JP7220864B2 - Thermally conductive insulating composition, thermally conductive insulating molded article, and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermally conductive insulating composition, a thermally conductive insulating molded product, and a method for producing the same, which are useful as materials for members such as electronic circuit boards that require insulation and heat dissipation.

2. Description of the Related Art With the miniaturization and high integration of electrical and electronic equipment, the heat generated by mounted parts and the high temperature of the operating environment have become conspicuous, and the demand for improving the heat dissipation of constituent members has increased. In particular, metals and ceramics with high thermal conductivity are currently used for automobile parts and heat dissipation parts for high-power LEDs. , and a thermally conductive resin material having moldability. In particular, polymer materials such as resins are inexpensive insulating materials with excellent moldability, so they are used in various electronic components such as substrates for electronic circuit boards, motor insulating materials, and insulating adhesives. . In recent years, the amount of heat generated from these electronic components has increased as the density and output of these electronic components have increased. Therefore, there is a strong demand for countermeasures for releasing heat from electronic components.

In order to solve this problem, in the prior art, a method is used in which a filler made of an inorganic substance such as alumina or silica is filled inside the resin to increase the thermal conductivity of the resin. For example, Patent Literatures 1 and 2 propose a technique of adding crystalline silica and an inorganic filler such as aluminum oxide to a polymer resin to impart thermal conductivity. In this case, a continuum formed by connecting inorganic fillers functions as a heat conducting path. That is, the inorganic filler filled in the resin must be in contact with each other, and a large amount of inorganic filler must be filled for efficient heat conduction. Furthermore, conventional thermally conductive insulating resin moldings require the addition of a large amount of inorganic filler, and thus have the following technical problems. (1) Heavy weight. (2) Inorganic fillers are hard and have poor workability. (3) Air gaps are likely to occur at the interface between the inorganic filler and the resin, and water stays there, resulting in low moisture resistance. (4) Inorganic fillers are expensive, resulting in high production costs. (5) A resin molded article with a large amount of inorganic filler filled therein requires a certain thickness in order to retain its shape, and it is difficult to make it thinner. In order to solve these problems, Patent Document 3 discloses a core/shell particle comprising a core particle containing a polymer compound and a shell containing a thermally conductive and insulating inorganic compound covering the core particle. A thermally conductive insulating resin molded body formed from an aggregate has been proposed.

JP-A-11-233694 Japanese Patent No. 3559137 Japanese Patent No. 5278488

However, the thermally conductive insulating resin molded article described in Patent Document 3 has a problem of low thermal conductivity because core particles containing a polymer compound are coated with a shell containing an inorganic compound. In addition, in the conventional thermally conductive insulating resin molded product, the inorganic filler filled in the resin tends to aggregate, and it is difficult to form a continuous body formed by connecting the inorganic filler, so sufficient thermal conductivity cannot be obtained. There was no problem.

The present invention provides a thermally conductive insulating molded article that has excellent thermal conductivity and insulating properties even when the content of inorganic filler is small, a method for producing the same, and a thermally conductive insulating composition for obtaining the thermally conductive insulating molded article. intended to provide

The present inventors have made intensive studies to solve the above problems, and as a result, found that the above objects can be achieved by adding a triazinedithiol-based compound together with an inorganic filler to a thermally conductive insulating composition. I have perfected my invention.

（式中、Ｍ^１及びＭ^２はそれぞれ独立にＨ、Ｌｉ、Ｎａ、Ｋ、又はＣｓであり、Ｒ^１はＳ、Ｏ、又はＮＲ^３であり、Ｒ^３はＨ、又はアルキル基、ハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシアルキル基、アルケニル基、ハロゲン化アルケニル基、ヒドロキシアルケニル基、アルコキシアルケニル基、フェニル基、ハロゲン化フェニル基、ヒドロキシフェニル基、アルコキシフェニル基、ビフェニル基、ハロゲン化ビフェニル基、ヒドロキシビフェニル基、アルコキシビフェニル基、ナフチル基、ハロゲン化ナフチル基、ヒドロキシナフチル基、アルコキシナフチル基、カルボキシル基、エステル基、ウレタン基、アゾ基、シアノ基、アミノ基、アミド基、及びアルコキシシリル基からなる群より選択される少なくとも１種の官能基を有する有機基であり、Ｒ^２は前記有機基と同じであり、あるいはＮＲ^３とＲ^２はヘテロ環を構成する。）
［２］
前記トリアジンジチオール系化合物は、下記一般式（２）～（４）で表されるトリアジンジチオール系化合物の少なくとも１種である［１］に記載の熱伝導性絶縁組成物。

（式中、Ｍ^１、Ｍ^２、Ｒ^２、及びＲ^３は前記と同じである。）

（式中、Ｍ^１及びＭ^２は前記と同じであり、Ｒ^１はＳ、Ｏ、－ＮＨＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_３）ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（Ｃ_３Ｈ_７）ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（Ｃ_２Ｈ_５）ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２（ＣＨ_２）_８ＣＨ_２Ｏ－、－ＮＨＣＨ_２ＣＨ（ＣＨ_３）Ｏ－、－ＮＨＣ_６Ｈ_４Ｏ－、－Ｎ（Ｃ_２Ｈ_５）Ｃ_６Ｈ_４Ｏ－、－ＮＨＣ_１０Ｈ_６Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２）_２ＣＨＯ－、－Ｎ（ＣＨ_２ＣＨ_２）_２ＮＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ（ＣＨ_３）ＯＨ）ＣＨ_２ＣＨ（ＣＨ_３）Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２Ｃ_６Ｈ_４Ｏ－、－ＮＨＣ_６Ｈ_１１Ｏ－、又は－Ｎ（Ｃ_３Ｈ_７）Ｃ_６Ｈ_４Ｏ－であり、Ｒ^４はアルキレン基であり、Ｒ^５はアルコキシ基であり、Ｒ^６及びＲ^７はそれぞれ独立にアルコキシ基又はアルキル基である。）

（式中、Ｍ^１、Ｍ^２、及びＲ^５～Ｒ^７は前記と同じであり、Ｒ^８は水素又はアルキル基であり、Ｒ^９はアルキレン基又はアルキレンオキシ基であり、Ｒ^８とＲ^９は互いに結合して環を形成してもよい。）
［３］
前記高分子材料は、エラストマーを含む［１］又は［２］に記載の熱伝導性絶縁組成物。
［４］
前記エラストマーは、ポリエステル系エラストマー及びポリアミド系エラストマーからなる群より選択される少なくとも１種である［３］に記載の熱伝導性絶縁組成物。
［５］
前記無機フィラーは、窒化アルミニウムフィラー及び窒化ホウ素フィラーからなる群より選択される少なくとも１種を含む［１］～［４］のいずれかに記載の熱伝導性絶縁組成物。
［６］
前記無機フィラーの含有量は、前記高分子材料１００質量部に対して２０～４００質量部である［１］～［５］のいずれかに記載の熱伝導性絶縁組成物。
［７］
前記トリアジンジチオール系化合物の含有量は、前記無機フィラー１００質量部に対して５×１０^－７～５質量部である［１］～［６］のいずれかに記載の熱伝導性絶縁組成物。
［８］
［１］～［７］のいずれかに記載の熱伝導性絶縁組成物から得られる熱伝導性絶縁成形体。
［９］
前記熱伝導性絶縁成形体は、熱伝導性絶縁シートである［８］に記載の熱伝導性絶縁成形体。
［１０］
［８］又は［９］に記載の熱伝導性絶縁成形体の製造方法であって、前記無機フィラーと前記トリアジンジチオール系化合物とを接触させて、前記無機フィラーの表面に前記トリアジンジチオール系化合物を付着させて表面修飾無機フィラーを得る工程Ａ、前記表面修飾無機フィラーを前記高分子材料中に分散させて前記熱伝導性絶縁組成物を得る工程Ｂ、及び前記熱伝導性絶縁組成物を成形する工程Ｃを含む熱伝導性絶縁成形体の製造方法。
［１１］
前記工程Ｃにおいて、前記熱伝導性絶縁組成物を加圧及び／又は加熱して成形する［１０］に記載の熱伝導性絶縁成形体の製造方法。 That is, the present invention consists of the following configurations.
[1]
A thermally conductive insulating composition containing a polymeric material, an inorganic filler, and a triazinedithiol-based compound represented by the following general formula (1).

(wherein M ¹ and M ² are each independently H, Li, Na, K, or Cs, R ¹ is S, O, or NR ³ , R ³ is H, or an alkyl group, halogenated Alkyl group, hydroxyalkyl group, alkoxyalkyl group, alkenyl group, halogenated alkenyl group, hydroxyalkenyl group, alkoxyalkenyl group, phenyl group, halogenated phenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, halogenated biphenyl group , hydroxybiphenyl group, alkoxybiphenyl group, naphthyl group, halogenated naphthyl group, hydroxynaphthyl group, alkoxynaphthyl group, carboxyl group, ester group, urethane group, azo group, cyano group, amino group, amide group, and alkoxysilyl group is an organic group having at least one functional group selected from the group consisting of R ² is the same as the above organic group, or NR ³ and R ² form a heterocyclic ring.)
[2]
The thermally conductive insulating composition according to [1], wherein the triazinedithiol-based compound is at least one triazinedithiol-based compound represented by the following general formulas (2) to (4).

