JP2022020217A - Heat radiating member composition, heat radiating member, electronic device, and method for producing heat radiating member - Google Patents

Abstract

To provide a composition that can form a heat radiating member having high heat resistance and, furthermore, high heat conductivity.SOLUTION: Provided is a heat radiating member composition that comprises: a heat conductive inorganic filler; and a polysiloxane copolymer composed of a cage-type silsesquioxane repeating unit represented by the formula (A) and a particular chain-type siloxane repeating unit.SELECTED DRAWING: None

Description

The present invention relates to a composition capable of forming a heat radiating member used for an electronic device such as an electronic substrate. In particular, the present invention relates to a heat radiating member that has both the workability of a resin and extremely high heat resistance, and can dissipate heat by efficiently conducting and transmitting heat generated inside an electronic device.

In recent years, the operating temperature has risen due to the use of wide-gap semiconductors in semiconductor elements for power control of trains, hybrid automobiles, electric automobiles, and the like. Silicon carbide (SiC) semiconductors, which are attracting particular attention, have an operating temperature of 200 ° C. or higher, and therefore, the packaging material is required to have high heat resistance of 250 ° C. or higher. Further, as the operating temperature rises, thermal strain occurs due to the difference in the thermal expansion rate between the materials used in the package, and there is a problem that the life is shortened due to peeling of wiring or the like.

As a method for solving such heat resistance problems, high heat conductive ceramic substrates such as aluminum nitride and silicon nitride, and high heat resistant organic resins and silicone resins compounded with an inorganic filler for improving thermal conductivity have been developed. In particular, the development of high heat resistant resins such as oxazine and high heat resistant silicone resins is progressing. Patent Document 1 discloses a polybenzoxazine-modified bismaleimide resin having excellent heat resistance. However, those compounds that exhibit sufficient heat resistance and durability have not yet been put into practical use, and therefore, materials having higher heat resistance are being developed.

Another method for solving the heat resistance problem of the member is to improve the thermal conductivity to reduce the temperature unevenness, and as a result, to reduce the local high temperature. In addition, if the thermal conductivity is high, it is expected that the temperature of the parts in contact will not rise easily. In order to increase the thermal conductivity of the resin component, it is generally considered to introduce many cyclic structures into the main chain of the molecule. Further, it is said that it is better that the linearity of the molecular chain is high in order to improve the thermal conductivity of these resins. As a compound having many cyclic structures and good linearity, a liquid crystal compound can be considered.
In Patent Document 2, as a method for improving the thermal conductivity of the resin, the orientation of a liquid crystal composition containing a liquid crystal compound having a polymerization group at both ends is controlled by an orientation control additive, a rubbing treatment method, or the like to maintain the orientation state. Disclosed is a method for obtaining a resin film having high thermal conductivity by polymerizing in a state of being in the state of being polymerized.

Polymers containing silsesquioxane having a cage-type structure are attracting attention from various fields because they have a unique structure and are expected to have a unique effect. As a polymer containing such a silsesquioxane skeleton, a silicon-based polymer having a silsesquioxane skeleton in the main chain is known (see, for example, Patent Document 3). Further, a silicone film having excellent heat resistance has been developed by introducing a crosslinkable functional group into a silicon compound having a silsesquioxane skeleton having a cage structure in the main chain to form a crosslinkable polymer (Patent Document 4). ..

Japanese Unexamined Patent Publication No. 2012-97207 Japanese Unexamined Patent Publication No. 2006-265527 Japanese Unexamined Patent Publication No. 2006-333007 Japanese Unexamined Patent Publication No. 2010-116464

As described above, a material having high heat resistance and thermal conductivity is desired for a substrate of a semiconductor device used at a high temperature.
Therefore, it is an object of the present invention to provide a composition capable of forming a heat radiating member having high heat resistance and high thermal conductivity.

The present inventors have made heat resistance (heat resistance) by using a siloxane polymer containing a hydroxyl group in the main chain by reacting a silsesquioxane compound with a compound containing a chain siloxane structure in the compounding of an organic compound and an inorganic material. The present invention has been completed by finding that a heat-dissipating member having an extremely high 1% or 5% weight loss temperature (1% or 5% weight loss temperature) of approximately 350 ° C. or higher and a high thermal conductivity can be formed.

