JP2015160862A - Resin composition, cured body containing mesogenic group, and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel addition-curable resin composition suitably usable as a resin material for heat radiation materials, semiconductor devices, and electronic components; a cured boy of the composition; and a method of producing the same.SOLUTION: A resin composition contains (A) a specific polyester-based mesogen-silicon compound copolymer containing, in one molecule, two or more unsaturated hydrocarbon groups obtainable by carrying out condensation using, as essential ingredients, a carboxylic acid ingredient containing a siloxane chain and aromatic diol of bicyclic or polycyclic aromatic having an unsaturated group on an aromatic ring; (B) an organohydrogenpolysiloxane having two or more SiH groups in one molecule; and (C) a platinum group metal catalyst.

Description

  The present invention relates to a resin composition containing an addition-curable mesogen / silicon compound copolymer, a cured product of the composition, and a method for producing the same.

  In recent years, the development of electronic devices has been remarkable, but the amount of heat generated per unit area has increased with the improvement in performance and miniaturization. Since heat adversely affects the device, it is an important issue to efficiently release the heat to the outside. In response to these problems, thermosetting resins are widely used for members of electronic devices from the viewpoint of high insulation performance, ease of molding, heat resistance, and the like. However, a general thermosetting resin has a low thermal conductivity, and has a great disadvantage from the viewpoint of heat dissipation. As a solution to this problem, the filling of inorganic compound particles with high thermal conductivity into a resin is widely performed, and as a result, heat conduction can be performed more efficiently than a resin alone. However, since there is a limit to the filling amount of inorganic compound particles with respect to a certain amount of resin, this method has a limit in improving thermal conductivity. In addition, the inorganic compound is expensive.

  From such a background, it has been desired to improve the thermal conductivity of the resin itself. Improvement in thermal conductivity can be achieved by providing the resin with a portion where the resins called mesogenic groups tend to overlap each other. However, a resin containing a large amount of mesogenic groups has a drawback in handling such as having a high melting point and softening point even before thermosetting, and remarkably worsening the solubility of the resin in a solvent. For this reason, it has not been possible to develop a highly thermally conductive resin having utility value by simply increasing the number of mesogenic groups.

  Patent Document 1 (Japanese Patent Laid-Open No. 2011-84714) discloses a thermoplastic resin obtained by copolymerizing a mesogenic group and a spacer. It is described that the polymer compound is excellent in thermal conductivity due to mesogen stacking. However, it is known that a resin having a mesogenic group becomes hard and brittle due to stacking of the mesogenic group, and further hardly soluble in a solvent, and the above resin is no exception.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-231161) discloses a thermosetting resin in which a crosslinking site is introduced into the resin of Patent Document 1, but it is improved in that it is hardly soluble in a solvent. Not. Since such a resin is brittle, there are problems in that its use location is limited, and since it is difficult to dissolve in a solvent, it is limited to use without solvent such as extrusion.

JP 2011-84714 A JP 2011-231161 A

  The present invention has been made in view of the above circumstances, and is a novel addition-curable resin composition that can be suitably used as a heat dissipation material, a resin material for semiconductor devices and electronic components, a cured product of the composition, and its An object is to provide a manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have used an unsaturated hydrocarbon group-containing mesogen / silicon compound copolymer represented by the following average composition formula (1) as a main agent. The resin composition is soluble or dispersible in a solvent, can be selected from a wide range of molding methods, and an easy-to-handle resin composition is obtained. The cured product of the resin composition has good thermal conductivity, a heat dissipation material, It has been found that it can be suitably used as a resin material for a semiconductor device or an electronic component, and has led to the present invention.

〔式中、Ｒ¹、Ｒ⁵はそれぞれ同一でも異なっていてもよい炭素原子数１〜２０の２価炭化水素基である。また、Ｒ²は下記式

で示される構造から選ばれる２価の基である。ｐは０又は１である。Ｒ³及びＲ⁴はそれぞれ炭素原子数２〜１０の不飽和基を含む１価炭化水素基であり、相互に異なっていても同一でもよい。また、ｑ、ｒはそれぞれ０、１又は２であり、ｑ、ｒは同時に０ではない。ｌ、ｍ、ｎはそれぞれ１未満の正数であり、ｏは０又は０．５以下の正数である。更にｌ、ｍ、ｎ、ｏはｌ＋ｍ＋ｎ＋ｏ＝１を満たす。Ｚ、Ｘはそれぞれ下記一般式（２）

（式中、Ｍｅはメチル基であり、ａは０〜６０の整数であり、ｂは０〜６０の整数である。Ｒ⁶及びＲ⁷はそれぞれ炭素原子数１〜２０の１価炭化水素基であり、相互に異なっていても同一でもよい。但し、Ｒ⁶、Ｒ⁷は同時にメチル基ではない。）
で示されるケイ素原子を含む２価の有機基である。〕
〔２〕
（Ｂ）１分子内に２個以上のＳｉＨ基を含有するオルガノハイドロジェンポリシロキサンが、下記一般式（３）、（４）

（式中、Ｍｅはメチル基であり、Ｒ⁸〜Ｒ¹⁰はそれぞれ同一でも異なっていてもよい脂肪族不飽和結合を有さない炭素原子数１〜１２の１価の炭化水素基である。Ａは水素原子又はメチル基である。ｃ、ｄ、ｅはそれぞれ０〜６０の整数である。但し、Ａが１つメチル基の場合、ｃは１以上６０以下の整数であり、Ａが２つメチル基の場合、ｃは２以上６０以下の整数である。ｆ、ｈはそれぞれ０〜１０の整数であり、ｇは２〜１０の整数である。）
で示される１種以上のオルガノハイドロジェンポリシロキサンである〔１〕の樹脂組成物。
〔３〕
更に、（Ｄ）反応制御剤を含有する〔１〕又は〔２〕記載の樹脂組成物。
〔４〕
更に、（Ｅ）酸化防止剤を含有する〔１〕〜〔３〕のいずれかに記載の樹脂組成物。
〔５〕
更に、（Ｆ）無機充填剤を含有する〔１〕〜〔４〕のいずれかに記載の樹脂組成物。
〔６〕
更に、（Ｇ）有機溶剤を含有する〔１〕〜〔５〕のいずれかに記載の樹脂組成物。
〔７〕
〔１〕〜〔６〕のいずれかに記載の樹脂組成物を硬化させて得られるメソゲン基含有硬化物。
〔８〕
（Ａ）成分を含む溶液又は分散液に、（Ｂ）、（Ｃ）成分及びその他の成分を添加して加熱硬化させることを特徴とする〔７〕記載のメソゲン基含有硬化物の製造方法。 Therefore, this invention provides the resin composition shown below, the hardened | cured material of this composition, and its manufacturing method.
[1]
(A) a mesogen / silicon compound copolymer containing two or more unsaturated hydrocarbon groups represented by the following average composition formula (1) in one molecule;
(B) an organohydrogenpolysiloxane containing two or more SiH groups in one molecule;
(C) A resin composition comprising a platinum group metal catalyst.