(In the formula, M ¹ , M ² , R ² and R ³ are the same as above.)

(wherein M ¹ and M ² are the same as above, R ¹ is S, O, -NHCH ₂ CH ₂ O-, -N(CH ₃ )CH ₂ CH ₂ O-, -N(C ₃ H _{7 ) CH2CH2O- , -NHCH2CH2CH2CH2O- , -N ( C2H5 ) CH2CH2CH2CH2O- , -NHCH2 ( CH2 ) 8CH2} O—, —NHCH ₂ CH(CH ₃ )O—, —NHC ₆ H ₄ O—, —N(C ₂ H ₅ )C ₆ H ₄ O—, —NHC ₁₀ H ₆ O—, —N(CH _{2 CH2} ) _{2CHO- , -N} ( _{CH2CH2 )2NCH2CH2O- , -N ( CH2CH2OH ) CH2CH2O-} , -N( _{CH2CH2CH2OH ) CH2CH2CH2O- ,} -N _{( CH2CH ( CH3 )} OH _{) CH2CH} ( _{CH3 ) O-} , _-N (CH2CH2CH2CH2OH) _CH2CH2CH2 CH ₂ O—, —NHCH ₂ C ₆ H ₄ O—, —NHC ₆ H ₁₁ O—, or —N(C ₃ H ₇ )C ₆ H ₄ O—, R ⁴ is an alkylene group, R ⁵ is an alkoxy group, and ^R6 and ^R7 are each independently an alkoxy group or an alkyl group.)

(wherein M ¹ , M ² and R ⁵ to R ⁷ are the same as above, R ⁸ is hydrogen or an alkyl group, R ⁹ is an alkylene group or an alkyleneoxy group, R ⁸ and R ⁹ may combine with each other to form a ring.)
[3]
The thermally conductive insulating composition according to [1] or [2], wherein the polymer material contains an elastomer.
[4]
The thermally conductive insulating composition according to [3], wherein the elastomer is at least one selected from the group consisting of polyester elastomers and polyamide elastomers.
[5]
The thermally conductive insulating composition according to any one of [1] to [4], wherein the inorganic filler contains at least one selected from the group consisting of aluminum nitride filler and boron nitride filler.
[6]
The thermally conductive insulating composition according to any one of [1] to [5], wherein the content of the inorganic filler is 20 to 400 parts by mass with respect to 100 parts by mass of the polymer material.
[7]
The thermally conductive insulating composition according to any one of [1] to [6], wherein the content of the triazinedithiol-based compound is 5×10 ⁻⁷ to 5 parts by mass with respect to 100 parts by mass of the inorganic filler.
[8]
A thermally conductive insulating molded article obtained from the thermally conductive insulating composition according to any one of [1] to [7].
[9]
The thermally conductive insulating molded article according to [8], wherein the thermally conductive insulating molded article is a thermally conductive insulating sheet.
[10]
[8] or [9] The method for producing a thermally conductive insulating molded article, wherein the inorganic filler and the triazinedithiol-based compound are brought into contact with each other, and the triazinedithiol-based compound is applied to the surface of the inorganic filler. Step A of attaching to obtain a surface-modified inorganic filler, Step B of dispersing the surface-modified inorganic filler in the polymer material to obtain the thermally conductive insulating composition, and molding the thermally conductive insulating composition A method for producing a thermally conductive insulating molded body including step C.
[11]
The method for producing a thermally conductive insulating molded article according to [10], wherein in the step C, the thermally conductive insulating composition is molded by pressing and/or heating.

The thermally conductive insulating composition of the present invention contains a triazinedithiol compound together with an inorganic filler. By attaching the triazinedithiol-based compound to the surface of the inorganic filler, an inorganic filler surface-modified with the triazinedithiol-based compound (surface-modified inorganic filler) is obtained. Since the surface-modified inorganic filler has higher dispersibility than conventional inorganic fillers, it is less likely to agglomerate in the polymer material. Therefore, a continuum formed by connecting the surface-modified inorganic fillers is likely to be formed in the polymer material. As a result, the thermally conductive insulating molded article obtained from the thermally conductive insulating composition of the present invention has excellent thermal conductivity even when the content of the inorganic filler is small.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

（式中、Ｍ^１及びＭ^２はそれぞれ独立にＨ、Ｌｉ、Ｎａ、Ｋ、又はＣｓであり、Ｒ^１はＳ、Ｏ、又はＮＲ^３であり、Ｒ^３はＨ、又はアルキル基、ハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシアルキル基、アルケニル基、ハロゲン化アルケニル基、ヒドロキシアルケニル基、アルコキシアルケニル基、フェニル基、ハロゲン化フェニル基、ヒドロキシフェニル基、アルコキシフェニル基、ビフェニル基、ハロゲン化ビフェニル基、ヒドロキシビフェニル基、アルコキシビフェニル基、ナフチル基、ハロゲン化ナフチル基、ヒドロキシナフチル基、アルコキシナフチル基、カルボキシル基、エステル基、ウレタン基、アゾ基、シアノ基、アミノ基、アミド基、及びアルコキシシリル基からなる群より選択される少なくとも１種の官能基を有する有機基であり、Ｒ^２は前記有機基と同じであり、あるいはＮＲ^３とＲ^２はヘテロ環を構成する。） The thermally conductive insulating composition of the present invention contains a polymeric material, an inorganic filler, and a triazinedithiol-based compound represented by the following general formula (1).

(wherein M ¹ and M ² are each independently H, Li, Na, K, or Cs, R ¹ is S, O, or NR ³ , R ³ is H, or an alkyl group, halogenated Alkyl group, hydroxyalkyl group, alkoxyalkyl group, alkenyl group, halogenated alkenyl group, hydroxyalkenyl group, alkoxyalkenyl group, phenyl group, halogenated phenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, halogenated biphenyl group , hydroxybiphenyl group, alkoxybiphenyl group, naphthyl group, halogenated naphthyl group, hydroxynaphthyl group, alkoxynaphthyl group, carboxyl group, ester group, urethane group, azo group, cyano group, amino group, amide group, and alkoxysilyl group is an organic group having at least one functional group selected from the group consisting of R ² is the same as the above organic group, or NR ³ and R ² form a heterocyclic ring.)

<Polymer material>
Any known polymeric material can be used without particular limitation, and is appropriately selected according to the application of the thermally conductive insulating molding. Polymeric materials include, for example, elastomers, thermoplastics, thermosets, and rubbers. These may be used alone or in combination of two or more.

Examples of elastomers include silicone-based elastomers, fluorine-based elastomers, polyester-based elastomers, polyamide-based elastomers, rubber-based elastomers, olefin-based elastomers, styrene-based elastomers, vinyl chloride-based elastomers, and polyurethane-based elastomers. These may be used alone or in combination of two or more.

Examples of thermoplastic resins include general-purpose plastics such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, thermoplastic polyurethanes, fluororesins, ABS resins, AS resins, and (meth)acrylic resins; Engineering plastics such as polyester, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, and cyclic polyolefin; polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, amorphous polyarylate, liquid crystal polymer, polyetheretherketone, thermoplastic polyimide , and super engineering plastics such as polyamideimide. These may be used alone or in combination of two or more.

Thermosetting resins include, for example, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, thermosetting polyurethanes, and thermosetting polyimides. These may be used alone or in combination of two or more.

Examples of rubber include natural rubber, isoprene rubber, styrene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile rubber, ethylene propylene rubber, acrylic rubber, urethane rubber, and fluororubber. These may be used alone or in combination of two or more.

In the present invention, it is preferable to use an elastomer as the polymeric material, more preferably at least one selected from the group consisting of polyester elastomers and polyamide elastomers, and still more preferably polyester elastomers.

The elastomer content is preferably 20% by weight or more, more preferably 30% by weight or more, still more preferably 40% by weight or more, and particularly preferably 100% by weight, based on the entire polymeric material.

A known polyester-based elastomer can be used without particular limitation. Examples of polyester-based elastomers include reaction products of dicarboxylic acids and diols.

Dicarboxylic acids are not particularly limited, and examples thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and unsaturated dicarboxylic acids. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 1 , 3-phenylenedioxydiacetic acid, and functional derivatives thereof. Examples of aliphatic dicarboxylic acids and alicyclic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2 , 5-norbornanedicarboxylic acid, dimer acid, and hydrogenated dimer acid. Examples of unsaturated dicarboxylic acids include fumaric acid and itaconic acid. Also, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof may be used. These may be used alone or in combination of two or more.

Diols are not particularly limited and include, for example, aromatic glycols, aliphatic glycols, alicyclic glycols, and unsaturated glycols. Examples of aromatic glycols include hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 1,4-bis(β-hydroxyethoxyphenyl)sulfone, bis(p-hydroxy phenyl)ether, bis(p-hydroxyphenyl)sulfone, bis(p-hydroxyphenyl)methane, 1,2-bis(p-hydroxyphenyl)ethane, bisphenol A, and alkylene oxide adducts of bisphenol A. . Examples of aliphatic glycols and alicyclic glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3 -butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3 -cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-1,3- Propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl- 2-n-butyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 2-ethyl -2-n-hexyl-1,3-propanediol, 2,2-di-n-hexyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecane Diol, diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypropylene glycol and the like. These may be used alone or in combination of two or more.