式（Ａ）および（Ｂ）中、
Ｒ^０は独立して、炭素数６～２０のアリールまたは炭素数５～６のシクロアルキルであり、炭素数６～２０のアリールおよび前記炭素数５～６のシクロアルキルにおいて、少なくとも1つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく；
Ｒ^１は独立して、水素、ビニル、アリル、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、および炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも1つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく；
Ｒ^２は独立して、水素、ビニル、アリル、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、および炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも１つの水素が、ハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく；
ｘおよびｙは独立して、１以上である。 The composition for a heat radiating member according to the first aspect of the present invention is
With thermally conductive inorganic fillers;
A polysiloxane copolymer consisting of a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B);
including.

In formulas (A) and (B),
^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms, at least one hydrogen is contained. It may be replaced with a halogen or an alkyl having 1 to 20 carbon atoms;
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
^R2 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an arylalkyl having 7 to 40 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-,. Alternatively, it may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O-. Alternatively, it may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
x and y are independently 1 or more.

With this configuration, the thermally conductive inorganic filler can efficiently transfer heat via the polysiloxane copolymer having high adhesion to the metal member, and can have high thermal conductivity.

In the composition for a heat radiating member according to the second aspect of the present invention, the heat conductive inorganic filler is surface-treated with a surface treatment agent in the composition for a heat radiating member according to the first aspect of the present invention. ..
With this configuration, a composite can be formed in an affinity between the polysiloxane copolymer and the thermally conductive inorganic filler, and the thermally conductive inorganic filler can be used together with the polysiloxane having high adhesion to the metal member. Heat can be efficiently transferred through the polymer and can have high thermal conductivity.

The composition for a heat radiating member according to a third aspect of the present invention comprises a first inorganic filler having thermal conductivity bonded to one end of a first surface treatment agent;
Containing; with a thermally conductive second inorganic filler coupled to one end of the second surface treatment agent;
By hardening treatment
The other end of the first surface treatment agent and the other end of the second surface treatment agent are bonded to the polysiloxane copolymer, or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer in its structure, and the other end of the first surface treatment agent and the second surface treatment agent. The other ends join each other.
With this structure, the heat-dissipating inorganic fillers can be directly bonded to each other via the surface treatment agent and the polysiloxane copolymer to form a heat-dissipating member. Therefore, it is possible to directly propagate phonons, which are the main elements of heat conduction. Further, the polysiloxane copolymer and the thermally conductive inorganic filler can form a composite in an affinity manner, and the thermally conductive inorganic filler is via the polysiloxane copolymer having high adhesion to the metal member. Therefore, heat can be efficiently transferred, and the heat radiating member after curing can have high thermal conductivity.

The composition for heat-dissipating member according to the fourth aspect of the present invention is a siloxane polymer further containing a cross-linking agent or a transition metal catalyst in the composition for heat-dissipating member according to the first aspect of the present invention.
With such a configuration, the heat radiating member can contain a more preferable compound because the siloxane polymer is compounded with the heat-conducting inorganic filler in a state via a cross-linking agent.

In the composition for a heat radiating member according to the fifth aspect of the present invention, the cross-linking agent is the formula (2-1) or the formula (2-2) in the composition for a heat radiating member according to the fourth aspect of the present invention. ) Is a compound.

R ³ O- [Si (OR ³ ) ₂ -O-] _m -R ³ (2-1)

R ³ O- [Si (OR ³ ) ₂ ] -A ^1- [Z] _n -A ^2- [Si (OR ³ ) ₂ ] -OR ³ (2-2)

In equations (2-1) and (2-2),
^R3 is independently methyl or ethyl;
A ¹ and A ² are independently single-bonded or alkyl having 1 to 10 carbon atoms, in which at least one hydrogen may be replaced by fluorine and at least one-in the alkyl having 1 to 10 carbon atoms. CH _2- may be replaced by -O- or -CH = CH-;
Z is an independently aryl with 6 to 20 carbon atoms;
m is 1 to 10;
n is 1 to 4.
With such a configuration, the heat radiating member becomes a member in which the siloxane polymer is firmly bonded to the cross-linking agent and has good adhesion to a metal or the like.