Wherein a divalent hydrocarbon group R ^1, R ⁵ is carbon atoms which may be the same or different, respectively 20. R ² is the following formula

Is a divalent group selected from the structure represented by: p is 0 or 1. R ³ and R ⁴ are each a monovalent hydrocarbon group containing an unsaturated group having 2 to 10 carbon atoms, and may be different or the same. Moreover, q and r are 0, 1 or 2, respectively, and q and r are not 0 at the same time. l, m, and n are each a positive number less than 1, and o is a positive number that is 0 or 0.5 or less. Further, l, m, n, and o satisfy l + m + n + o = 1. Z and X are the following general formula (2)

(In the formula, Me is a methyl group, a is an integer of 0 to 60, and b is an integer of 0 to 60. R ⁶ and R ⁷ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms. And may be the same or different from each other, provided that R ⁶ and R ⁷ are not methyl groups at the same time.)
And a divalent organic group containing a silicon atom. ]
[2]
(B) Organohydrogenpolysiloxanes containing two or more SiH groups in one molecule are represented by the following general formulas (3) and (4).

(In the formula, Me is a methyl group, and R ^{8 to} R ¹⁰ are each a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have the same or different aliphatic unsaturated bonds. A is a hydrogen atom or a methyl group, and c, d and e are each an integer of 0 to 60. However, when A is one methyl group, c is an integer of 1 to 60 and A is 2 In the case of one methyl group, c is an integer of 2 to 60. f and h are each an integer of 0 to 10, and g is an integer of 2 to 10.)
The resin composition according to [1], which is one or more organohydrogenpolysiloxanes represented by the formula:
[3]
The resin composition according to [1] or [2], further comprising (D) a reaction control agent.
[4]
Furthermore, (E) The resin composition in any one of [1]-[3] containing antioxidant.
[5]
Furthermore, (F) The resin composition in any one of [1]-[4] containing an inorganic filler.
[6]
Furthermore, (G) The resin composition in any one of [1]-[5] containing an organic solvent.
[7]
A mesogenic group-containing cured product obtained by curing the resin composition according to any one of [1] to [6].
[8]
The method for producing a mesogenic group-containing cured product according to [7], wherein the components (B), (C) and other components are added to a solution or dispersion containing the component (A) and cured by heating.

  The resin composition of the present invention is easy to handle because it can be selected from a wide range of molding methods because it is soluble or dispersible in a solvent by using a mesogen-silicon compound copolymer, and further has a thermal conductivity. Therefore, it can be suitably used as a heat dissipation material, a resin material for semiconductor devices and electronic parts.

  Hereinafter, although the resin composition of this invention is demonstrated in detail, this invention is not limited to these.

<Resin composition>
The resin composition of the present invention is
(A) a mesogen / silicon compound copolymer containing two or more unsaturated hydrocarbon groups represented by the average composition formula (1) in one molecule;
(B) an organohydrogenpolysiloxane containing two or more SiH groups in one molecule;
(C) A platinum group metal catalyst is contained.

〔式中、Ｒ¹、Ｒ⁵はそれぞれ同一でも異なっていてもよい炭素原子数１〜２０の２価炭化水素基である。また、Ｒ²は下記式

で示される構造から選ばれる２価の基である。ｐは０又は１である。Ｒ³及びＲ⁴はそれぞれ炭素原子数２〜１０の不飽和基を含む１価炭化水素基であり、相互に異なっていても同一でもよい。また、ｑ、ｒはそれぞれ０、１又は２である。但し、ｑ、ｒは同時に０ではない。ｌ、ｍ、ｎはそれぞれ１未満の正数であり、ｏは０又は０．５以下の正数である。更にｌ、ｍ、ｎ、ｏはｌ＋ｍ＋ｎ＋ｏ＝１を満たす。Ｚ、Ｘはそれぞれ下記一般式（２）

（式中、Ｍｅはメチル基であり、ａは０〜６０の整数であり、ｂは０〜６０の整数である。Ｒ⁶及びＲ⁷はそれぞれ炭素原子数１〜２０の１価炭化水素基であり、相互に異なっていても同一でもよい。但し、Ｒ⁶、Ｒ⁷は同時にメチル基ではない。）
で示されるケイ素原子を含む２価の有機基である。〕 [(A) component]
The component (A) of the present invention is a mesogen / silicon compound copolymer containing two or more unsaturated hydrocarbon groups represented by the following average composition formula (1) in one molecule.

Wherein a divalent hydrocarbon group R ^1, R ⁵ is carbon atoms which may be the same or different, respectively 20. R ² is the following formula

Is a divalent group selected from the structure represented by: p is 0 or 1. R ³ and R ⁴ are each a monovalent hydrocarbon group containing an unsaturated group having 2 to 10 carbon atoms, and may be different or the same. Q and r are 0, 1 or 2, respectively. However, q and r are not 0 at the same time. l, m, and n are each a positive number less than 1, and o is a positive number that is 0 or 0.5 or less. Further, l, m, n, and o satisfy l + m + n + o = 1. Z and X are the following general formula (2)

(In the formula, Me is a methyl group, a is an integer of 0 to 60, and b is an integer of 0 to 60. R ⁶ and R ⁷ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms. And may be the same or different from each other, provided that R ⁶ and R ⁷ are not methyl groups at the same time.)
And a divalent organic group containing a silicon atom. ]