Moreover, you may use polyhydric carboxylic acid more than trifunctional. Examples of the polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, methylcyclohexene tricarboxylic acid, oxydiphthalic dianhydride (ODPA), and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride. (BTDA), 3,3′,4,4′-diphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 '-(Hexafluoroisopropylidene)diphthalic dianhydride (6FDA) and 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA). These may be used alone or in combination of two or more.

Moreover, you may use the polyhydric alcohol more than trifunctional. Examples of the polyhydric alcohol include glycerin, pentaerythritol, trimethylolethane, trimethylolpentane, and trimethylolpropane. These may be used alone or in combination of two or more.

The polyester-based elastomer is preferably selected from the group in which the hard segment is composed of a polyester of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and the soft segment is composed of an aliphatic polyether, an aliphatic polyester, and an aliphatic polycarbonate. It is composed of one or more selected types, and is formed by combining the hard segment and the soft segment.

As the aromatic dicarboxylic acid constituting the polyester of the hard segment, a general aromatic dicarboxylic acid is widely used, for example, terephthalic acid or naphthalenedicarboxylic acid (among the isomers, 2,6-naphthalenedicarboxylic acid is preferred). is mentioned. Other dicarboxylic acids include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid, and 5-sodiumsulfoisophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride, succinic acid, and glutaric acid. , adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These may be used alone or in combination of two or more.

As the aliphatic or alicyclic diol constituting the hard segment polyester, general aliphatic or alicyclic diols are widely used, and alkylene glycols having 2 to 8 carbon atoms are preferred. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in combination of two or more. Among these, at least one selected from ethylene glycol and 1,4-butanediol is preferable.

From the viewpoint of physical properties, moldability, and cost performance, the components that make up the hard segment polyester include butylene terephthalate units (units consisting of terephthalic acid and 1,4-butanediol) or butylene naphthalate units (2,6- Units consisting of naphthalenedicarboxylic acid and 1,4-butanediol) are preferred.

When an aromatic polyester suitable as the polyester constituting the hard segment is produced in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained according to a normal polyester production method. Moreover, the number average molecular weight of such polyester is preferably 1,000 to 40,000.

The soft segment is at least one selected from aliphatic polyethers, aliphatic polyesters, and aliphatic polycarbonates.

Aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, poly(trimethylene oxide) glycol, co-polymer of ethylene oxide and propylene oxide. polymers, ethylene oxide adducts of poly(propylene oxide) glycol, and copolymers of ethylene oxide and tetrahydrofuran. These may be used alone or in combination of two or more. Among these, at least one selected from poly(tetramethylene oxide) glycol and an ethylene oxide adduct of poly(propylene oxide) glycol is preferred from the viewpoint of elastic properties.

Aliphatic polyesters include poly(ε-caprolactone), polyenantholactone, polycapryrolactone, and polybutylene adipate. These may be used alone or in combination of two or more. Among these, at least one selected from poly(ε-caprolactone) and polybutylene adipate is preferable from the viewpoint of elastic properties.

The aliphatic polycarbonate preferably contains an aliphatic diol residue having 2 to 12 carbon atoms. Examples of the aliphatic diol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2 -dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8- octanediol and the like. These may be used alone or in combination of two or more. In particular, aliphatic diols having 5 to 12 carbon atoms are preferred from the viewpoint of the flexibility and low-temperature properties of the resulting polyester-based elastomer.

As the aliphatic polycarbonate diol which constitutes the soft segment and which has good low-temperature properties, one having a low melting point (for example, 70° C. or lower) and a low glass transition temperature is preferred. Aliphatic polycarbonate diols containing 1,6-hexanediol, which are generally used to form soft segments of polyester elastomers, have a low glass transition temperature of around -60°C and a melting point of around 50°C. The low-temperature characteristics of are good. In addition, an aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of, for example, 3-methyl-1,5-pentanediol with the above-mentioned aliphatic polycarbonate diol has a glass transition point higher than that of the original aliphatic polycarbonate diol. Although the melting point is lowered or becomes amorphous, the aliphatic polycarbonate diol has good low-temperature properties. In addition, for example, an aliphatic polycarbonate diol containing 1,9-nonanediol and 2-methyl-1,8-octanediol has a melting point of about 30°C and a glass transition temperature of about -70°C, which are sufficiently low. It is an aliphatic polycarbonate diol with good properties.

From the viewpoint of solving the problems of the present invention, the soft segment of the polyester-based elastomer is preferably an aliphatic polyether.

The polyester-based elastomer is preferably a copolymer containing terephthalic acid, isophthalic acid, 1,4-butanediol, and poly(tetramethylene oxide) glycol as main components. The total amount of terephthalic acid and isophthalic acid in the dicarboxylic acid component constituting the polyester elastomer is preferably 40 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. , is particularly preferably 90 mol % or more. Among the diol components constituting the polyester elastomer, the total amount of 1,4-butanediol and poly(tetramethylene oxide) glycol is preferably 40 mol% or more, more preferably 70 mol% or more, and 80 mol. % or more, and particularly preferably 90 mol % or more.

The poly(tetramethylene oxide) glycol preferably has a number average molecular weight of 500-4000. If the number average molecular weight is less than 500, it may be difficult to develop elastomeric properties. On the other hand, if the number average molecular weight exceeds 4,000, the compatibility with the hard segment component may be lowered, making block-like copolymerization difficult. The number average molecular weight of poly(tetramethylene oxide) glycol is more preferably 800-3000, more preferably 1000-2500.

In the polyester-based elastomer, the soft segment content is preferably 20 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 20 to 50% by mass. If the content of the soft segment is less than 20% by mass, the crystallinity is too high, resulting in poor impact absorption. .

A polyester-based elastomer can be produced by a known method. For example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol, and a soft segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product, a dicarboxylic acid and an excessive amount of glycol. and the soft segment component are subjected to an esterification reaction in the presence of a catalyst, and the resulting reaction product is polycondensed. A method of randomizing, a method of connecting the hard segment and the soft segment with a chain linking agent, and a method of adding ε-caprolactone monomer to the hard segment when poly (ε-caprolactone) is used for the soft segment. You can take the method of

Methods for determining the composition and composition ratio of the polyester elastomer include, for example, a method of calculating from the proton integral ratio of ¹ H-NMR measured by dissolving a sample in a solvent such as heavy chloroform.

Known polyamide-based elastomers can be used without particular limitations. As the polyamide-based elastomer, for example, the hard segment is nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, or their copolymerized nylon, and the soft segment has an average molecular weight of about 300 to 5000. polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide-propylene oxide copolymer containing one or more blocks composed of polyalkylenediol. Furthermore, those in which non-elastomeric components are blended or copolymerized may be mentioned.

<Inorganic filler>
Any known inorganic filler can be used without any particular limitation. Examples of inorganic fillers include aluminum, copper, nickel; alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide; boron nitride, aluminum nitride, silicon nitride, titanium nitride, tantalum nitride, chromium nitride; titanium boride, boron Zirconium boride, hafnium boride, yttrium boride, vanadium boride, magnesium diboride, niobium boride, tantalum boride, thallium boride; boron carbide, titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, tantalum carbide, Chromium carbide, molybdenum carbide, tungsten carbide, tungsten carbide II, silicon carbide; Fe—Si alloy, Fe—Al alloy, Fe—Si—Al alloy, Fe—Si—Cr alloy, Fe—Ni alloy, Fe—Ni—Co alloy , Fe—Ni—Mo alloy, Fe—Co alloy, Fe—Si—Al—Cr alloy, Fe—Si—B alloy, Fe—Si—Co—B alloy; Mn—Zn ferrite, Mn—Mg—Zn ferrite, Examples include Mg--Cu--Zn ferrite, Ni--Zn ferrite, Ni--Cu--Zn ferrite and Cu--Zn ferrite. These may be used alone or in combination of two or more.

Among these, from the viewpoint of thermal conductivity and electrical insulation, preferably alumina, magnesium oxide, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, boron nitride, aluminum nitride, silicon nitride, titanium nitride, chromium nitride, selected from the group consisting of tantalum nitride, titanium boride, zirconium boride, hafnium boride, yttrium boride, vanadium boride, magnesium diboride, niobium boride, tantalum boride, thallium boride, and molybdenum boride More preferably, alumina, magnesium oxide, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, boron nitride, aluminum nitride, silicon nitride, titanium nitride, chromium nitride, titanium boride, zirconium boride , hafnium boride, yttrium boride, vanadium boride, magnesium diboride, niobium boride, tantalum boride, thallium boride, and molybdenum boride, more preferably , aluminum nitride and boron nitride.

The inorganic filler is preferably particles with no extreme difference in the length, width, and thickness directions, and preferably has an aspect ratio of 0.8 to 1.0. The shape of the inorganic filler may be not only spherical but also polyhedral such as acicular, massive, cubic, or dodecahedron.