In the composition for a heat radiating member according to the sixth aspect of the present invention, the heat conductive inorganic filler is surface-treated with a surface treatment agent in the composition for a heat radiating member according to the fifth aspect of the present invention. It is characterized by that.
With this structure, the heat radiating member obtained from the composition for the heat radiating member has a siloxane polymer that is firmly bonded to the cross-linking agent and has good adhesion to a metal or the like. Further, the polysiloxane copolymer and the thermally conductive inorganic filler can form a composite in an affinity manner, and the thermally conductive inorganic filler is via the polysiloxane copolymer having high adhesion to the metal member. Therefore, heat can be efficiently transferred, and the heat radiating member after curing can have high thermal conductivity.

The composition for heat-dissipating member according to the seventh aspect of the present invention is the first composition for heat-dissipating member according to the sixth aspect of the present invention, which has thermal conductivity bonded to one end of the first surface treatment agent. With an inorganic filler;
Containing; with a thermally conductive second inorganic filler coupled to one end of the second surface treatment agent;
By hardening treatment
The other end of the first surface treatment agent and the other end of the second surface treatment agent are characterized by binding to the polysiloxane copolymer and the cross-linking agent, respectively, or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer or a cross-linking agent, and the other end of the first surface treatment agent and the other of the second surface treatment agent. It is characterized in that the ends are joined to each other.
With this configuration, a heat radiating member having a high thermal conductivity of the thermally conductive inorganic filler and a very small thermal expansion rate can be obtained.

In the composition for heat-dissipating member according to the eighth aspect of the present invention, the surface treatment agent is cupped in the composition for heat-dissipating member according to any one of the second to third and sixth to seventh aspects of the present invention. It is characterized by being a ring agent.
With this configuration, a heat radiating member having a high thermal conductivity of the thermally conductive inorganic filler and a very small thermal expansion rate can be obtained.

In the composition for heat-dissipating member according to the ninth aspect of the present invention, the surface treatment agent is siloxane in the composition for heat-dissipating member according to any one of the second to third and sixth to seventh aspects of the present invention. It is characterized by being a compound.
With this configuration, a heat radiating member having a high thermal conductivity of the thermally conductive inorganic filler and a very small thermal expansion rate can be obtained.

The composition for a heat radiating member according to the tenth aspect of the present invention has a weight average molecular weight of 2 for the polysiloxane copolymer in the composition for a heat radiating member according to any one of the first to ninth aspects of the present invention. It is characterized in that it is in the range of 000 to 10,000,000.
With such a configuration, the adhesion to the thermally conductive inorganic filler can be further improved, and the thermal conductivity of the thermally conductive inorganic filler can be improved.

The composition for a heat radiating member according to the eleventh aspect of the present invention is the composition for a heat radiating member according to any one of the first to tenth aspects of the present invention, in the formulas (A) and (B). It is preferred that R ⁰ is independently phenyl or cyclohexyl and R ¹ and R ² are independently methyl or phenyl compounds.
With this configuration, the heat dissipation member has high heat resistance.

The heat-dissipating member composition according to the twelfth aspect of the present invention is the heat-dissipating member composition according to any one of the first to eleventh aspects of the present invention, and is a thermally conductive inorganic filler or a thermally conductive composition. The first inorganic filler and the second inorganic filler having thermal conductivity are nitrides, metals, metal oxides, silicate compounds, or carbon materials.
When configured in this way, it becomes a heat radiating member having high thermal conductivity.

The composition for a heat radiating member according to the thirteenth aspect of the present invention is the heat radiating member according to any one of the first to twelfth aspects of the present invention, which is a heat conductive inorganic filler or a heat conductive first. Inorganic filler and heat conductive second inorganic filler are selected from boron nitride, aluminum nitride, boron carbide, carbon nitride carbon, graphite, carbon fiber, carbon nanotubes, alumina, zinc oxide, gold, silver and cordierite. It is characterized by being at least one.
When configured in this way, it becomes a heat radiating member having high thermal conductivity.

The composition for a heat radiating member according to the fourteenth aspect of the present invention is the heat radiating member according to any one of the first to thirteenth aspects of the present invention, and is a heat conductive inorganic filler or a heat conductive material. It is characterized by further containing a polymerizable or polymer compound; which is not bound to a first inorganic filler and a thermally conductive second inorganic filler.
With this configuration, the heat-conducting inorganic fillers form a heat-dissipating member in which the surface treatment agent and the siloxane polymer are bonded to each other.

