, and may be used by etching the metal foil without peeling off. As the metal foil, for example, copper, a copper alloy, aluminum, an aluminum alloy, iron, an iron alloy, a silver, a silver alloy, a gold, a gold alloy, a zinc, a zinc alloy, a nickel, or a nickel system can be suitably used. Metal foil such as alloy, tin or tin alloy. Further, as the metal foil, an extremely thin metal with a carrier foil may be used.

In the case where the thermally conductive cured product of the present invention is in the form of a sheet, the sheet-like shape The thickness of the thermally conductive cured product can be appropriately set depending on the application, and is usually in the range of 20 to 150 μm.

Since the thermally conductive cured product of the present invention exhibits good thermal conductivity, A resin substrate which is various members of the electric and electronic fields such as a printed wiring board, a semiconductor sealing insulating material, a power semiconductor, an LED lighting, an LED backlight, a power LED, and a solar battery can be widely used. More specifically, it can be used for a prepreg, a sealant, a laminated substrate, a coatable adhesive, a heat dissipation sheet, an adhesive sheet, and the like.

The oxime compound of the present invention is represented by the following general formula (2). The invention The compound is particularly suitable as a decane coupling agent carried on a thermally conductive filler which is used in a resin composition which is a raw material for the production of a thermally conductive cured product.

(In the above general formula (2), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, A ² represents an alkanediyl group having 1 to 4 carbon atoms, and X represents the following a group represented by any one of the formulae (X-1) to (X-6), wherein Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and a carbon number of 1 to 12; Linear or branched oxyalkyl, dimethylamino, diethylamino or ethylmethylamino.)

The R ¹ , Y and X systems in the general formula (2) are synonymous with R ¹ , Y and X in the above general formula (1), respectively. Further, in the general formula (2), A ² represents an alkanediyl group having 1 to 4 carbon atoms. Examples of the alkanediyl group having 1 to 4 carbon atoms include a methylene group, an exoethyl group, a propyl group, and a butyl group.

X in the general formula (2) is preferably a group represented by the formula (X-1), the formula (X-3), the formula (X-4) or the formula (X-6). If the oxime compound in which the X in the general formula (2) is a group represented by the formula (X-1), the formula (X-3), the formula (X-4) or the formula (X-6) is used, the obtained product can be obtained. The thermal conductivity of the thermally conductive hardened material is greatly improved. Further, when A ² in the general formula (2) is a stretching propyl group, it is preferable from the economical side.

As a preferable specific example of the hydrazine compound represented by the general formula (2), for example, Compound Nos. 1 to 54 shown in the above Chemical Formulas No. 1 to No. 54. Further, in the ruthenium compound represented by the above general formula (2), two kinds of geometric isomers caused by an azo group may be present. This is not to be distinguished in the present invention, and may be one geometric isomer or a mixture of two geometric isomers.

The hydrazine compound represented by the general formula (2) can be produced by a well-known reaction. It is made without any limitation depending on its manufacturing method. The hydrazine compound represented by the general formula (2) can be, for example, a carboxylic acid having a structure corresponding to the target compound and a trialkoxy decane having an amine group represented by 3-aminopropyltrialkoxydecane. It is produced by reacting with a condensing agent typified by O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate under basic conditions.

The hydrazine compound of the present invention can be suitably used as a heat conductive filler A decane coupling agent is used. In addition to the decane coupling agent for a thermally conductive filler, the ruthenium compound of the present invention may suitably be used as a synthetic intermediate for optical recording materials, pharmaceuticals, agricultural chemicals, perfumes, dyes, and the like; various functional materials, various polymerizations. Raw materials; photoelectrochemical cells, non-linear optical devices, electrochromic displays, holograms, organic semiconductors, organic EL; silver halide photo-sensitive materials, photosensitizers; used in printing inks, inkjet, electronic photo color toners Coloring agent for cosmetics, plastics, etc.; dyeing agent for protein, luminescent dye for substance detection; synthetic quartz raw material, coating, synthetic catalyst, catalyst carrier, The surface is coated with a film material, a polyoxyethylene rubber crosslinking agent, a binder, and the like.

The decane coupling agent composition of the present invention contains the general formula (2) The indole compound of the invention can be carried, for example, on the carrier. The decane coupling agent composition of the present invention may further contain an organic solvent as a component other than the oxime compound represented by the general formula (2).