Although the particle size of the inorganic filler is not particularly limited, it is preferably 0.1 to 500 μm, more preferably 0.5 to 300 μm, and still more preferably 1 to 200 μm or more. It is not preferable from the viewpoint of surface appearance, and if the particle size is less than 0.1 μm, the dispersibility tends to decrease and the cost increases, which is not preferable.

The content of the inorganic filler in the thermally conductive insulating composition is not particularly limited, but from the viewpoint of obtaining excellent thermal conductivity, it is preferably 20 to 400 parts by mass with respect to 100 parts by mass of the polymer material, More preferably 25 to 350 parts by mass, more preferably 30 to 300 parts by mass. If it is less than 20 parts by mass, thermal conductivity tends to decrease, and if it exceeds 400 parts by mass, flexibility decreases. There is a tendency.

（式中、Ｍ^１及びＭ^２はそれぞれ独立にＨ、Ｌｉ、Ｎａ、Ｋ、又はＣｓであり、Ｒ^１はＳ、Ｏ、又はＮＲ^３であり、Ｒ^３はＨ、又はアルキル基、ハロゲン化アルキル基、ヒドロキシアルキル基、アルコキシアルキル基、アルケニル基、ハロゲン化アルケニル基、ヒドロキシアルケニル基、アルコキシアルケニル基、フェニル基、ハロゲン化フェニル基、ヒドロキシフェニル基、アルコキシフェニル基、ビフェニル基、ハロゲン化ビフェニル基、ヒドロキシビフェニル基、アルコキシビフェニル基、ナフチル基、ハロゲン化ナフチル基、ヒドロキシナフチル基、アルコキシナフチル基、カルボキシル基、エステル基、ウレタン基、アゾ基、シアノ基、アミノ基、アミド基、及びアルコキシシリル基からなる群より選択される少なくとも１種の官能基を有する有機基であり、Ｒ^２は前記有機基と同じであり、あるいはＮＲ^３とＲ^２はヘテロ環を構成する。） <Triazinedithiol compound>
The triazinedithiol-based compound used in the present invention is represented by the following general formula (1). The triazinedithiol-based compound may be used singly or in combination of two or more.

(wherein M ¹ and M ² are each independently H, Li, Na, K, or Cs, R ¹ is S, O, or NR ³ , R ³ is H, or an alkyl group, halogenated Alkyl group, hydroxyalkyl group, alkoxyalkyl group, alkenyl group, halogenated alkenyl group, hydroxyalkenyl group, alkoxyalkenyl group, phenyl group, halogenated phenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, halogenated biphenyl group , hydroxybiphenyl group, alkoxybiphenyl group, naphthyl group, halogenated naphthyl group, hydroxynaphthyl group, alkoxynaphthyl group, carboxyl group, ester group, urethane group, azo group, cyano group, amino group, amide group, and alkoxysilyl group is an organic group having at least one functional group selected from the group consisting of R ² is the same as the above organic group, or NR ³ and R ² form a heterocyclic ring.)

The alkyl group may be linear, branched, or cyclic. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-40, more preferably 1-30.

The alkenyl group may be linear, branched or cyclic. Although the number of carbon atoms in the alkenyl group is not particularly limited, it is preferably 1-40, more preferably 1-30.

The halogen is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine.

Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably 1-40, more preferably 1-30.

（式中、Ｍ^１、Ｍ^２、Ｒ^２、及びＲ^３は前記と同じである。） The triazinedithiol-based compound is preferably at least one triazinedithiol-based compound represented by the following general formulas (2) to (4).

(In the formula, M ¹ , M ² , R ² and R ³ are the same as above.)

In the general formula (2), R ³ is preferably -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -CH ₂ CH ₂ CN, or -CH ₂ CH=CH ₂ and R ² is preferably -C ₈ H ₁₆ CH=CHC ₈ H ₁₇ , -C ₈ H ₁₆ CH=CH ₂ , -C ₆ H ₄ CH=CHC ₆ H ₅ , -C ₆ H ₄ CH= _{CHC6H4OCH3 , -C6H4CH = CH2 , -CH2C6H4CH} =CH2 _{, -CH2CH} = _CH2 , _-CH2NHCOC ( _CH3 )= _{CH2 , - C6H4NHC6H5 , -C6H4N = NC6H5 , -C6H2 [ C ( CH3 ) 3 ] 2OH} , _{-C6H4C6H5 , -C6 H4C6H4C6H5 , -CH2COOH , -CH2COOC2H5 , -CH2COOC8H17 , -CH2CH ( C6H5 ) 2 , -CH2CH2OH _ _ _} , —CH ₂ CH ₂ CH ₂ CH ₂ OH, —CH ₂ (CH ₂ ) ₈ CH ₂ OH, —CH ₂ CH(CH ₃ )OH, —C ₆ H ₄ OH, —C ₁₀ H ₆ OH, —CH _{2C4F9 , -CH2C6F13 , -CH2C7F15 , -CH2C8F17 , -CH2CH2C4F9 , -CH2CH2C6F13 , _ _ _ _ _ _ _ _ -CH2CH2C8F17 , -CH2CH2C10F21 , -CH2CH2CH2C8F17 , -C6H4C8F17 , -C6H4C4F _ _ _ _ _ _ _ _ _ _ _ 9} , —C ₆ F ₅ , —C ₃ H ₆ Si(OCH ₃ ) ₃ , —C ₄ H ₈ Si(OCH ₃ ) ₃ , —C ₆ H ₁₂ Si(OCH ₃ ) ₃ , —C ₁₀ H ₂₀ Si _{( OCH3} ) _{3 , -CH2CH2NHC3H6Si ( OCH3 ) 3 , -C3H6Si ( OC2H5} ) _{3 ,} -C3H6Si( _OCH3 ) _{2CH3 ,} —C ₃ H ₆ Si(CH ₃ ) ₂ OCH ₃ , or —C _3H6Si ( _{CH3 ) 2OSi} ( _CH3 ) ₃ .

Alternatively, in the general formula (2), R ³ and R ² are the same, preferably -CH ₂ CH=CH ₂ , -C ₈ H ₁₆ CH=CHC ₈ H ₁₇ , -C ₈ H ₁₆ CH _{= CH2} , _{-C6H4CH = CHC6H5 , -C6H4CH = CHC6H4OCH3 , -C6H4CH = CH2 , -CH2C6H4CH} = _{CH 2} , _-CH2CH = _{CH2 , -CH2NHCOC ( CH3 ) = CH2 , -C6H4NHC6H5 ,} -C6H4N= _NC6H5 , _{-C6H2 [ C ( CH3 ) 3 ] 2OH , -C6H4C6H5 , -C6H4C6H4C6H5 , -CH2COOH , -CH2COOC2H5 , -CH2 _ COOC8H17 , -CH2CH ( C6H5 ) 2 , -CH2CH2OH , -CH2CH2CH2CH2OH} , _-CH2 ( _{CH2 ) 8CH2OH , -CH2 CH ( CH3} ) _{OH , -C6H4OH , -C10H6OH , -CH2C4F9 , -CH2C6F13 , -CH2C8F17 , -CH2CH2 C4F9 , -CH2CH2C6F13 , -CH2CH2C8F17 , -CH2CH2C10F21 , -CH2CH2CH2C8F17 , -C6 _ _ _ _ _ _ _ _ _ H4C8F17 , -C6H4C4F9 , -C6F5 , -C3H6Si ( OCH3 ) 3 , -C4H8Si ( OCH3} ) _{3 , -C6 H12Si} ( _OCH3 ) _{3 , -C10H20Si ( OCH3 ) 3 , -CH2CH2NHC3H6Si ( OCH3 ) 3} , _-C3H6Si ( _OC2H5 ) ₃ , —C ₃ H ₆ Si(OCH ₃ ) ₂ CH ₃ , —C ₃ H ₆ Si(CH ₃ ) ₂ OCH ₃ , or —C ₃ H ₆ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₃ .

Alternatively, in the general formula (2), N, R ³ and R ² form a heterocyclic ring, and R ³ and R ² are preferably —(CH ₂ CH ₂ ) ₂ CHOH, —(CH ₂ CH ₂ ) _{2CHOCOC 8} H ₁₇ CH=CH ₂ , -(CH ₂ CH ₂ ) ₂ CHOCH ₃ , or -(CH ₂ CH ₂ ) ₂ CHOCOC(CH ₃ )=CH ₂ .