The heat radiating member according to the fifteenth aspect of the present invention is a heat radiating member obtained by curing the heat radiating member composition in the heat radiating member according to any one of the first to the fourteenth aspects of the present invention.
With this configuration, the heat-conducting inorganic fillers form a heat-dissipating member in which the surface treatment agent and the siloxane polymer are bonded to each other.

The electronic device according to the sixteenth aspect of the present invention includes the heat radiating member according to the fifteenth aspect of the present invention; an electronic device having a heat generating portion; so that the heat radiating member comes into contact with the heat generating portion. An electronic device arranged in the electronic device.
With such a configuration, the heat radiating member has good heat resistance and can control the thermal expansion rate up to a high temperature, so that thermal strain that may occur in the electronic device can be suppressed.

The method for producing a composition for a heat radiating member according to a seventeenth aspect of the present invention includes a step of binding a first inorganic filler having thermal conductivity to one end of a first surface treatment agent;
It comprises a step of binding the second inorganic filler of thermal conductivity to one end of the second surface treatment agent;
A step of binding the other end of the first surface treatment agent and the other end of the second surface treatment agent to the polysiloxane copolymer; or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer in its structure, and the other end of the first surface treatment agent and the second surface treatment agent. A step of joining the other ends to each other;
With this configuration, the heat-conducting inorganic fillers form a heat-dissipating member in which the surface treatment agent and the siloxane polymer are bonded to each other.

The method for producing a composition for a heat radiating member according to an eighteenth aspect of the present invention includes a step of binding a first inorganic filler having thermal conductivity to one end of a first surface treatment agent;
It comprises a step of binding the second inorganic filler of thermal conductivity to one end of the second surface treatment agent;
A step of binding the other end of the first surface treatment agent and the other end of the second surface treatment agent to the first polysiloxane copolymer and the second polysiloxane copolymer; or
At least one of the first surface treatment agent and the second surface treatment agent contains a first polysiloxane copolymer or a second polysiloxane copolymer in its structure, and the first surface treatment agent. A step of bonding the other end of the surface treatment agent and the other end of the second surface treatment agent to each other;

The heat radiating member formed from the composition for a heat radiating member of the present invention has extremely high thermal conductivity and heat resistance. Furthermore, it has excellent properties such as controllability of thermal expansion rate, chemical stability, hardness and mechanical strength. The heat radiating member is suitable for, for example, a heat radiating substrate, a heat radiating plate (plane heat sink), a heat radiating sheet, a heat radiating coating film, a heat radiating adhesive, or the like.

In the heat dissipation member of the present invention, it is a conceptual diagram showing the bonding between thermally conductive inorganic fillers by taking boron nitride as an example. It is a conceptual diagram showing that the other end of the polysiloxane copolymer 21 bonded to the first surface treatment agent 11 is bonded to the other end of the second surface treatment agent 12 by the curing treatment of the composition for a heat radiating member. be.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each figure, parts that are the same as or correspond to each other are designated by the same or similar reference numerals, and duplicated description will be omitted. Further, the present invention is not limited to the following embodiments.

The terms used in the present invention will be described. The compound represented by the formula (1) may be referred to as a compound (1). The same applies to compounds represented by other formulas. The expression "at least one A may be replaced by B or C" means that at least one A is replaced by B and at least one A is replaced by C. It means that at the same time as being replaced by B, at least one of the other A's may be replaced by C. In the chemical formulas described herein, Me is methyl and Ph is phenyl. In the examples, the display data of the electronic balance is shown using g (gram) which is a mass unit. Weight% and weight ratio are data based on such numerical values.