（式中、波線は結合手を示す。）
等が例示できる。 In the above formula (1), R ¹ and R ⁵ may be the same or different, and may be a linear, branched or cyclic alkylene group, alkenylene group, alkynylene group, arylene group, aralkylene group, A divalent hydrocarbon group having 1 to 20 carbon atoms such as a group in which two or more are bonded, and a divalent hydrocarbon group having 2 to 10 carbon atoms is preferable from the viewpoint of obtaining raw materials. As R ¹ and R ⁵ , specifically,
_{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 5 -,
_{- (CH 2) 6 -,} - (CH 2) 8 -, - (CH 2) 10 -, - (CH 2) 15 -,
_{- (CH 2) 20 -,} - CH (CH 3) -, - C (CH 3) (CH 3) -,
_{-CH 2 -CH (CH 3) -} , - CH 2 CH (CH 3) CH 2 -, - CH = CH-,
-C≡C-, -CH = CH-CH = CH-, -CH = CH-C≡C-,
_{-CH 2 -CH (CH 3) -CH} (CH 3) -, - CH 2 -CH (CH 2 CH 2 CH 3) -,
_{-CH 2 -C (CH 2 CH 2} CH 3) (CH 2 CH 2 CH 3) -,
_{-CH 2 -C (CH 2 CH (} CH 3) CH 3) (CH 2 CH 2 CH 3) -,
_{-CH 2 -C (CH 2 CH (} CH 3) CH 3) (CH 2 C (CH 3) (CH 3) CH 3) -,

(In the formula, a wavy line indicates a bond.)
Etc. can be illustrated.

で示される構造から選ばれる２価の基である。
ｐは０又は１である。 R ² is the following formula

Is a divalent group selected from the structure represented by:
p is 0 or 1.

R ³ and R ⁴ are each a monovalent hydrocarbon group containing an unsaturated group having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, and may be different or the same. Specific examples of R ³ and R ⁴ include monovalent aliphatic unsaturated groups such as alkenyl groups such as vinyl group, allyl group and methallyl group, alkynyl groups such as ethynyl group and 2-propynyl group. Among these, an allyl group and 2-propynyl group are preferable from the viewpoint of introduction of a functional group imparting thermosetting properties.
Moreover, q and r are 0, 1 or 2, respectively, preferably 0 or 1. However, q and r are not 0 at the same time.

  l is a positive number less than 1, preferably 0.1 to 0.7, more preferably 0.2 to 0.5, and m is a positive number less than 1, preferably 0.1. A positive number of ˜0.7, more preferably a positive number of 0.2 to 0.5, and n is a positive number of less than 1, preferably a positive number of 0.5 or less, more preferably 0.05 to 0. .4 is a positive number, and o is a positive number of 0 or 0.5 or less, preferably a positive number of 0.05 to 0.2. However, l, m, n, and o satisfy l + m + n + o = 1.

（式中、Ｍｅはメチル基であり、ａは０〜６０の整数であり、ｂは０〜６０の整数である。Ｒ⁶及びＲ⁷はそれぞれ炭素原子数１〜２０の１価炭化水素基であり、相互に異なっていても同一でもよい。但し、Ｒ⁶、Ｒ⁷は同時にメチル基ではない。） Z and X are each a divalent organic group containing a silicon atom represented by the following general formula (2).

(In the formula, Me is a methyl group, a is an integer of 0 to 60, and b is an integer of 0 to 60. R ⁶ and R ⁷ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms. And may be the same or different from each other, provided that R ⁶ and R ⁷ are not methyl groups at the same time.)

In the above formula (2), R ⁶ and R ⁷ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, and a decyl group. Alkyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl And an aralkyl group such as a group. Among these, a methyl group, a decyl group, and a phenyl group are preferable from the viewpoint of heat resistance. However, R ⁶ and R ⁷ are not methyl groups at the same time.
a is an integer of 0 to 60, preferably an integer of 1 to 10, and b is an integer of 0 to 60, preferably an integer of 0 to 10.

Examples of the group represented by the formula (2) include the following.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

  The mesogen / silicon compound copolymer of the present invention has at least 2, preferably 3-20, more preferably 5-10, unsaturated hydrocarbon groups bonded to a silicon atom in one molecule. When there are too few unsaturated hydrocarbon groups, poor curing may occur, and when there are too many, physical properties may deteriorate due to excessive crosslinking.

  The mesogen / silicon compound copolymer of the present invention has a polystyrene-reduced weight average molecular weight of 450 to 500,000, preferably 3,000 to 50,000, as measured by gel permeation chromatography using tetrahydrofuran as a developing solvent. It is a copolymer. If the weight average molecular weight is too small, the resin is fragile and the handleability may be difficult. If it is too large, the solubility in a solvent is deteriorated.

  In the mesogen-silicon compound copolymer containing the repeating unit represented by the above formula (1), each unit may be bonded randomly or may be bonded as a block polymer, but has a random structure. It is preferable.

Examples of such mesogen / silicon compound copolymers include the following.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

Next, although the manufacturing method of the mesogen silicon compound copolymer of this invention is shown, it is not this limitation.
The mesogen / silicon compound copolymer of the present invention comprises a compound selected from compounds represented by the following general formula (5), the following general formula (6), the following general formula (7), and the following general formula (8). And can be produced by the method shown below. In addition, in the said Formula (1), when o is 0, it manufactures without using the compound represented by following formula (8).

（式中、Ｒ²、Ｒ³、Ｒ⁴、ｐ、ｑ、ｒは上記と同じである。） After the compounds represented by the following general formula (5) and the following general formula (6) are reacted with an anhydride of a lower fatty acid such as acetic anhydride and acetylated, they and the following general formula (7) and the following general formula ( The mesogen / silicon compound copolymer of the present invention can be produced by subjecting the compound represented by 8) to a deacidification (acetic acid) polycondensation reaction.

(In the formula, R ² , R ³ , R ⁴ , p, q and r are the same as above.)

Examples of the compound represented by the formula (6) include the following.

（式中、Ｒ¹、Ｚは上記と同じである。）

(In the formula, R ¹ and Z are the same as above.)

（式中、Ｒ⁵、Ｘは上記と同じである。）
但し、式（８）で表される化合物は、式（７）で表される化合物とは異なる化合物である。

(In the formula, R ⁵ and X are the same as above.)
However, the compound represented by Formula (8) is a compound different from the compound represented by Formula (7).

Examples of such compounds represented by formulas (7) and (8) include the following.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

  As a method for producing the mesogen / silicon compound copolymer of the present invention, the compounds represented by the formulas (5) and (6) may be prepared by dehydrating lower fatty acids such as acetic anhydride, propionic anhydride, butyric anhydride, and valeric anhydride. The product is individually or collectively converted into an acetate ester, and then deoxidized (acetic acid) polycondensation with the compounds represented by formulas (7) and (8) in a separate reaction tank or the same reaction tank. The method of making it react is mentioned. As described above, the compound represented by formula (8) may or may not be used.