（式中、Ｍ^１及びＭ^２は前記と同じであり、Ｒ^１はＳ、Ｏ、－ＮＨＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_３）ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（Ｃ_３Ｈ_７）ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（Ｃ_２Ｈ_５）ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２（ＣＨ_２）_８ＣＨ_２Ｏ－、－ＮＨＣＨ_２ＣＨ（ＣＨ_３）Ｏ－、－ＮＨＣ_６Ｈ_４Ｏ－、－Ｎ（Ｃ_２Ｈ_５）Ｃ_６Ｈ_４Ｏ－、－ＮＨＣ_１０Ｈ_６Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２）_２ＣＨＯ－、－Ｎ（ＣＨ_２ＣＨ_２）_２ＮＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－Ｎ（ＣＨ_２ＣＨ（ＣＨ_３）ＯＨ）ＣＨ_２ＣＨ（ＣＨ_３）Ｏ－、－Ｎ（ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２ＯＨ）ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２Ｏ－、－ＮＨＣＨ_２Ｃ_６Ｈ_４Ｏ－、－ＮＨＣ_６Ｈ_１１Ｏ－、又は－Ｎ（Ｃ_３Ｈ_７）Ｃ_６Ｈ_４Ｏ－であり、Ｒ^４はアルキレン基であり、Ｒ^５はアルコキシ基であり、Ｒ^６及びＲ^７はそれぞれ独立にアルコキシ基又はアルキル基である。）

(wherein M ¹ and M ² are the same as above, R ¹ is S, O, -NHCH ₂ CH ₂ O-, -N(CH ₃ )CH ₂ CH ₂ O-, -N(C ₃ H _{7 ) CH2CH2O- , -NHCH2CH2CH2CH2O- , -N ( C2H5 ) CH2CH2CH2CH2O- , -NHCH2 ( CH2 ) 8CH2} O—, —NHCH ₂ CH(CH ₃ )O—, —NHC ₆ H ₄ O—, —N(C ₂ H ₅ )C ₆ H ₄ O—, —NHC ₁₀ H ₆ O—, —N(CH _{2 CH2 ) 2CHO- ,} -N( _{CH2CH2 ) 2NCH2CH2O- , -N ( CH2CH2OH} ) _CH2CH2O- , -N( _{CH2CH2CH2OH ) CH2CH2CH2O- ,} -N _{( CH2CH ( CH3 )} OH _{) CH2CH} ( _{CH3 ) O-} , _-N (CH2CH2CH2CH2OH) _CH2CH2CH2 CH ₂ O—, —NHCH ₂ C ₆ H ₄ O—, —NHC ₆ H ₁₁ O—, or —N(C ₃ H ₇ )C ₆ H ₄ O—, R ⁴ is an alkylene group, R ⁵ is an alkoxy group, and ^R6 and ^R7 are each independently an alkoxy group or an alkyl group.)

In general formula (3), the number of carbon atoms in the alkylene group of R ⁴ is not particularly limited, but is preferably 1-40, more preferably 1-30. Although the number of carbon atoms in the alkoxy groups of R ⁵ to R ⁷ is not particularly limited, it is preferably 1-30, more preferably 1-20. Although the number of carbon atoms in the alkyl groups of R ⁶ and R ⁷ is not particularly limited, it is preferably 1-30, more preferably 1-20.

（式中、Ｍ^１、Ｍ^２、及びＲ^５～Ｒ^７は前記と同じであり、Ｒ^８は水素又はアルキル基であり、Ｒ^９はアルキレン基又はアルキレンオキシ基であり、Ｒ^８とＲ^９は互いに結合して環を形成してもよい。）

(wherein M ¹ , M ² and R ⁵ to R ⁷ are the same as above, R ⁸ is hydrogen or an alkyl group, R ⁹ is an alkylene group or an alkyleneoxy group, R ⁸ and R ⁹ may combine with each other to form a ring.)

In general formula (4), the number of carbon atoms in the alkoxy group represented by R ⁵ to R ⁷ is not particularly limited, but is preferably 1-30, more preferably 1-20. Although the number of carbon atoms in the alkyl groups of R ⁶ and R ⁷ is not particularly limited, it is preferably 1-30, more preferably 1-20. Although the number of carbon atoms in the alkyl group of R ⁸ is not particularly limited, it is preferably 1-30, more preferably 1-20. The number of carbon atoms in the alkylene group or alkyleneoxy group of R ⁹ is not particularly limited, but is preferably 1-20, more preferably 1-15. Examples of the ring formed by combining R ⁸ and R ⁹ include a 5-membered ring and a 6-membered ring. R ⁸ and R ⁹ combine to form a propanetriyl group (a 5-membered ring case), butanetriyl group (when forming a 6-membered ring), and the like.

The triazinedithiol compound represented by the general formula (1) can be produced by a known method.

For example, the triazinedithiol-based compound represented by the general formula (2) can be synthesized by mixing and reacting triazinetrithiol or a derivative thereof with an amine represented by NHR ² R ³ . . Hydrogen sulfide is produced as a by-product in this reaction.

Further, the triazinedithiol-based compound represented by the general formula (3) is obtained by mixing triazinetrithiol or a derivative thereof with an alkoxysilylalkylisocyanate represented by NCO--R ⁴ --SiR ⁵ R ⁶ R ⁷ , It can be synthesized by reacting. Examples of the alkoxysilylalkyl isocyanate include 3-trimethoxysilylpropyl isocyanate and 3-triethoxysilylpropyl isocyanate.

（式中、Ｒ^５～Ｒ^９は前記と同じである。） Further, the triazinedithiol-based compound represented by the general formula (4) can be obtained by mixing and reacting a triazinetrithiol or a derivative thereof with an epoxy group-containing alkoxysilane represented by the following general formula (5). Can be synthesized.

(In the formula, R ⁵ to R ⁹ are the same as above.)

Examples of the epoxy group-containing alkoxysilane include diethoxy(3-glycidyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyl(dimethoxy)methylsilane, and 3-glycidylpropyltrimethoxysilane. , diethoxy(3-glycidyloxy)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 3-glycidyloxypropyltrimethoxysilane.

The reaction is preferably carried out by dispersing or dissolving the raw materials in a solvent, mixing them, and further reacting them by heating. As a result, the desired product can be easily synthesized in a short time.

Examples of solvents include water; alcohols such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, carbitol, and cellosolve; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, methyl benzoate, and phthalic acid. Ethers such as diethyl, diethyl adipate, dibutyl ether, and anisole; Aromatic hydrocarbons such as benzene, toluene, xylene, and decalin; Polar solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoamide, and methylpyrrolidone. , or a mixed solvent thereof.

The concentration of triazinetrithiol or its derivative in the solvent is not particularly limited, but is usually 0.1-500 g/L, preferably 1-100 g/L. When the concentration of the triazine trithiol or its derivative is less than 1 g/L, the reaction efficiency tends to be poor. becomes difficult, and a homogeneous reaction becomes difficult to occur.

Although the reaction temperature is related to the boiling point of the solvent used, it cannot be set unambiguously, but it is usually 0 to 200°C, preferably 30 to 160°C. If the temperature is less than 30°C, the reaction time tends to be long and the productivity tends to decrease. On the other hand, when the temperature exceeds 160°C, the reaction rate increases and the productivity improves, but by-products such as dimers are produced, and a special operation may be required for separation from the desired product.

After completion of the reaction, the solvent is distilled off to obtain the triazinedithiol compound as white crystals or liquid, which can be purified by solvent extraction, washing, distillation or crystallization. is. In addition, when a by-product is generated, a step of converting the target product into a sodium salt in water, removing insoluble matter, and neutralizing and purifying the soluble matter with a 1%-HCl solution should be added. is preferred.

The content of the triazinedithiol-based compound in the thermally conductive insulating composition is not particularly limited, but from the viewpoint of obtaining excellent thermal conductivity, it is preferably 5 × 10 ^-7 to 5 Parts by mass, more preferably 1×10 ⁻⁶ to 4 parts by mass, more preferably 1.5× ^{10 −6} to 3 parts by mass. The amount tends to decrease, and if it exceeds 5 parts by mass, the cost tends to increase.

<Other ingredients>
The thermally conductive insulating composition preferably contains an aromatic amine-based, hindered phenol-based, phosphorus-based, and sulfur-based antioxidant. These may be used alone or in combination of two or more.

Examples of aromatic amine antioxidants include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 4-isopropoxydiphenylamine. These may be used alone or in combination of two or more.

Examples of hindered phenol antioxidants include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β-(4'-hydroxy-3',5'-di-t- butylphenyl)propionate, tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6′-tris (3,5-di-t-butyl-4-hydroxybenzyl)benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis[3 -(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], penterithrityl-tetrakis [3-(3,5-di-t-butylanilino)-1,3,5-triazine, 3,9- Bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5] undecane, bis[3,3-bis(4′-hydroxy-3′-t-butylphenyl)butyric acid] glycol ester, triphenol, 2,2′-ethylidenebis(4,6-di-t-butylphenol), N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxamidebis[ethyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate], 1,1,3-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic Hydrotriester with-1,3,5-tris(2-hydroxyethyl)-S-triazine-2,4,6(1H,3H,5H) and N,N-hexamethylenebis(3,5-di -t-butyl-4-hydroxy-hydrocinnamide) and the like. These may be used alone or in combination of two or more.

Phosphorus-based antioxidants include, for example, phosphorus-containing compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonates, and diphosphite-based compounds. Specific examples include triphenylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tri(nonylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, and bis( 2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite and the like. These may be used alone or in combination of two or more.

Examples of sulfur-based antioxidants include sulfur-containing compounds such as thioether-based, dithioate-based, mercaptobenzimidazole-based, thiocarbanilide-based, and thiodipropionate-based antioxidants. Specific examples include dilaurylthiodipropionate, distearylthiodipropionate, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate pionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, and and trilauryl trithiophosphite. These may be used alone or in combination of two or more.