[Composition for heat dissipation member]
The composition for a heat-dissipating member of the present invention is a composition containing a thermally conductive inorganic filler and a polysiloxane copolymer and capable of forming a heat-dissipating member by thermosetting or the like. FIG. 1 is an example in which boron nitride is used as a thermally conductive inorganic filler. When boron nitride (h-BN) is treated with a surface treatment agent, since boron nitride has no reactive group on the plane of the particles, the surface treatment agent is bonded only to the periphery thereof. Boron nitride treated with a surface treatment agent can form a bond with a polysiloxane copolymer or a cross-linking agent. Therefore, by bonding the other end of the surface treatment agent bonded to boron nitride and the other end of the polysiloxane copolymer or the cross-linking agent further bonded to the surface treatment agent bonded to boron nitride (see FIG. 2). Boron nitrides are bonded to each other as shown in FIG.
In this way, by binding the thermally conductive inorganic fillers to each other with a surface treatment agent and a polysiloxane composite or a cross-linking agent, phonons can be directly propagated, so that the heat radiation member after curing is extremely high. It is possible to fabricate a composite material that has thermal conductivity and directly reflects the thermal expansion rate of the inorganic component.

<Polysiloxane copolymer>
The polysiloxane copolymer has a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B).

Cage-shaped silsesquioxane repeating unit represented by the formula (A)

In formula (A),
^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms, at least one hydrogen is independent. And may be replaced with halogen or alkyl with 1 to 20 carbon atoms;
R ¹ independently contains hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or alkyl with 1 to 40 carbon atoms. Represented in an aryl of 6 to 20 carbons, a cycloalkyl of 5 to 6 carbons and an arylalkyl of 7 to 40 carbons, at least one hydrogen is replaced by a halogen or an alkyl of 1 to 20 carbons. Also, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with halogen, and at least one -CH _2- is -O-, -CH = CH-, or carbon. Alkyl of number 5 to 20 may be replaced by an alkyl having 1 to 40 carbons, at least one hydrogen may be replaced by halogen, and at least one -CH _2- may be replaced with -O- or carbon. May be replaced with the number 5-20 cycloalkylene;
x is 1 or more.

(R ⁰ in equation (A))
^R0 is independently an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms.
Examples of the aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferred, with phenyl, naphthyl and anthryl being more preferred.
Examples of the cycloalkyl having 5 to 6 carbon atoms include cyclopentyl and cyclohexyl.
^R0 is preferably phenyl or cyclohexyl.

(R ¹ in equation (A))
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or alkyl with 1 to 40 carbon atoms. be.
Examples of the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are the same as those described in ^R0 .
Examples of the arylalkyl having 7 to 40 carbon atoms include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl and 4-phenylbutyl. , 5-Phenylpentyl.
Examples of alkyl having 1 to 40 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, and iso-. Examples include pentyl, tert-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl and octadecyl.
R ¹ is preferably selected from phenyl, cyclohexyl, and alkyl having 1-5 carbon atoms, preferably phenyl or methyl.

(X in formula (A))
x is 1 or more, and the total number of cage-type silsesquioxane repeating units represented by the formula (A) in the polysiloxane copolymer is, for example, 1 to 500.

Chained siloxane repeating unit represented by the formula (B)

In formula (B), R ² is independently hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or carbon number of carbon atoms. In the aryls of 1 to 40 alkyl, 6 to 20 carbon atoms, 5 to 6 carbon atoms cycloalkyl and 7 to 40 carbon atoms arylalkyl, at least one hydrogen is independently halogen or carbon number. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O-. , -CH = CH-, or a cycloalkylene having 5 to 20 carbon atoms may be substituted, and an alkyl having 1 to 40 carbon atoms may have at least one hydrogen substituted with a halogen, and at least one-. CH _2- may be replaced with —O— or a cycloalkylene with 5 to 20 carbon atoms;
y is 1 or more.

(R ² in equation (B))
^R2 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or alkyl with 1 to 40 carbon atoms. However, the arylalkyl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are the same as those described in ^R0 , and the arylalkyl having 7 to 40 carbon atoms and the cycloalkyl having 1 to 40 carbon atoms are mentioned. Alkyl may be similar to that described in ^R1 .

(Y in equation (B))
y is 1 or more, and the total number of chain siloxane repeating units represented by the formula (B) in the polysiloxane copolymer (y1 + y2 described later) is, for example, 1 to 3000.

The polysiloxane copolymer is bonded to the surface of a substance selected from an inorganic substance and an organic substance via a chain siloxane represented by the formula (B). Here, the bond is preferably a chemical bond. For example, a functional group such as a hydroxyl group may be imparted to the surface of the substance, and a chemical bond may be formed by a chemical reaction between the functional group and the terminal hydroxyl group of the chain siloxane represented by the formula (B). The chain siloxane represented by the formula (B) may be directly bonded to the surface of the substance, or may be bonded via a spacer or the like.