  When the compound represented by the formula (6) is used, the introduction amount is preferably 5 to 50 mol% of the total addition amount of the compounds represented by the formula (5) and the formula (6). Preferably it is 10-30 mol%. When the introduction amount of the compound represented by formula (6) is small, the introduction amount of the functional group is decreased, and there is a possibility that the change in physical properties due to the introduction of the functional group is less likely to occur. The introduction amount of the compound represented by formula (6) When there is much, thermal conductivity may fall.

The amount of the compound represented by the formulas (7) and (8) may be added so as to be equimolar with the compounds represented by the formulas (5) and (6). Molar ratio of the compound represented by (6) and the compound represented by formula (7) and formula (8) [formula (5) + formula (6)] / [formula (7) + formula (8)] Is preferably 0.90 to 1.10, more preferably 0.95 to 1.05. If the molar ratio of the introduction amount of the compound represented by formula (5) + formula (6) and the compound represented by formula (7) + formula (8) is too different, a high molecular weight resin may not be obtained. There is.
The compounds represented by the above formulas (7) and (8) may be added before reacting the compounds represented by the formulas (5) and (6) with the anhydride of the lower fatty acid. Good.

  The amount of the lower fatty acid anhydride used is preferably 1.01 to 1.50 times equivalent to the total of phenolic hydroxyl groups in the compounds represented by the above formulas (5) and (6). More preferably, it is 1.02-1.20 times equivalent.

  The reaction between the compounds represented by the above formulas (5) and (6) and the lower fatty acid anhydride is usually 100 to 180 ° C., more preferably 130 to 150 ° C., for 0.5 to 2 hours, particularly It is preferable to be performed for 1 to 1.5 hours. If the reaction temperature is too high, the anhydride of the lower fatty acid may volatilize, and if it is too low, the progress of the reaction may become extremely slow.

  The reaction is preferably carried out in the absence of solvent or in the presence of a solvent. Solvents used include toluene, benzene, xylene, chloroform, carbon tetrachloride, ethylcyclohexane, isododecane, isononane, tetrahydrofuran, 1,4-dioxane, cyclohexane. Examples include pentanone, ethyl acetate, and acetone. Further, it is particularly preferable to carry out the reaction under solvent-free conditions in order to increase the reaction temperature.

In the above production method, a catalyst may be used for the deoxidation (acetic acid) polycondensation reaction. Examples of the catalyst include germanium compounds such as germanium oxide, stannous oxalate, stannous acetate, and alkyltin oxide. , Tin compounds such as diaryltin oxide, titanium dioxide, titanium alkoxides, titanium compounds such as alkoxytitanium silicate, organic acids such as sodium acetate, potassium acetate, calcium acetate, zinc acetate, ferrous acetate Metal salts, Lewis acids such as BF ₃ and AlCl ₃ , amines, amides, hydrochloric acid, sulfuric acid and other inorganic acids. The amount of the catalyst may be appropriately adjusted, but is usually 0.1 to 10 mol%, preferably 0.5 to 5 mol%, based on the total resin used.

  The polycondensation reaction is usually at a temperature of 50 to 350 ° C., preferably 240 to 350 ° C., in the presence of an inert gas such as nitrogen, and under normal pressure or reduced pressure, usually for 0.5 to 24 hours, preferably 1 to It takes 5 hours. The ultimate degree of vacuum under reduced pressure is preferably 1 kPa or less, more preferably 0.6 kPa or less, and particularly preferably 0.3 kPa or less.

[Component (B)]
Component (B) is a cross-linking agent and is an organohydrogenpolysiloxane containing 2 or more, preferably 3 to 10 SiH groups in one molecule, which is linear, branched or cyclic. Can also be used, and examples include those shown below.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

（式中、Ｍｅはメチル基であり、Ｒ⁸〜Ｒ¹⁰はそれぞれ同一でも異なっていてもよい脂肪族不飽和結合を有さない炭素原子数１〜１２の１価の炭化水素基である。Ａは水素原子又はメチル基である。ｃ、ｄ、ｅはそれぞれ０〜６０の整数である。但し、Ａが１つメチル基の場合、ｃは１以上６０以下の整数であり、Ａが２つメチル基の場合、ｃは２以上６０以下の整数である。ｆ、ｈはそれぞれ０〜１０の整数であり、ｇは２〜１０の整数である。） As the component (B), one or more organohydrogenpolysiloxanes represented by the following general formulas (3) and (4) are preferable.

(In the formula, Me is a methyl group, and R ^{8 to} R ¹⁰ are each a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have the same or different aliphatic unsaturated bonds. A is a hydrogen atom or a methyl group, and c, d and e are each an integer of 0 to 60. However, when A is one methyl group, c is an integer of 1 to 60 and A is 2 In the case of one methyl group, c is an integer of 2 to 60. f and h are each an integer of 0 to 10, and g is an integer of 2 to 10.)

In the above formulas (3) and (4), R ^{8 to} R ¹⁰ may be the same or different and have 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, which do not have an aliphatic unsaturated bond. Monovalent hydrocarbon group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, etc. Examples thereof include cycloalkyl groups such as alkyl groups and cyclohexyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups and naphthyl groups, aralkyl groups such as benzyl groups, phenylethyl groups and phenylpropyl groups. Among these, a methyl group and a phenyl group are preferable from the viewpoint of obtaining raw materials.

In the above formula (3), A is a hydrogen atom or a methyl group.
C is an integer of 0-60, preferably 2-10, d is an integer of 0-60, preferably 1-30, and e is an integer of 0-60, preferably 1-60. It is an integer of 30, and c + d + e is preferably 2 to 130, particularly 2 to 70, and particularly 4 to 20. However, when A is a methyl group, c is not 0. When one of A is a methyl group and the other is a hydrogen atom, c is 1 or more, and when A is both a methyl group, c is 2 or more. It is.

  In said formula (4), f is an integer of 0-10, Preferably it is an integer of 1-3, g is an integer of 2-10, Preferably it is an integer of 2-5, h is an integer of 0-10. , Preferably an integer of 1 to 3, and f + g + h is preferably 3 to 10, particularly 3 to 6.

Examples of the compounds represented by these formulas (3) and (4) include those shown below.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

  The amount of the component (B) used is such that the molar ratio of the SiH group in the component (B) to the unsaturated group in the component (A) (SiH group / unsaturated group) is 0.1 to 10, particularly 0.5. It is preferable to mix in a range of ˜5. If the molar ratio of SiH groups to unsaturated groups is 0.1 or more, the crosslinking density does not decrease and the problem that the composition does not cure does not occur. If it is 10 or less, the crosslinking density does not become too high, and foaming due to residual SiH groups can be suppressed, which is preferable.