The content (content) of the antioxidant is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polymer material. Department. When two or more antioxidants are blended, the total amount of the antioxidants to be blended is preferably 5 parts by mass or less.

If necessary, the thermally conductive insulating composition may contain a cross-linking agent within a range that does not impair the effects of the present invention. The cross-linking agent is not particularly limited as long as it is a cross-linking agent that reacts with the functional groups possessed by the polymer material. cross-linking agents, melamine resin-based cross-linking agents, metal salt-based cross-linking agents, metal chelate-based cross-linking agents, and amino resin-based cross-linking agents. These may be used alone or in combination of two or more.

The epoxy-based cross-linking agent is not particularly limited as long as it is a polyfunctional epoxy compound having two or more epoxy groups (glycidyl groups) in the molecule. Naphthalene diglycidyl ether, 1,3-bis(oxiranylmethoxy)benzene, 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2, which has three epoxy groups, 4,6(1H,3H,5H)-trione, diglycerol triglycidyl ether, 1-chloro-2,3-epoxypropane/formaldehyde/2,7-naphthalenediol polycondensate with four epoxy groups and pentaerythritol Polyglycidyl ethers are mentioned. Among these, polyfunctional epoxy compounds having heat resistance in the skeleton are preferred. In particular, a bifunctional or tetrafunctional epoxy compound having a naphthalene structure in its skeleton or a trifunctional epoxy compound having a triazine structure in its skeleton is preferred.

In addition, it contains two or more glycidyl groups per molecule and has a weight average molecular weight of 4000 to 25000, and (X) 20 to 99% by mass of a vinyl aromatic monomer, (Y) 1 to 80% by mass of glycidyl (Meth)acrylates and (Z) styrenic copolymers composed of vinyl group-containing monomers other than (X) containing no epoxy groups in an amount of 0 to 79% by mass can be mentioned. More preferably, (X) is 20 to 99% by mass, (Y) is 1 to 80% by mass, and (Z) is 0 to 40% by mass. 10 to 75% by mass of (Y) and 0 to 35% by mass of (Z). Examples of the vinyl aromatic monomer (X) include styrene and α-methylstyrene. Examples of the (Y) glycidyl (meth)acrylate include glycidyl (meth)acrylate, (meth)acrylic acid ester having a cyclohexene oxide structure, (meth)acryl glycidyl ether, and the like. glycidyl (meth)acrylate is preferred in terms of high Examples of (Z) other vinyl group-containing monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (Meth) having an alkyl group having 1 to 22 carbon atoms (the alkyl group may be linear or branched) such as cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and methoxyethyl (meth)acrylate Alkyl acrylate, polyalkylene glycol (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylate, benzyl (meth)acrylate , (meth)acrylic acid phenoxyalkyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid alkoxysilylalkyl ester, and the like. In addition, vinyl esters such as (meth)acrylamide, (meth)acryldialkylamide, and vinyl acetate, aromatic vinyl monomers such as vinyl ethers and (meth)allyl ethers, α-olefins such as ethylene and propylene Monomers can also be used as (Z) other vinyl group-containing monomers.

The weight average molecular weight of the styrenic copolymer is preferably 4,000 to 25,000, more preferably 5,000 to 15,000. The epoxy value of the styrenic copolymer is preferably 400 to 2500 equivalents/1×10 ⁶ g, more preferably 500 to 1500 equivalents/1×10 ⁶ g, still more preferably 600 to 1000 equivalents/1. x 10 ⁶ g.

The carbodiimide-based cross-linking agent is not particularly limited as long as it is a polycarbodiimide having two or more carbodiimide groups (-N=C=N- structure) in one molecule. Carbodiimide, aromatic polycarbodiimide, copolymers thereof, and the like. Preferred are aliphatic polycarbodiimides and alicyclic polycarbodiimides.

Polycarbodiimide can be obtained, for example, by decarbonization reaction of a diisocyanate compound. Examples of diisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 1,3, and 5-triisopropylphenylene-2,4-diisocyanate. These may be used alone, or two or more may be copolymerized and used. Also, a branched structure may be introduced, or a functional group other than a carbodiimide group or an isocyanate group may be introduced by copolymerization. Furthermore, although the terminal isocyanate can be used as it is, the degree of polymerization may be controlled by reacting the terminal isocyanate, or a portion of the terminal isocyanate may be blocked.

As the polycarbodiimide, alicyclic polycarbodiimides derived from dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, etc. are preferred, and alicyclic polycarbodiimides derived from dicyclohexylmethane diisocyanate and isophorone diisocyanate are more preferred. is.

Polycarbodiimide preferably contains 2 to 50 carbodiimide groups per molecule, more preferably 5 to 30 groups, from the viewpoint of stability and handleability. The number of carbodiimides in a polycarbodiimide molecule (that is, the number of carbodiimide groups) corresponds to the degree of polymerization in the case of polycarbodiimide obtained from a diisocyanate compound. For example, the degree of polymerization of polycarbodiimide obtained by connecting 21 diisocyanate compounds in a chain is 20, and the number of carbodiimide groups in the molecular chain is 20. Polycarbodiimides are usually mixtures of molecules of various lengths and the number of carbodiimide groups is expressed as an average value. Polycarbodiimide, which has the number of carbodiimide groups within the above range and is solid at around room temperature, can be pulverized, and is therefore excellent in workability and compatibility when mixed with an elastomer, and is also preferable in terms of uniform reactivity and bleed-out resistance. . The number of carbodiimide groups can be measured, for example, by a conventional method (method of dissolving with amine and performing back titration with hydrochloric acid).

Polycarbodiimide has an isocyanate group at its end, and the isocyanate group content is preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass, from the viewpoint of stability and handleability. Particularly preferred are polycarbodiimides derived from dicyclohexylmethane diisocyanate and isophorone diisocyanate and having an isocyanate group content within the above range. The isocyanate group content can be measured by a conventional method (method of dissolving with amine and performing back titration with hydrochloric acid).

Examples of the isocyanate-based cross-linking agent include the polycarbodiimide compound containing the isocyanate group and the isocyanate compound used as the raw material of the polycarbodiimide compound.

As the acid anhydride cross-linking agent, a compound containing 2 to 4 anhydrides per molecule is preferable from the viewpoint of stability and handleability. Such compounds include, for example, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

The blending (content) amount of the cross-linking agent is appropriately adjusted depending on the extrusion conditions, the desired expansion ratio, etc., but it is preferably 0.1 to 4.5 parts by mass with respect to 100 parts by mass of the polymer material, and more It is preferably 0.1 to 4 parts by mass, more preferably 0.1 to 3 parts by mass.

Various additives other than the antioxidant and the cross-linking agent can be added to the thermally conductive insulating composition according to the purpose. Additives include, for example, hindered amine-based, benzotriazole-based, benzophenone-based, benzoate-based, triazole-based, nickel-based, and salicyl-based light stabilizers, lubricants, fillers, flame retardants, flame retardant aids, and release agents. agents, antistatic agents, molecular modifiers such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizers, antacids, antibacterial agents, fluorescent brighteners, organic and inorganic and organic and inorganic phosphorus compounds used for the purpose of imparting flame retardancy and thermal stability. When the additive is blended, the content (the total content when using a plurality of additives) is preferably 30% by mass or less in the thermally conductive insulating composition, more preferably 20% by mass. % or less, more preferably 10 mass % or less, and particularly preferably 5 mass % or less.

<Thermal conductive insulating composition>
The method for producing the thermally conductive insulating composition of the present invention is not particularly limited, and it can be produced by mixing the respective components described above. In the present invention, from the viewpoint of increasing the dispersibility of the inorganic filler in the composition and facilitating the formation of a continuous body formed by connecting the inorganic filler, the inorganic filler and the triazinedithiol compound are brought into contact with each other. Then, the triazinedithiol-based compound is attached to the surface of the inorganic filler to obtain a surface-modified inorganic filler, and then the obtained surface-modified inorganic filler is dispersed in the polymer material to form a thermally conductive insulating composition. is preferably produced.

The method of contacting the inorganic filler with the triazinedithiol-based compound is not particularly limited. For example, a method of mixing the inorganic filler and the triazinedithiol-based compound, a solution of the triazinedithiol-based compound dissolved in a solvent, or A method of immersing the inorganic filler in a dispersion of the triazinedithiol-based compound in a solvent, removing the inorganic filler, and then drying the inorganic filler may be used.

<Thermal conductive insulating molding>
The thermally conductive insulating molded article of the present invention is obtained by molding the thermally conductive insulating composition. Although the method for producing the thermally conductive insulating molded article is not particularly limited, it is preferable to pressurize and/or heat the thermally conductive insulating composition for molding. The molding method includes, for example, an extrusion molding method, a mold molding method, a hot press method, and the like. The temperature and pressure during molding are appropriately adjusted according to the type of polymeric material used.

The shape of the thermally conductive insulating molded product can be appropriately selected according to the application, and examples thereof include sheet-like, plate-like, film-like and block-like shapes.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these, and can be carried out with appropriate modifications within the scope that can conform to the spirit of the above and below. and all of them are included in the technical scope of the present invention.