As a method of supporting the decane coupling agent on the carrier, a known method can be used. Methods. For example, a method such as vapor phase adsorption or liquid phase adsorption can be used. Further, as an example of the liquid phase adsorption, for example, a method in which a carrier is immersed in a solution obtained by dissolving the ruthenium compound of the present invention in a solvent to adsorb the ruthenium compound to the carrier.

For example, in the manufacture of a thermally conductive filler such as aluminum nitride dispersed in an epoxy tree In the case of the resin composition in the fat, when the decane coupling agent composition of the present invention is carried on the thermally conductive filler, the dispersibility of the thermally conductive filler is improved. In addition, the thermal conductivity of the thermally conductive cured product obtained by curing the resin composition in which the aluminum nitride filler containing the decane coupling agent composition of the present invention is dispersed in an epoxy resin is thermally conductive. Significantly improved. Further, when the shape of the thermally conductive cured product is in the form of a sheet, it is possible to prevent the occurrence of voids, a decrease in dielectric breakdown voltage, and a decrease in sheet toughness due to a decrease in breaking elongation.

As an organic solvent which can be contained in the composition of the decane coupling agent of the present invention, For example, an alcohol solvent, a glycol solvent, a ketone solvent, an ester solvent, an ether solvent, an aliphatic or alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent having a cyano group, or a halogenated aromatic hydrocarbon Reagents, other solvents, etc.

Examples of the alcohol-based solvent include methanol, ethanol, propanol, and 2-propanol. 1-butanol, isobutanol, 2-butanol, tert-butanol, pentanol, isoamyl alcohol, 2-pentanol, neopentyl alcohol, third pentanol, hexanol, 2-hexanol, heptanol , 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, Cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2-( N,N-dimethylamino)ethanol, 3(N,N-dimethylamino)propanol, and the like.

Examples of the diol solvent include ethylene glycol, propylene glycol, and 1,2-butane. Alcohol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprenediol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3- Hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4- Cyclohexanediol, 1,4-cyclohexanedimethanol, and the like.

The ketone solvent may, for example, be acetone, ethyl methyl ketone or methyl isopropyl. Ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, ethyl butyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, A Kepentyl ketone, cyclohexanone, methylcyclohexanone, and the like.

Examples of the ester solvent include methyl formate, ethyl formate, and acetic acid. Ester, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, second butyl acetate, third butyl acetate, amyl acetate, isoamyl acetate, third amyl acetate, phenyl acetate , methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, second butyl propionate, tert-butyl propionate, amyl propionate, propionic acid Amyl ester, third amyl propionate, phenyl propionate, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate Ester, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate , ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether Acetate, ethylene glycol monobutyl ether Acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol single Third butyl ether acetate, butanediol monomethyl ether acetate, butanediol monoethyl ether acetate, butanediol monopropyl ether acetate, butanediol monoisopropyl ether acetate, Glycol monobutyl ether acetate, butanediol monobutyl ether acetate, butanediol monoisobutyl ether acetate, butanediol monobutyl ether acetate, methyl acetate methyl acetate, Ethyl acetate, ethyl acetobutanoate, ethyl acetobutanoate, γ-lactone, dimethyl malonate, dimethyl succinate, propylene glycol diacetate, δ-lactone, etc. .

Examples of the ether solvent include tetrahydrofuran and tetrahydropyran. Porphyrin, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, two Alkane, etc.

Examples of the aliphatic or alicyclic hydrocarbon-based solvent include pentane and hexane. Cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decahydronaphthalene, mineral spirits, turpentine, D-oxime, decene, ore, trade name "Swasol #310" (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and trade name "Solvesso #100" (manufactured by Exxon Chemical Co., Ltd.).

Examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, symmetrical trimethylbenzene, diethylbenzene, cumene, isobutylbenzene, isopropyltoluene, and tetrahydronaphthalene.

Examples of the hydrocarbon solvent having a cyano group include acetonitrile, 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, and 1,3-dicyanopropane. , 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene, and the like.

Examples of the halogenated aromatic hydrocarbon-based solvent include carbon tetrachloride and chloroform. Trichloroethylene, dichloromethane, etc.

As another organic solvent, N-methyl-2-pyrrolidone, for example, Methyl hydrazine, dimethylformamide, aniline, triethylamine, pyridine.