[Component (C)]
Component (C) is a platinum group metal catalyst, for example, chloroplatinic acid, alcohol solution of chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, platinum olefin compound complex, platinum vinyl group-containing siloxane complex, platinum support For example, carbon.

  The addition amount of the component (C) is an effective amount, and is usually preferably 1 to 5,000 ppm as platinum content (in terms of mass) with respect to the total of the components (A) and (B). More preferably, it is 2,000 ppm. If it is 1 ppm or more, the curability of the resin composition does not decrease and the crosslinking density does not decrease. If it is 5,000 ppm or less, the storage stability will be good.

[(D) component]
(D) Reaction control agent can be mix | blended with the resin composition of this invention. Component (D) is optionally added as necessary to prevent the composition liquid from thickening or gelling before heat-curing when the resin composition is prepared or applied to a substrate. It is.
Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl -1,3-divinyldisiloxane and the like, 1-ethynylcyclohexanol and 3-methyl-1-butyn-3-ol are preferred A.

  The blending amount in the case of using the component (D) is usually within the range of 0 to 8.0 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B), preferably 0. It is preferably 0.01 to 8.0 parts by mass, particularly 0.05 to 2.0 parts by mass. If it is 8.0 parts by mass or less, the curability of the resin composition does not decrease, and the effect of reaction control is sufficiently exhibited by adding.

[(E) component]
Furthermore, in order to improve thermal stability, (E) antioxidant may be mix | blended with the resin composition of this invention. The antioxidant is preferably at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, organic phosphorus compounds and organic sulfur compounds.

Hindered phenolic compounds;
Although the hindered phenol type compound used by this invention is not specifically limited, The hindered phenol type compound mentioned below is preferable.
1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330), 2,6-di-t-butyl- 4-methylphenol (trade name: Sumilizer BHT), 2,5-di-t-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-t-butyl-4-ethylphenol (trade name) : Nocrac M-17), 2,5-di-t-amylhydroquinone (trade name: Nocrac DAH), 2,2′-methylenebis (4-methyl-6-t-butylphenol) (trade name: Nocrac NS-6) ), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX 1222), 4,4′-thio (3-methyl-6-t-butylphenol) (trade name: Nocrac 300), 2,2′-methylenebis (4-ethyl-6-t-butylphenol) (trade name: Nocrac NS-5), 4,4 '-Butylidenebis (3-methyl-6-t-butylphenol) (Adekastab AO-40), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate (trade name: Sumilizer GM), 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (trade name: Sumilizer GS) ), 2,2′-methylenebis [4-methyl-6- (α-methyl-cyclohexyl) phenol], 4,4′-methylenebis (2, 6-di-t-butylphenol) (trade name: Cynox 226M), 4,6-bis (octylthiomethyl) -o-cresol (trade name: IRGANOX 1520L), 2,2′-ethylenebis (4,6 -Di-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1076), 1,1,3-tris- (2-methyl- 4-Hydroxy-5-t-butylphenyl) butane (trade name: ADK STAB AO-30), tetrakis [methylene- (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (trade name: ADK STAB AO-60), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) pro ONATE] (trade name: IRGANOX 245), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (trade name) : IRGANOX 565), N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] (trade name: IRGANOX 1035), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylpheny] L) propionyloxy] 1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA-80), tris- (3,5-di-t-) Butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114), bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax mixture (50:50) (trade name) : IRGANOX 1425WL), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1135), 4,4'-thiobis (6-t-butyl-3-methyl) Phenol) (trade name: Sumilizer WX-R), 6- [3- (3-t-butyl-4 Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra -t- butyldibenz [d, f] [1,3,2] dioxaphosphepin (trade name: Sumilizer GP) or the like.

Hindered amine compounds;
The hindered amine compound used in the present invention is not particularly limited, but the hindered amine compounds listed below are preferable.
p, p′-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (Nocrac PA), poly (2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: Nocrac 224,224) -S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N, N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N , N′-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N′-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N, N′-diallyl- p-Phenylenediamine (trade name: Nonflex TP), 4,4 ′ (α, α-dimethylbenzen ) Diphenylamine (trade name: Nocrac CD), p, p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N ′-(3-methacrylyloxy-2-hydroxypropyl) -p-phenylene Diamine (trade name: Nocrac G1), N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine (trade name: Ozonon 35), N, N′-di-sec-butyl-p-phenylenediamine (Trade name: Sumilizer BPA), N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl succinate-1 -(2-hydroxyethyl) -4-hydroxy- , 2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] (trade name: CHIMASSORB 944), N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino]- 6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate ( Product name: TINUVIN 123), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 770), 2- (3,5-di-t-butyl-4-hydroxybenzyl) 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) (trade name: TINUVIN 144), bis (1,2,2,6,6-pentamethyl-4- Piperidyl) sebacate (trade name: TINUVIN 765), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-57), Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-52), 1,2,3 -Mixed esterified product of butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), 1,2,3,4-butanetetracarboxylic Mixed esterified product of acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2,3,4-butanetetracarboxylic acid and 1,2 2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Mixed esterified product (trade name: LA-63P), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydride) Roxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: LA-68LD), (2,2,6,6- Tetramethylene-4-piperidyl) -2-propylene carboxylate (trade name: ADK STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl) -2-propylene carboxylate (trade name: ADK STAB LA-87) etc.