Production example 1
(Production of polyester elastomer (A1))
In a reactor equipped with a stirrer, a thermometer, and a condenser for distillation, 194 parts by mass of dimethyl terephthalate, 109 parts by mass of 1,4-butanediol, and polytetramethylene glycol having a number average molecular weight of 2000 "PTMG2000" (Mitsubishi Chemical 580 parts by mass of Co., Ltd. and 0.25 parts by mass of tetrabutyl titanate were added, and an esterification reaction was carried out at 170 to 220° C. for 2 hours. After completion of the esterification reaction, the temperature was raised to 255° C. while the pressure in the system was slowly reduced to 665 Pa at 255° C. over 60 minutes. Then, a polycondensation reaction was further carried out at 133 Pa or less for 30 minutes to obtain a polyester elastomer (A1). Table 1 shows the composition and physical properties of the polyester elastomer (A1).

Production Examples 2-6
(Production of polyester elastomers (A2) to (A6))
Polyester elastomers (A2) to (A6) were produced in the same manner as in Production Example 1, except that the compositions were changed to those shown in Table 1. Table 1 shows the compositions and physical properties of the polyester elastomers (A2) to (A6).

Production example 7
(Production of polyester elastomer (A7))
220 parts by mass of polybutylene terephthalate (PBT) and 269 parts by mass of ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd.) were charged into a reactor equipped with a stirrer, thermometer, and distillation cooler, and after purging with nitrogen gas. , and 230° C. with stirring for 120 minutes. Thereafter, unreacted ε-caprolactone was removed under vacuum to obtain a polyester elastomer (A7). Table 1 shows the composition and physical properties of the polyester elastomer (A7).

Production example 8
(Production of polyester elastomer (A8))
220 parts by mass of polybutylene terephthalate (PBT) and 118 parts by mass of polycarbonate diol (PCD) having a number average molecular weight of 10,000 were mixed and stirred at 230 to 245° C. under 130 Pa for 1 hour. After confirming that the reactant became transparent, the reactant was taken out and cooled to obtain a polyester elastomer (A8). Table 1 shows the composition and physical properties of the polyester elastomer (A8).

Production example 9
(Production of polyester elastomer (A9))
A polyester elastomer (A9) was produced in the same manner as in Production Example 8, except that the composition was changed to that shown in Table 1. Table 1 shows the composition and physical properties of the polyester elastomer (A9).

Production example 10
(Production of polyester elastomer (A10))
Assuming that the theoretical scale of the final copolyester elastomer is 11 kg, 5.38 kg of bishydroxyethylene terephthalate (BHET), 3.52 kg of terephthalic acid (TPA), and 0.5 kg of ethylene glycol are placed in a 30 L autoclave equipped with a rectifying column. under atmospheric pressure with nitrogen flow, the esterification reaction is carried out while raising the internal temperature to 250 ° C., and the water distilled by the reaction is distilled off and a predetermined amount is removed from the system, resulting in an esterification rate of 95%. The esterification reaction was carried out up to the above. Thereafter, 0.66 kg of ethylene glycol was introduced into the system to raise the decreasing internal temperature, and the polymerization reaction was carried out at 250° C. for 30 minutes or more. The obtained ester oligomer had a number average molecular weight of 340. Then, 2.75 kg of a polyester polyol having a number average molecular weight of 2200 obtained from hydrogenated dimer acid and 1,4 butanediol (Priplast 3199: manufactured by Croda; acid value 1 mgKOH/g) was added to the system and stirred for 30 minutes or more. An additional esterification reaction was carried out. Subsequently, tetrabutoxy titanate was added as a polycondensation catalyst at 60 ppm as a titanium element, and after stirring, the pressure was reduced to 13.3 kPa or less in 1 hour. A copolymerization reaction was carried out by stirring to a predetermined viscosity under vacuum, extruded into water from a spinneret in a cord shape, and cut with a pelletizer to obtain pellets of the polyester elastomer (A10). The appearance of the obtained pellets was pale yellow and transparent. The polyester elastomer (A10) had a soft segment content of 60% by mass, a melting point of 210°C, and a melt viscosity of 3000 dPa·s at a measurement temperature of 220°C.

The compounds in Table 1 are as follows.
DMT: dimethyl terephthalate DMN: dimethyl naphthalate BD: 1,4-butanediol PTMG2000: polytetramethylene glycol with a number average molecular weight of 2000 PTMG1000: polytetramethylene glycol with a number average molecular weight of 1000 PBT: polybutylene terephthalate PCL: ε-caprolactone PCD : Polycarbonate diol with a number average molecular weight of 10,000

Production Example 11
(Production of a triazinedithiol compound represented by the following formula (6))

17.72 g (0.1 mol) of triazinetrithiol and 0.102 mol of 3-triethoxysilylpropylamine were added to 100 mL of toluene to obtain a mixture. Here, triazinetrithiol is dispersed in toluene and 3-triethoxysilylpropylamine is dissolved in toluene. The mixture was then stirred at 140° C. for 30 minutes to allow the reaction to proceed. After completion of the reaction, the toluene was distilled off under reduced pressure and recovered, and the gas component was absorbed in a 20% NaOH aqueous solution to remove the generated hydrogen sulfide. The obtained solid was washed with ethyl ether to remove a trace amount of unreacted amine to obtain a crude triazinedithiol compound in a yield of 96% or more. Thereafter, the crude triazinedithiol-based compound was recrystallized with isopropanol and purified to obtain the triazinedithiol-based compound represented by the above formula (6). The melting point of the triazinedithiol compound after recrystallization was 235 to 236° C., and the elemental analysis values were C: 40.2%, N: 16.0%, S: 18.2%. For melting point analysis, a melting point measuring instrument manufactured by Mita Riken Kogyo Co., Ltd. was used. Also, a Yanagimoto CHN coder was used for carbon and nitrogen analysis, and a CHN coder manufactured by PerkinElmer was used for sulfur analysis.

Production example 12
(Production of surface-modified aluminum nitride filler (B1))
The triazinedithiol-based compound produced in Production Example 11 was dissolved in ion-exchanged water to obtain an aqueous solution containing 0.1 wt % of the triazinedithiol-based compound. Then, 100 g of aluminum nitride filler (manufactured by Furukawa Electronics Co., Ltd., FAN-05) was immersed in the aqueous solution for 10 minutes, then taken out and dried at 100° C. for 60 minutes to obtain the surface-modified aluminum nitride filler (B1). Obtained.

Production example 13
(Production of surface-modified boron nitride filler (B2))
The triazinedithiol-based compound produced in Production Example 11 was dissolved in ion-exchanged water to obtain an aqueous solution containing 0.1 wt % of the triazinedithiol-based compound. Then, 100 g of boron nitride filler (manufactured by Denka Co., Ltd., SP-2) is immersed in the aqueous solution for 10 minutes, then taken out and dried at 100 ° C. for 60 minutes to obtain surface-modified boron nitride filler (B2). rice field.

Example 1
(Production of thermally conductive insulating composition)
After mixing 60 parts by mass of the polyester-based elastomer (A1) and 40 parts by mass of the surface-modified aluminum nitride filler (B1), the resulting mixture was preheated to 180 ° C. A desktop kneader manufactured by Toyo Seiki Co., Ltd. (Laboplast It was put into a mill 20C200) and kneaded at 40 rpm for 10 minutes to obtain a thermally conductive insulating composition.

Example 2
(Production of thermally conductive insulating composition)
After mixing 60 parts by mass of the polyester-based elastomer (A1) and 40 parts by mass of the surface-modified boron nitride filler (B2), the resulting mixture was preheated to 180 ° C. A desktop kneader manufactured by Toyo Seiki Co., Ltd. (Laboplast It was put into a mill 20C200) and kneaded at 40 rpm for 10 minutes to obtain a thermally conductive insulating composition.

Example 3
(Production of thermally conductive insulating composition)
After mixing 50 parts by mass of the polyester-based elastomer (A1) and 2 parts by mass of the surface-modified aluminum nitride filler (B1), the resulting mixture was preheated to 180 ° C. A desktop kneader manufactured by Toyo Seiki Co., Ltd. (Laboplast It was put into a mill 20C200) and kneaded at 40 rpm for 10 minutes. After taking out the obtained kneaded material, cutting it into chips, mixing the obtained chips with 48 parts by mass of alumina filler, and then kneading again at 40 rpm for 10 minutes to produce a thermally conductive insulating composition. bottom.

Examples 4-14
(Production of thermally conductive insulating composition)
A thermally conductive insulating composition was produced in the same manner as in Example 3, except that the types and blending amounts of the polyester elastomer and filler were changed as shown in Table 2. The kneading temperature was set to be the melting point of the polyester elastomer used plus 20°C.

Comparative Examples 1-4
(Production of thermally conductive insulating composition)
A thermally conductive insulating composition was produced in the same manner as in Example 1, except that the types and blending amounts of the polyester elastomer and filler were changed as shown in Table 2. The kneading temperature was set to be the melting point of the polyester elastomer used plus 20°C.