"The polysiloxane copolymer binds to the surface of a substance selected from an inorganic substance and an organic substance via a chain siloxane represented by the formula (B)" means that the chain represented by the formula (B). The siloxane (linker moiety) first binds to the surface of the substance, followed by the cage-type silsesquioxane repeating unit represented by the formula (A) and the chain siloxane repeating unit represented by the formula (B). It means that they are combined in any proportion and in any order.
[Substances selected from inorganic and organic substances] _{-By 1- (} A _x By 2)
The number of repetitions y1 in the chain siloxane (linker portion) represented by the formula (B) bonded to the surface of the substance is, for example, 1 to 1000.
In (A _x By 2), the number of cage-type _{silsesquioxane} repeating units (x) represented by the continuous formula (A) is, for example, 1 to 5, and is represented by the continuous formula (B). The number of chain siloxane repeating units (y2) is, for example, 1 to 30.

式（３）中、Ｒ^４は独立して、水素、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、炭素数１～４０のアルキル、炭素数１～４０のアルコキシ、ビニル、またはアリルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキルおよび炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも１つの水素が、ハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルは、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルコキシは、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよい。 In the polysiloxane copolymer according to the present invention, the terminal different from the terminal bonded to the substance selected from the inorganic substance and the organic substance is not particularly limited and may be a hydroxyl group, but has the following group. May be good.

In formula (3), ^R4 is independently hydrogen, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, and alkyl having 1 to 40 carbon atoms. , An alkoxy, vinyl, or allyl having 1 to 40 carbon atoms, and at least one hydrogen in the aryl in an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, and an arylalkyl having 7 to 40 carbon atoms. May be replaced with halogen or an alkyl having 1 to 20 carbon atoms, and at least one hydrogen may be replaced with a halogen in the alkylene in the arylalkyl having 7 to 40 carbon atoms, and at least one -CH ₂ -May be replaced with -O-, -CH = CH-, or a cycloalkylene having 5 to 20 carbon atoms, and an alkyl having 1 to 40 carbon atoms may have at least one hydrogen replaced by a halogen. , At least one -CH _2- may be replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms, and an alkoxy having 1 to 40 carbon atoms may be replaced with at least one hydrogen by halogen. , At least one -CH _2- may be replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms.

Examples of the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are the same as those described by ^R0 in the formula (A).
Examples of the arylalkyl having 7 to 40 carbon atoms and the alkyl having 1 to 40 carbon atoms are the same as those described by ^R1 in the formula (A).
The alkoxy having 1 to 40 carbon atoms is not particularly limited, but is preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, and propoxy.
R3 is preferably hydrogen ^, methylphenyl, vinyl, allyl, or a hydroxyl group.

In the polysiloxane in the polysiloxane copolymer used in the present invention, the ratio (x: y) of the repeating unit represented by the formula (A) to the repeating unit represented by the formula (B) is not particularly limited. For example, 1: 1 to 1:30.
In the polysiloxane in the polysiloxane copolymer, the mass% occupied by the repeating units represented by the formulas (A) and (B) is usually 10% or more, preferably 30% or more, more preferably 50%. As mentioned above, it is particularly preferably 70% or more, usually less than 100%, preferably 99% or less. That is, a unit other than the repeating unit represented by the formula (A) may be included as long as the effect of the present invention is not significantly impaired. Examples of such a unit include-(CH ₂ -CH ₂ )-,-(CH = CH)-,-(O-SiMe ₂ -C ₆ H ₄ -SiMe ₂ )-.

The weight average molecular weight (Mw) of the polysiloxane in the polysiloxane copolymer used in the present invention is not particularly limited, but is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000. Below, it is more preferably 500,000 or less, still more preferably 200,000 or less. The weight average molecular weight is determined by calculating a chromatogram obtained by gel permeation chromatography (GPC) from a calibration curve obtained with a molecular weight standard sample, as described in Examples described later.
The polydispersity is, for example, 1 to 4.