Organophosphorus compounds;
The organophosphorus compound used in the present invention is not particularly limited, but the organophosphorus compounds listed below are preferable.
Bis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Trade name: SANKO-HCA), triethyl phosphite (trade name: JP302), tri-n-butyl phosphite (trade name: 304), triphenyl phosphite (trade name: ADK STAB TPP), diphenyl monooctyl phosphite (Trade name: Adeka Stub C), tri (p-cresyl) phosphite (trade name: Chelex-PC), diphenyl monodecyl phosphite (trade name: Adeka Stub 135A), diphenyl mono (tridecyl) phosphite (trade name: JPM313) ), Tris (2-ethylhexyl) phosphite (trade name: J P308), phenyl didecyl phosphite (Adeka Stub 517), tridecyl phosphite (trade name: Adeka Stub 3010), tetraphenyldipropylene glycol diphosphite (trade name: JPP100), bis (2,4-di-t-) Butylphenyl) pentaerythritol diphosphite (trade name: Adekastab PEP-24G), tris (tridecyl) phosphite (trade name: JP333E), bis (nonylphenyl) pentaerythritol diphosphite (trade name: Adekastab PEP-4C) Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36), bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol Diphos Lite (trade name: ADK STAB PEP-45), trilauryl trithiophosphite (trade name: JPS312), tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS 168), tris (nonylphenyl) phosphite (Trade name: ADK STAB 1178), distearyl pentaerythritol diphosphite (trade name: ADK STAB PEP-8), tris (mono, dinonylphenyl) phosphite (trade name: ADK STAB 329K), trioleyl phosphite (trade name) : Chelex-OL), tristearyl phosphite (trade name: JP318E), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl) phosphite (trade name: JPH1200), tetra (C12- C15 mixed alk ) -4,4′-isopropylidene diphenyl diphosphite (trade name: Adekastab 1500), tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite (trade name: Adekastab) 260), hexa (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane-triphosphite (trade name: ADK STAB 522A), hydrogenated bisphenol A phosphite polymer (HBP), tetrakis (2,4-di-t-butylphenyloxy) 4,4′-biphenylene-di-phosphine (trade name: P-EPQ), tetrakis (2,4-di-t-butyl-5) -Methylphenyloxy) 4,4'-biphenylene-di-phosphine (trade name: GSY-101P), 2 -[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N- Bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl ] Etanamin (trade name: IRGAFOS 12), 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (trade name: ADK STAB HP-10) and the like.

Organic sulfur compounds;
The organic sulfur compound used in the present invention is not particularly limited, but the organic sulfur compounds listed below are preferable.
Dilauryl-3,3′-thiodipropionate (trade name: Sumilizer TPL-R), dimyristyl-3,3′-thiodipropionate (trade name: Sumilizer TPM), distearyl-3,3′-thiodipro Pionate (trade name: Sumilizer TPS), pentaerythritol tetrakis (3-lauryl thiopropionate) (trade name: Sumilizer TP-D), ditridecyl-3,3′-thiodipropionate (trade name: Sumilizer TL) 2-mercaptobenzimidazole (trade name: Sumilizer MB), ditridecyl-3,3′-thiodipropionate (trade name: Adekastab AO-503A), 1,3,5-tris-β-stearylthiopropionyloxyethyl Isocyanurate, 3, '- thiobis acid didodecyl ester (trade name: IRGANOX PS 800FL), 3,3'- thiobis acid Geographic click decyl ester (trade name: IRGANOX PS 802FL) and the like.

Among the above antioxidants, tetrakis [methylene- (3,5-di-t-butyl-4-] is particularly preferable in consideration of compatibility between the components (A) and (B) and the organic solvent. Hydroxyhydrocinnamate)] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) And propionate, 4,6-bis (octylthiomethyl) -o-cresol.
In addition, (E) component is not limited to 1 type, You may use multiple types together.

  (E) As addition amount of a component, it is 0-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.1-5 mass parts, More preferably, it is 0.2-3 mass parts. When blending the component (E), if the amount is too small, a sufficient effect cannot be obtained, and if it is too much, compatibility may not be obtained.

[(F) component]
Furthermore, in order to improve thermal conductivity and strength, the resin composition of the present invention may contain (F) an inorganic filler.
As the component (F), known inorganic fillers can be widely used. Specific examples include metal oxides, metal nitrides, metal hydroxides, conductive metal powders, conductive metal fibers, and ferrites.

  Examples of the metal oxide include zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride. Examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, and aluminum hydroxide. The conductive metal powder is a conductive metal powder obtained by atomizing various metals, the conductive metal fiber is a conductive metal fiber obtained by processing various metals into fibers, and the ferrites are various ferrites such as soft magnetic ferrite. There can be mentioned. Others such as diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, quartz powder, crystalline silica, kaolin, talc, antimony trioxide, fine powder mica, molybdenum disulfide, rock wool, ceramic fiber, asbestos, etc. Examples thereof include inorganic fibers and glass fillers such as glass fibers, glass powder, glass cloth, and fused silica. These can be used alone or in combination.

  Various shapes of the inorganic filler can be applied. Specifically, for example, particles, fine particles, nanoparticles, aggregated particles, composite particles in which large particles and fine particles are combined, tubes, nanotubes, wires, rods, needles, plates Various shapes such as a shape, an indeterminate shape, a rugby ball shape, a hexahedron shape, and a liquid. These inorganic fillers can be used regardless of natural products or synthetic products. These can be used alone or in combination.

  The average particle diameter of the inorganic filler is preferably 0.1 to 500 μm, more preferably 0.5 to 300 μm, and particularly preferably 1 to 100 μm. In the present invention, the average particle diameter can be determined, for example, as a weight average value (or median diameter) by a laser light diffraction method or the like.

  These inorganic fillers may be surface-treated with a surface treatment agent. A surface treating agent is not restrict | limited, A well-known thing can be used. Specifically, a silane coupling agent, a titanate coupling agent, etc. are mentioned, for example.

  When the inorganic filler is filled, the amount used is preferably 5 to 90% by volume in the resin composition (total of the components (A), (B) and (F)), and is 20 to 70% by volume. More preferably, it is preferably 25 to 60% by volume. If the filling amount is less than these ranges, the effect of adding the inorganic filler is small, and if it is more than this range, the strength of the resin is lowered.

[(G) component]
In the resin composition of the present invention, (G) an organic solvent can be used. The component (G) is preferably an organic solvent that dissolves or disperses the components (A), (B), (C), (D), and (E).
As a means for filling the mesogen group-containing resin with the inorganic filler, a method in which the resin is heated and melted and the inorganic filler is added in that state is common. However, in the present invention, since a mesogen / silicon compound copolymer that is soluble or dispersible in a solvent is used, it is possible to obtain a resin composition in which the mesogen / silicon compound copolymer is dissolved or dispersed in a solvent. is there.

Examples of the organic solvent (G) include ketones, esters, hydrocarbons, alkyl halides, ethers and the like, and organic solvents having 1 to 10 carbon atoms are preferable.
(G) Specific examples of the organic solvent include toluene, benzene, xylene, chloroform, carbon tetrachloride, tetrahydrofuran, 1,4-dioxane, cyclopentanone, ethyl acetate, acetone and the like.
In addition, (G) component is not limited to 1 type, You may use multiple types together.

  (G) As addition amount of a component, it is 10-1,000 mass parts with respect to a total of 100 mass parts of (A) and (B) component, Preferably it is 20-200 mass parts. If it is less than this, it may be difficult to dissolve each component of the resin composition, and if it is more than this, it may take time to remove the solvent and the productivity may be deteriorated.