The carrier system of the present invention carries the above-described decane coupling agent group of the present invention. Adult. The decane coupling agent composition is carried, for example, on a carrier or the like. Examples of the carrier to be supported include an organic resin such as an acrylic resin or a fluororesin, a metal oxide such as tantalum carbide, titanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or aluminum nitride, boron nitride or tantalum nitride. , cerium oxide, diatomaceous earth, activated carbon, and the like. As a method of supporting the decane coupling agent composition on the carrier, a known method such as vapor phase adsorption or liquid phase adsorption can be used. Further, as an example of the liquid phase adsorption, for example, a method in which a carrier is immersed in a solution obtained by dissolving a decane coupling agent composition in a solvent to adsorb a decane coupling agent composition to a carrier. .

For example, the decane coupling agent composition is carried on the nitrogen as the carrier The carrier obtained by the aluminum filler is dispersed in an epoxy resin to obtain a resin composition. When the obtained resin composition is hardened, a thermally conductive cured product having high thermal conductivity can be produced.

The shape of the carrier to be carried is not particularly limited, and it may be used by the use of the carrier. For example, a shape such as a film form, a powder form, or a granular shape is appropriately selected. Further, the size of the carrier to be carried or the amount of the decane coupling agent composition contained in the carrier is not particularly limited, and may be appropriately selected depending on the use of the carrier. For example, when a resin composition for obtaining a sheet-shaped thermally conductive cured product is produced, when the average particle diameter of the carrier is from 1 to 100 μm, the effect of improving the thermal conductivity is high, which is preferable. In addition, the "average particle diameter" in this specification means the particle diameter at 50% of the integrated value in the particle size distribution obtained by the laser diffraction ‧ scattering method.

The carrier of the present invention, in addition to being formulated for use as a manufacturing heat conductive hard In addition to the resin composition of the material of the compound, it can also be used for a photoelectric conversion element, a catalyst, a carbon powder, or the like.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples and the like.

<Synthesis of hydrazine compounds> [Example 1] Synthesis of Compound No. 19

Biphenyl-4-carboxylic acid (5.0 mmol, 1.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.), o-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium Fluorophosphate (5.0 mmol, 1.9 g) and dimethylformamide (10.0 ml) were placed in a flask and stirred at 40 ° C for 0.5 hour. Thereafter, N,N-diisopropylethylamine (10.0 mm, 1.3 g) and 3-aminopropyltriethoxydecane (5.0 mmol, 1.12 g) were added and stirred for 2 hr. Water (5 ml) and chloroform (5 ml) were added to the reaction mixture to carry out an oily water solution. The obtained organic layer was purified by column chromatography (mobile phase: hexane/ethyl acetate=3/1 (mass ratio)) to yield 1.49 g (yield: 74%) of white solid. The solid obtained was confirmed to be Compound No. 19 using UV-VIS (λmax) and ¹ H-NMR (deuterated solvent: CDCl ₃ ). The yield and appearance observation results are shown in Table 1. Further, the results of ¹ H-NMR are shown in Table 2.

[Examples 2 to 9] Synthesis of Compound Nos. 1, 10, 20, 24, 28, 37, 43 and 46

Compound No. 1, 10, 20, 24, 28 was synthesized in the same manner as in Example 1 except that the biphenyl-4-carboxylic acid used in Example 1 was changed to a carboxylic acid having a structure corresponding to the target compound. , 37, 43 and 46. The compound synthesized was confirmed to be the target compound by using UV-VIS (λmax) and ¹ H-NMR (deuterated solvent: CDCl ₃ ). The yield and appearance observation results are shown in Table 1. Further, the results of ¹ H-NMR are shown in Table 2.

[Manufacturing Example 1] Synthesis of Compound No. 88

Compound No. 88 was synthesized in the same manner as in Example 1 except that a carboxylic acid compound and an amine compound having a structure corresponding to the target compound were used. The compound synthesized was confirmed to be the target compound by using UV-VIS (λmax) and ¹ H-NMR (deuterated solvent: CDCl ₃ ). The yield and appearance observation results are shown in Table 1. Further, the results of ¹ H-NMR are shown in Table 2.