These polysiloxane copolymers can be produced, for example, by the following steps.
(I) Equilibrium polymerization of chain or cyclic siloxanes on the surface of a substance selected from inorganic and organic substances, followed by
(Ii) Step of equilibrium polymerization of cage-type silsesquioxane

For example, a chain siloxane is grafted on the silica surface by reacting an inorganic oxide (silica) whose surface is a hydroxyl group with a chain or cyclic siloxane, an acid catalyst, or a solvent. Next, by adding terminal silanol-type cage-type silsesquioxane to the solution being polymerized, equilibrium polymerization with the grafted siloxane polymer is carried out, and cage-type silsesquioxane is incorporated in the middle of the chain siloxane, and the molecular necklace. Polymer-grafted silica is obtained.

Examples of the chain or cyclic siloxane include compounds represented by the formula (b) or the formula (c). Either or both of these can be used. It is preferable that a reactive functional group such as a hydroxyl group is present on the surface of the substance selected from the inorganic substance and the organic substance, and a surface treatment may be performed to introduce such a reactive functional group.

R ^{2 in formula (b) and formula (c) is defined in the same way as R 2 in} formula (A), as is the preferred example. n is an integer of 2 to 30.

Examples of the compound represented by the formula (b) include 2,2,4,4,6,6-hexamethylcyclotrisiloxane and 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane. , 2,2,4,4,6,6-hexaethylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-triethyl-2,4 , 6-Tripropylcyclotrisiloxane, 2,2,4,4,6,6-hexapropylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (1-methylethyl) cyclotri Siloxane, 2,4,6-triethyl-2,4,6-tris (1-methylethyl) cyclotrisiloxane 2,2,4,4,6,6-hexakis (1-methylethyl) cyclotrisiloxane, 2, , 4,6-Tributyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tributyl-2,4,6-triethylcyclotrisiloxane, 2,2,4,4,6,6-hexa Butylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (1,1-dimethylethyl) cyclotrisiloxane, 2,46-triethyl-2,4,6-tris (1,1-tris) Dimethylethyl) cyclotrisiloxane, 2,4,6-tris (1,1-dimethylethyl) -2,4,6-tripropylcyclotrisiloxane, 2,2,4,4,66-hexakis (1,1) -Dimethylethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (trifluoromethyl) cyclotrisiloxane, 2,2,4,4,6,6-hexakis (trifluoromethyl) Cyclotrisiloxane, 2,2,4,4,6,6-hexakis (1,1,2,2,2-pentafluoroethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6- Tris (3,3,3-trifluoropropyl) cyclotrisiloxane, 2,2,4,4,6,6-hexakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 2,4,6- Trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,2,4,4,6,6-hexaphenylcyclotrisiloxane, 2,4,6-tricyclohexyl-2,4,6-trimethylcyclo Trisiloxane, 2,2,4,4,6,6-hexacyclohexylcyclotrisiloxane, 2,2,4,4,6,6-hexavinylcyclotrisiloxane, 2 , 4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane, 2,4,6,8-tetraethyl -2,4,6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaethylcyclotrisiloxane, 2,4,6,8-tetramethyl-2, 4,6,8-Tetrapropylcyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8, 8-octapropylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (1-methylethyl) cyclotetrasiloxane, 2,4,6,8-tetraethyl-2, 4,6,8-Tetraxane (1-methylethyl) cyclotetrasiloxane 2,2,4,4,6,6,8,8-octakis (1-methylethyl) cyclotetrasiloxane, 2,4,6,8 -Tetrabutyl-2,4,6,8-Tetramethylcyclotetrasiloxane, 2,4,6,8-Tetrabutyl-2,4,6,8-Tetraethylcyclotetrasiloxane, 2,2,4,4,6 6,8,8-Octabutylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6 8-Tetraethyl-2,4,6,8-tetrakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6,8-tetrakis (1,1-dimethylethyl) -2,4,6,8 -Tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (1,1-dimethylethyl) cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4 , 6,8-Tetrakiss (trifluoromethyl) cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (trifluoromethyl) cyclotetrasiloxane, 2,2,4,4,6 , 6,8,8-octakis (1,1,2,2,2-pentafluoroethyl) cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (3, 3,3-Trifluoropropyl) cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 2,4,6 8-Tetramethyl-2, 4,6,8-Tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaphenylcyclotetrasiloxane, 2,4,6,8-tetracyclohexyl-2,4 6,8-Tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octacyclohexylcyclotetrasiloxane, 2,2,4,4,6,6,8-octa Vinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,6-dietinyl-2,4,4,6,8,8-hexamethyl Cyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8, 10-Pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaethylcyclotrisiloxane, 2,4,6,8.10-pentamethyl-2,4 6,8-Pentapropylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8,10-pentapropylcyclopentasiloxane, 2,2,4,4,6,6 8,8,10,10-decapropylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentakis (1-methylethyl) cyclopentasiloxane, 2,4 , 6,8,10-Pentaethyl-2,4,6,8,10-pentakis (1-methylethyl) cyclopentasiloxane 2,2,4,4,6,6,8,8,10,10-decakis (1-Methylethyl) Cyclopentasiloxane, 2,4,6,8,10-Pentabutyl-2,4,6,8,10-Pentamethylcyclopentasiloxane, 2,4,6,8,10-Pentabutyl- 2,4,6,8,10-pentaethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decabutylcyclopentasiloxane, 2,4,6,8, 10,10-Pentamethyl-2,4,6,8,10,10-pentakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8 , 10-Pentakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentakis (1,1-dimethylethyl) -2,4,6,8,10-pentapropylcyclopenta Siloxane, 2,2,4,4,6 , 6,8,8,10,10-decakis (1,1-dimethylethyl) cyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8-pentakis (trifluoromethyl) Cyclopentasiloxane, 2,2,4,4,6,6,8,8,10.10-decakis (trifluoromethyl) cyclopentasiloxane, 2,2,4,4,6,6,8,8, 10,10-decakis (1,1,2,2,2-pentafluoroethyl) cyclopentasiloxane, 2,4,6,8,10,10-pentamethyl-2,4,6,8-pentakis (3, 3,3-Trifluoropropyl) cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 2, 4,6,8,10-Pentamethyl-2,4,6,8-pentaphenylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaphenylcyclopentasiloxane, 2,4,6,8,10-pentacyclohexyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10- Decacyclohexylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decavinylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6 , 8,10-Pentavinylcyclopentasiloxane, among which low molecular weight cyclic siloxanes in which ^R2 is an alkyl having 1 to 40 carbon atoms are preferable, hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D3). Cyclic siloxanes such as D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are more preferred, and octamethylcyclotetrasiloxane is particularly preferred from the standpoint of availability, cost, and handling.