〔Evaluation methods〕
Thermal conductivity, heat resistance, moist heat resistance, thermal resistance, and dielectric breakdown voltage were evaluated by the following methods.
(Preparation of Sheet Sample for Evaluation)
A sheet sample for evaluation was produced using a heat press (SA-302-I, manufactured by Tester Sangyo Co., Ltd.). The thermally conductive insulating compositions prepared in Examples and Comparative Examples were placed in a mold having a predetermined thickness, and melted for 2 minutes at a temperature of +20° C., the melting point of the polyester elastomer. A load of 100 kgf/cm ² was applied to the obtained melt, and after 1 minute, it was immersed in water and rapidly cooled to obtain a sheet sample for evaluation having a predetermined thickness.

(Measurement of thermal conductivity)
Specific heat was measured using DSC2920 manufactured by TA Instruments. 10.0 mg of the thermally conductive insulating composition (sample) prepared in Examples and Comparative Examples was placed in an aluminum pan, heated from room temperature to 200 ° C. at a temperature increase of 10 ° C./min, and after reaching 200 ° C. Hold for 5 minutes. After that, the temperature was lowered at 10°C/min. Similarly, 26.8 mg of sapphire was placed in an aluminum pan as a reference substance and measured under the same conditions. Furthermore, as a blank, an empty aluminum pan containing no sample was measured under the same conditions. The heat flow value at 23° C. of each DSC curve was read, and the specific heat capacity was calculated by the following formula.

Cp = (h/H) x (m'/m) x C'p

Cp: specific heat of the sample C'p: specific heat of the reference material (sapphire) at 23 ° C. h: difference between the DSC curves of the blank and the sample H: difference between the DSC curves of the blank and the reference material (sapphire) m: mass of the sample (g )
m': Mass (g) of reference material (sapphire)

The specific gravity was measured using an automatic hydrometer D-H100 manufactured by Toyo Seiki Co., Ltd. The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 0.5 mm. Then, the sheet was cut into a size of 10 mm×10 mm to obtain a sample for specific gravity measurement. Using the prepared sample for specific gravity measurement, the specific gravity was measured by the water substitution method.
The thermal diffusivity was measured using a thermal diffusivity measuring device ai-phase Mobile 1 manufactured by i-Phase Co., Ltd. The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 0.5 mm. Using the produced sheet, the thermal diffusivity in the thickness direction was measured.
Then, the thermal conductivity was calculated from the specific heat, specific gravity, and thermal diffusivity determined by the above method, using the following formula.

Thermal conductivity (W/m·K) = specific gravity x specific heat (J/g·K) x thermal diffusivity (m ² /sec)

(Evaluation of heat resistance)
The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 1 mm. Then, the sheet was cut into a size of 10 mm×50 mm to obtain a sample for heat resistance evaluation. A sample for heat resistance evaluation was placed in a constant temperature bath, and after 1000 hours at a temperature of 85° C., its tensile elongation was measured, and the temperature at which it reached 50% of the initial value was investigated. And it evaluated by the following reference|standard. The higher the temperature at which the initial value is 50%, the higher the heat resistance.
◎: 160 ° C. or higher ○: 130 ° C. or higher and lower than 160 ° C. △: 110 ° C. or higher and lower than 130 ° C. ×: lower than 110 ° C.

(Evaluation of moist heat resistance)
The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 1 mm. Then, the sheet was cut into a size of 10 mm×50 mm to obtain a sample for wet heat resistance evaluation. A sample for moist heat resistance evaluation was placed in a constant temperature and humidity chamber, and the expansion rate of the sample was observed under conditions of 85° C.×85% Rh. The length, width, and thickness (mm) of the sample were measured before and after 1000 hours from the constant temperature and humidity bath, and the expansion rate (%) in each direction was calculated. Furthermore, the volume expansion rate (%) was calculated by taking the product of them. At this time, the expansion rate before being put into the constant temperature and humidity bath is assumed to be 100%. A constant pressure vernier caliper was used for the measurement. The smaller the volumetric expansion rate, the better. When the volume expansion coefficient is 110% or less, deterioration of brittleness is small and favorable. If the volume expansion rate exceeds 110%, the brittleness worsens, so use under high humidity is not preferable.

(Measurement of thermal resistance)
The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 0.3 mm. The thermal resistance of the sheets was measured according to ASTM D5470. The thermal resistance is preferably 0.6×10e ⁻³ (m ² K/W) or less. Note that the thermal resistance is approximately proportional to the thickness of the sheet.

(Measurement of dielectric breakdown voltage)
The prepared sheet sample for evaluation was heat-pressed to obtain a sheet having a thickness of 0.1 mm. The dielectric breakdown voltage of the sheet was measured according to JIS K6249. The dielectric breakdown voltage is preferably 3 kV or higher. Note that the dielectric breakdown voltage is approximately proportional to the thickness of the sheet.

The thermally conductive insulating molded article of the present invention is useful as a material for members requiring insulation and heat dissipation, such as automobile members and electronic circuit boards.

Claims (10)

A thermally conductive insulating composition containing a polymeric material containing an elastomer , an inorganic filler, and a triazinedithiol-based compound represented by the following general formula (1).

(wherein M ¹ and M ² are each independently H, Li, Na, K, or Cs, R ¹ is S, O, or NR ³ , R ³ is H, or an alkyl group, halogenated Alkyl group, hydroxyalkyl group, alkoxyalkyl group, alkenyl group, halogenated alkenyl group, hydroxyalkenyl group, alkoxyalkenyl group, phenyl group, halogenated phenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, halogenated biphenyl group , hydroxybiphenyl group, alkoxybiphenyl group, naphthyl group, halogenated naphthyl group, hydroxynaphthyl group, alkoxynaphthyl group, carboxyl group, ester group, urethane group, azo group, cyano group, amino group, amide group, and alkoxysilyl group is an organic group having at least one functional group selected from the group consisting of R ² is the same as the above organic group, or NR ³ and R ² form a heterocyclic ring.) 2. The thermally conductive insulating composition according to claim 1, wherein the triazinedithiol-based compound is at least one triazinedithiol-based compound represented by the following general formulas (2) to (4).

(In the formula, M ¹ , M ² , R ² and R ³ are the same as above.)

(wherein M ¹ and M ² are the same as above, R ¹ is S, O, -NHCH ₂ CH ₂ O-, -N(CH ₃ )CH ₂ CH ₂ O-, -N(C ₃ H _{7 ) CH2CH2O- , -NHCH2CH2CH2CH2O- , -N ( C2H5 ) CH2CH2CH2CH2O- , -NHCH2 ( CH2 ) 8CH2} O—, —NHCH ₂ CH(CH ₃ )O—, —NHC ₆ H ₄ O—, —N(C ₂ H ₅ )C ₆ H ₄ O—, —NHC ₁₀ H ₆ O—, —N(CH _{2 CH2} ) _{2CHO- , -N} ( _{CH2CH2 )2NCH2CH2O- , -N ( CH2CH2OH ) CH2CH2O-} , -N( _{CH2CH2CH2OH ) CH2CH2CH2O- ,} -N _{( CH2CH ( CH3 )} OH _{) CH2CH} ( _{CH3 ) O-} , _-N (CH2CH2CH2CH2OH) _CH2CH2CH2 CH ₂ O—, —NHCH ₂ C ₆ H ₄ O—, —NHC ₆ H ₁₁ O—, or —N(C ₃ H ₇ )C ₆ H ₄ O—, R ⁴ is an alkylene group, R ⁵ is an alkoxy group, and ^R6 and ^R7 are each independently an alkoxy group or an alkyl group.)

(wherein M ¹ , M ² and R ⁵ to R ⁷ are the same as above, R ⁸ is hydrogen or an alkyl group, R ⁹ is an alkylene group or an alkyleneoxy group, R ⁸ and R ⁹ may combine with each other to form a ring.) 3. The thermally conductive insulating composition according to claim 1, wherein said elastomer is at least one selected from the group consisting of polyester elastomers and polyamide elastomers. The thermally conductive insulating composition according to any one of claims 1 to 3 , wherein the inorganic filler contains at least one selected from the group consisting of aluminum nitride filler and boron nitride filler. The thermally conductive insulating composition according to any one of claims 1 to 4 , wherein the content of the inorganic filler is 20 to 400 parts by mass with respect to 100 parts by mass of the polymer material. The thermally conductive insulating composition according to any one of claims 1 to 5 , wherein the content of said triazinedithiol-based compound is 5 × 10 ^-7 to 5 parts by mass with respect to 100 parts by mass of said inorganic filler. A thermally conductive insulating molded article obtained from the thermally conductive insulating composition according to any one of claims 1 to 6 . The thermally conductive insulating molded article according to claim 7 , wherein the thermally conductive insulating molded article is a thermally conductive insulating sheet. 9. The method for producing a thermally conductive insulating molded article according to claim 7 or 8 , wherein the inorganic filler and the triazinedithiol compound are brought into contact to adhere the triazinedithiol compound to the surface of the inorganic filler. step A of obtaining a surface-modified inorganic filler by dispersing the surface-modified inorganic filler in the polymer material to obtain the thermally conductive insulating composition; and step C of molding the thermally conductive insulating composition. A method for producing a thermally conductive insulating molded body comprising: 10. The method for producing a thermally conductive insulating molded article according to claim 9 , wherein in said step C, said thermally conductive insulating composition is molded by pressing and/or heating.