  Other polymers may be blended in the resin composition of the present invention to such an extent that the characteristic that the mesogen / silicon compound copolymer can be prepared after being dissolved or dispersed in a solvent is not lost. For example, epoxy resin, polyolefin resin, bismaleimide resin, polyimide resin, polyether resin, phenol resin, silicone resin, polycarbonate resin, polyamide resin, polyester resin, fluorine resin, acrylic resin, melamine resin, urea resin, urethane resin, etc. Can be mentioned. When using these resin together, the usage-amount is the range of 0-10,000 mass part with respect to 100 mass parts of (A) component.

  In the resin composition of the present invention, as an additive other than the above-described components, any other component, for example, a reinforcing agent, a thickener, a release agent, a flame retardant, a stabilizer, a flame retardant, Pigments, colorants, other auxiliaries, and the like can be added as long as the effects of the present invention are not lost. It is preferable that the usage-amount of these additives is the range of 0-40 mass parts in total with respect to 100 mass parts of (A) component.

  Although it does not specifically limit as a manufacturing method of the resin composition of this invention, (A) A component is used as a solvent, after dissolving or disperse | distributing it to the said (G) organic solvent, each said additive ((B ), (C) and other components) are added, and the mixture is stirred until uniform, and then the solvent is preferably removed. In that case, you may heat from normal temperature to 80 degreeC.

  Moreover, as a viscosity (23 degreeC) range before solvent removal, 100-100,000 mPa * s is preferable, and 500-50,000 mPa * s is still more preferable when the ease of a process or a shaping | molding is considered. The removal of the solvent is preferably carried out at a temperature not higher than the boiling point of the solvent used so as not to generate bubbles for 1 hour or longer, particularly 1.5 to 12 hours. At that time, the pressure may or may not be reduced. In the present invention, the viscosity can be measured with a rotational viscometer.

  The resin composition of the present invention can be cured by heating at 100 to 250 ° C. for 0.5 to 5 hours, preferably 120 to 200 ° C. for 0.5 to 3 hours.

As a method for molding the cured product, a known method can be used. Preferably, the solution / dispersion solution before removing the solvent is put into an arbitrary mold, the solvent is removed, and the sheet-like heat is formed by heating and curing. A cured product can be obtained.
The resin composition of the present invention includes circuit board materials, sealing materials such as resistors, inductors and capacitors, or cases for electronic parts, sealing materials for IC / power transistor elements, cooling parts such as heat radiation fins, heat sinks and heat pipes. It is extremely effective for OA / communication equipment.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following example. Unless otherwise specified, “parts” and “%” are mass units. In the following examples, Me represents a methyl group, the alkenyl group amount is a value calculated from the molecular weight and the composition ratio of the polymer, and the viscosity is a value measured with a BN rotational viscometer at 23 ° C.

[Synthesis of Mesogen / Silicon Compound Copolymer]
The compounds used in the synthesis examples are shown below.

[Synthesis Example 1]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 50.00 g (0.269 mol) of the compound represented by the above formula (S-1), 93.44 g (0.336 mol) of the compound represented by S-2), 20.69 g (0.067 mol) of the compound represented by the above formula (S-3), and 71.96 g (0.705 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as resin (1). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (1) was 4,000 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis), and was found to be a compound represented by the following average structural formula. (Alkenyl group amount = 0.087 mol / 100 g)

[Synthesis Example 2]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 50.00 g (0.269 mol) of the compound represented by the above formula (S-1), 93.44 g (0.336 mol) of the compound represented by S-2), 17.84 g (0.067 mol) of the compound represented by the above formula (S-4), and 71.96 g (0.705 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was named Resin (2). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (2) was 5,500 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis), and was found to be a compound represented by the following average structural formula. (Alkenyl group amount = 0.088 mol / 100 g)

[Synthesis Example 3]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 50.00 g (0.269 mol) of the compound represented by the above formula (S-1), 270.67 g (0.336 mol) of the compound represented by S-6), 28.81 g (0.067 mol) of the compound represented by the above formula (S-5), and 71.96 g (0.705 mol) of acetic anhydride. Then, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as resin (3). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (3) was 12,000 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis), and was found to be a compound represented by the following average structural formula. (Alkenyl group amount = 0.039 mol / 100 g)

[Synthesis Example 4]
In a 500 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device, a Dean-Stark device and a reflux condenser, 50.00 g (0.269 mol) of the compound represented by the above formula (S-1), 46.72 g (0.168 mol) of the compound represented by S-2), 135.34 g (0.168 mol) of the compound represented by the above formula (S-6), and a compound represented by the above formula (S-4). After adding 17.84 g (0.067 mol) and 71.96 g (0.705 mol) of acetic anhydride, the mixture was heated to 150 ° C. in a nitrogen gas atmosphere and stirred for 1 hour. Thereafter, the mixture was heated to 240 ° C., and further stirred for 2 hours to distill off about 90% of the theoretical acetic acid production amount, and then reduced in pressure at 240 ° C., and melt polymerization was carried out for 1.5 hours. . As a result, the obtained resin was designated as resin (4). Gel permeation chromatography using GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a standard and monodisperse polystyrene as a standard under analysis conditions of flow rate 0.6 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. The weight average molecular weight of the resin (4) was 21,000 as measured by chromatography (GPC). This was subjected to ¹ H-nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis) and infrared absorption spectrum analysis (IR analysis), and was found to be a compound represented by the following average structural formula. (Alkenyl group amount = 0.056 mol / 100 g)

[Preparation of resin composition and cured product thereof]
The resins (1), (2), (3) and (4) synthesized above as the component (A) are replaced with the components (B), (C), (D), (E), (F The following compounds were used as component (G) and component (G).

As the component (B), (BI) and (B-II) shown below were used.

  In addition, 0.5% Carlsted catalyst (platinum olefin compound complex) as component (C), ethynylcyclohexanol as component (D), Adekastab AO-60 (tetrakis [methylene- (3,5-di) as component (E)) -T-butyl-4-hydroxyhydrocinnamate)] methane, manufactured by ADEKA), toluene was used as component (G). As component (F), DAW-45 (alumina, average particle size 45 μm) (manufactured by Denki Kagaku Kogyo), R972 (hydrophobic silica, average particle size 16 μm) (manufactured by Nippon Aerosil), UHP-2 (average particle size 10 μm) ( Hexagonal boron nitride (manufactured by Showa Denko) was used.