<Manufacture of carrier body> [Example 10] Production of carrier No. 1

10.0 g of an aluminum nitride filler (manufactured by Tokuyama Co., Ltd., H grade, spherical shape, particle diameter: 1 μm) was weighed in a 100 ml eggplant type flask, and 50.0 mg of the compound No. 19 and 50 ml of toluene were added thereto to carry out ultrasonic treatment 30. minute. Thereafter, the solvent was evaporated by a vacuum heat treatment at 50 °C. Further, vacuum heat treatment at 100 ° C was carried out for 2 hours, and Compound No. 19 was immobilized on the surface of the aluminum nitride filler to obtain a carrier No. 1.

[Examples 11 to 18] Manufacturing of carrier Nos. 2 to 9

The carrier No. 2 was obtained in the same manner as in Example 10 except that the compound No. 19 used in Example 10 was changed to No. 1, 10, 20, 24, 28, 37, 43 and 46, respectively. 9.

[Examples 19 to 21] Manufacturing of carrier Nos. 10 to 12

In addition, the aluminum nitride filler used in the tenth embodiment was changed to a mixed filler (aluminum nitride filler (H grade, spherical shape, particle diameter: 1 μm, manufactured by Tokuyama Co., Ltd.), 0.83 g, alumina filler (electrical Chemical Industry Co., Ltd., DAW-20, spherical, particle size: 20 μm) 5.50 g, alumina filler (manufactured by Electric Chemical Industry Co., Ltd., DAW-03, spherical, particle size: 3 μm) 1.38 g, and alumina filled The material (manufactured by Showa Denko Co., Ltd., AL-47-1, broken form, particle size: 1 μm) 2.29 g), and the compound No. 19 were changed to the compound Nos. 20, 24, and 43, respectively, and Example 10 The carrier No. 10 to 12 was obtained by the same method.

[Manufacturing Example 2] Production of Carrier No. 13

The carrier No. 13 was obtained by the same method as in Example 10 except that the compound No. 19 used in Example 10 was changed to the compound No. 88.

[Manufacturing Examples 3 to 5] Comparison of Manufacturing of Carrier Nos. 1 to 3

A comparison load was obtained in the same manner as in Example 10 except that the compound No. 19 used in Example 10 was changed to Comparative Compounds 1 to 3 represented by the following formulas (C-1) to (C-3), respectively. Hold body 1~3.

Regarding the carrier Nos. 1 to 13 and the comparative carriers 1 to 3, the correspondence between the filler and the ruthenium compound used is shown in Table 3.

<evaluation> [Evaluation Example 1] Confirmation of immobilized amount

50 ml of toluene was added to the carrier No. 1 and stirred for 30 minutes, and then left to stand for 30 minutes to completely settle the solid to obtain a sample for analysis 1. The supernatant of the sample for analysis 1 was divided into 1 ml, and diluted to 25 times with toluene to obtain a sample for analysis 2. The analysis sample 2 was subjected to UV-VIS measurement to calculate the molar concentration of the compound No. 19 in the sample for analysis 2. Then, the immobilization amount of the compound No. 19 immobilized on the carrier No. 1 was calculated by the following calculation formula 1. As a result, it was found that the carrier No. 1 was attached to the surface of 10 g of the aluminum nitride filler, and 31.6 mg (6.7 × 10 ^-5 mol) of the compound No. 19 was immobilized.

Formula 1: S ¹ = S ² - (C × 25 × molecular weight of compound No. 19 × L)

S ¹ : immobilization amount (g) of the compound No. 19 immobilized on the carrier No. 1

S ² : the amount of the compound No. 19 used in the production of the carrier No. 1 (g)

L: total volume of supernatant (l)

C: molar concentration (mol/l) of compound No. 19 in sample 2 for analysis

<Manufacture of Resin Composition> [Examples 22 to 34] Production of Resin Composition Nos. 1 to 13

7 g of a biphenyl aralkyl type epoxy resin (trade name "NC-3000H", manufactured by Nippon Kayaku Co., Ltd.) and a biphenyl aralkyl phenol were added to the carrier No. 1 to 13 (50 g). Resin (product name "MEH-7851H", manufactured by Megumi Kasei Co., Ltd.) 3.5 g of a solution dissolved in 10.5 g of methyl ethyl ketone, and an imidazole-based curing agent (trade name "2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.) 0.1 g was dispersed using three roll mills to obtain resin compositions No. 1 to 13.