Furthermore, as a comparison with component (A), the following resin (5) having no biphenyl group was used (alkenyl group amount = 0.39 mol / 100 g).

[Examples 1 to 5]
Each component was blended according to the composition described in Table 1. Specifically, the component (A) was dissolved in the component (G), the components (B), (D), and (E) were mixed therein, and the mixture was stirred at 2,000 rpm for 20 minutes with a Nertaro mixer. . Next, the component (C) was added, followed by stirring at 2,000 rpm for 5 minutes using a Nertaro mixer. (F) component was added there, and it stirred at 2,000 rpm for 10 minutes with the Nertaro mixer. The obtained mixture is put into a mold and heated at 110 ° C. for 2 hours to volatilize toluene as a solvent, and then heated to 180 ° C. and the mixture is heated and cured for 1 hour to obtain a sheet-like cured product. Obtained. In addition, the viscosity of the mixture before solvent volatilization was 1,500 mPa · s in Example 1, 1,200 mPa · s in Example 2, 1,900 mPa · s in Example 3, and 2,800 mPa · s in Example 4. In Example 5, it was 1,800 mPa · s.

[Example 6]
Each component was blended according to the composition described in Table 1. Specifically, the component (A) was dissolved in the component (G), and the components (B) and (D) were stirred at 2,000 rpm for 20 minutes with a Nertaro mixer. Next, the component (C) was added, followed by stirring at 2,000 rpm for 5 minutes using a Nertaro mixer. The viscosity of the obtained mixture was 700 mPa · s. The obtained mixture is put into a mold and heated at 110 ° C. for 2 hours to volatilize toluene as a solvent, and then heated to 180 ° C. and the mixture is heated and cured for 1 hour to obtain a sheet-like cured product. Obtained.

[Comparative Example 1]
Each component was blended according to the composition described in Table 1. Specifically, the components (A), (B), (D), (E), and (G) were stirred at 2,000 rpm for 20 minutes with a Nertaro mixer. Next, the component (C) was added, followed by stirring at 2,000 rpm for 5 minutes using a Nertaro mixer. The viscosity of the obtained mixture was 450 mPa · s. The obtained mixture is put into a mold and heated at 110 ° C. for 2 hours to volatilize toluene as a solvent, and then heated to 180 ° C. and the mixture is heated and cured for 1 hour to obtain a sheet-like cured product. Obtained.

[Comparative Example 2]
Each component was blended according to the composition described in Table 1. Specifically, the components (A), (B), (D), (E), and (G) were stirred at 2,000 rpm for 20 minutes with a Nertaro mixer. Next, the component (C) was added, followed by stirring at 2,000 rpm for 5 minutes using a Nertaro mixer. (F) component was added there, and it stirred at 2,000 rpm for 10 minutes with the Nertaro mixer. The viscosity of the obtained mixture was 600 mPa · s. The obtained mixture is put into a mold and heated at 110 ° C. for 2 hours to volatilize toluene as a solvent, and then heated to 180 ° C. and the mixture is heated and cured for 1 hour to obtain a sheet-like cured product. Obtained.

[Thermal conductivity evaluation]
As a result of measuring the thermal conductivity of the cured products prepared in Examples 1 to 6 and Comparative Examples 1 and 2 with a 4φ sensor using a hot disk method thermal conductivity measuring device manufactured by Kyoto Electronics Industry, the thermal conductivity is shown in Table 1. It was as follows.

  As described above, since the resin composition of the present invention is soluble or dispersible in a solvent, large-scale equipment such as an injection molding machine is not required for filling and molding of the heat conductive filler. Moreover, the state before the solvent volatilization is also fluid at normal temperature, and is easy to handle. Nevertheless, the high thermal conductivity of the cured product of the resin composition by introduction of the mesogenic group is not impaired, and it can be said that the cured product of the resin composition of the present invention is suitable as a heat dissipation material for electric and electronic equipment.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (8)

(A) a mesogen / silicon compound copolymer containing two or more unsaturated hydrocarbon groups represented by the following average composition formula (1) in one molecule;
(B) an organohydrogenpolysiloxane containing two or more SiH groups in one molecule;
(C) A resin composition comprising a platinum group metal catalyst.

Wherein a divalent hydrocarbon group R ^1, R ⁵ is carbon atoms which may be the same or different, respectively 20. R ² is the following formula

Is a divalent group selected from the structure represented by: p is 0 or 1. R ³ and R ⁴ are each a monovalent hydrocarbon group containing an unsaturated group having 2 to 10 carbon atoms, and may be different or the same. Moreover, q and r are 0, 1 or 2, respectively, and q and r are not 0 at the same time. l, m, and n are each a positive number less than 1, and o is a positive number that is 0 or 0.5 or less. Further, l, m, n, and o satisfy l + m + n + o = 1. Z and X are the following general formula (2)

(In the formula, Me is a methyl group, a is an integer of 0 to 60, and b is an integer of 0 to 60. R ⁶ and R ⁷ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms. And may be the same or different from each other, provided that R ⁶ and R ⁷ are not methyl groups at the same time.)
And a divalent organic group containing a silicon atom. ] (B) Organohydrogenpolysiloxanes containing two or more SiH groups in one molecule are represented by the following general formulas (3) and (4).

(In the formula, Me is a methyl group, and R ^{8 to} R ¹⁰ are each a monovalent hydrocarbon group having 1 to 12 carbon atoms that may have the same or different aliphatic unsaturated bonds. A is a hydrogen atom or a methyl group, and c, d and e are each an integer of 0 to 60. However, when A is one methyl group, c is an integer of 1 to 60 and A is 2 In the case of one methyl group, c is an integer of 2 to 60. f and h are each an integer of 0 to 10, and g is an integer of 2 to 10.)
The resin composition according to claim 1, which is at least one organohydrogenpolysiloxane represented by the formula:   Furthermore, the resin composition of Claim 1 or 2 containing (D) reaction control agent.   Furthermore, the resin composition of any one of Claims 1-3 containing (E) antioxidant.   Furthermore, (F) The resin composition of any one of Claims 1-4 containing an inorganic filler.   Furthermore, (G) The resin composition of any one of Claims 1-5 containing an organic solvent.   A mesogenic group-containing cured product obtained by curing the resin composition according to any one of claims 1 to 6.   The method for producing a mesogenic group-containing cured product according to claim 7, wherein the components (B), (C) and other components are added to a solution or dispersion containing the component (A) and cured by heating.