[Manufacturing Examples 6 to 10] Comparison of Manufacturing of Resin Compositions 1 to 5

50 g of (i) aluminum nitride filler (manufactured by Tokuyama Co., Ltd., H grade, spherical, particle size: 1 μm), (ii) mixed filler (aluminum nitride filler (manufactured by Tokuyama, H grade, spherical) , Particle size: 1 μm) 0.83 g, alumina filler (DAW-20, spherical, particle size: 20 μm), 5.50 g, alumina filler (manufactured by Electric Chemical Industry Co., Ltd., DAW-03, ball) Shape, particle size: 3 μm) 1.38 g, and alumina filler (manufactured by Showa Denko, AL-47-1, crushed, particle size: 1 μm) 2.29 g), or (iii) comparative carrier 1 to 3 And 7 g of a biphenyl aralkyl type epoxy resin (trade name "NC-3000H", manufactured by Nippon Kayaku Co., Ltd.) and a biphenyl aralkyl type phenol resin (trade name "MEH-7851H") were added. 3.5 g of a solution prepared by dissolving methyl ketone (10.5 g) and 0.1 g of an imidazole-based curing agent (trade name "2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.). Then, it was dispersed using three roll mills to obtain comparative resin compositions 1 to 5.

Regarding resin compositions No. 1 to 13 and comparative resin compositions 1 to 5, The correspondence between the carriers used is shown in Table 4.

<Manufacture of Thermal Conductive Sheet> [Examples 35 to 47] Production of cured materials No. 1 to 13

The resin composition Nos. 1 to 13 were applied to the PET film by a bar coater method at a thickness of 100 μm, and dried by heating at 100 ° C for 10 minutes. After heating at 190 ° C for 90 minutes to cure the film, the PET film was peeled off to produce cured products No. 1 to 13 which were sheet-shaped thermally conductive cured products.

[Manufacturing Examples 11 to 15] Comparison of the manufacture of cured products 1 to 5

The comparative resin compositions 1 to 5 were applied to the PET film by a bar coater method to a thickness of 100 μm, and dried by heating at 100 ° C for 10 minutes. After heating at 190 ° C for 90 minutes to cure the film, the PET film was peeled off to produce comparative hardened materials 1 to 5 which were sheet-shaped thermally conductive cured products.

The correspondence between the cured materials No. 1 to 13 and the comparative cured materials 1 to 5 and the resin compositions used is shown in Table 5.

<evaluation> [Evaluation Example 2] Evaluation of Thermal Conductivity

For the cured materials No. 1 to 13 and the comparative hardened materials 1 to 5, the thermal diffusivity was measured by a periodic heating method using a thermal diffusivity ‧ thermal conductivity measuring device (trade name "ai-Phase Mobile", manufactured by ai-Phase Co., Ltd.) . The results are shown in Table 6.

As shown in Table 6, it can be seen that compared with the thermal diffusivity of the comparative hardened materials 1 to 5, The thermal diffusivity of the cured materials No. 1 to 13 is increased by about 10 to 38%. Among them, it was found that the cured materials No. 1, 4, and 8 showed particularly high thermal conductivity. From the above, it is understood that the cured product produced by using the resin composition of the present invention is a thermally conductive cured product having high thermal conductivity.

Claims (5)

A resin composition comprising a carrier carrying a composition of a decane coupling agent, wherein the decane coupling agent composition comprises a hydrazine compound represented by the following general formula (1); (In the above general formula (1), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and A ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched oxyalkyl group having 1 to 12 carbon atoms, a dimethylamino group, a diethylamino group or an ethyl group. Methylamino group; X represents a group represented by any one of the following formulas (X-1) to (X-6), and when X is a group represented by the following formula (X-1), Z is - When NHCO-, X is a group represented by any one of the following formulas (X-2) to (X-6), Z is a single bond or -NHCO-) A thermally conductive cured product obtained by hardening a resin composition of the first aspect of the patent application. An anthracene compound represented by the following general formula (2); (In the above general formula (2), R ¹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, A ² represents an alkanediyl group having 1 to 4 carbon atoms, and X represents the following a group represented by any one of the formulae (X-1) to (X-6), wherein Y represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and a carbon number of 1 to 12; Linear or branched oxyalkyl, dimethylamino, diethylamino or ethylmethylamino) A decane coupling agent composition containing the quinone compound of claim 3 of the patent application. A carrier comprising a decane coupling agent composition of claim 4 of the patent application.