Examples of the compound represented by the formula (c) include, for example.
1,1,3,3-Tetramethyl-1,3-disiloxanediol, 1,1,3,3,5,5-hexamethyl-1,5-trisiloxanediol, 1,1,3,3,5 , 5,7,7-Octamethyl-1,7-tetrasiloxanediol, 1,1,3,3,5,5,7,7,9,9-decamethyl-1,9-pentasiloxanediol, 1,1 , 3,3-Tetraphenyl-1,3-disiloxanediol, 1,1,3,3,5,5-hexaphenyl-1,5-trisiloxanediol, DMS-S12 (trade name, manufactured by Gelest), DMS-S14 (trade name, manufactured by Gelest), DMS-S15 (trade name, manufactured by Gelest)
1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,5,5,5-octamethyltrisiloxane, 1,1,1,3,3,5 5,7,7-Decamethyltetrasiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1 , 5-Divinyl-1,1,3,3,5,5-heptamethyltrisiloxane, 1,5-diallyl-1,1,3,3,5,5-heptamethyltrisiloxane, DMS-V00 (Product name, manufactured by Gelest), DMS-V03 (Product name, manufactured by Gelest), DMS-V05 (Product name, manufactured by Gelest)
1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyldisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11- Dodecamethylhexasiloxane, 1,3-dimethyl-1,3-diphenyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,3-cyclohexyl-1,3-dimethyldisiloxane, 1,1, 1,3,3-Tetracyclohexamethyldisiloxane, 1,3-diethyl-1,3-dimethyldisiloxane, 1,1,3,3-tetraethyldisiloxane, 1,3-dimethyl-1,3-dipropyl Disiloxane, 1,3-diethyl-1,3-dipropyldisiloxane, 1,1,3,3-tetrapropyldisiloxane, 1,3-dimethyl-1,3-bis (1-methylethyl) disiloxane 1,1,3-diethyl-1,3-bis (1-methylethyl) disiloxane, 1,1,3,3-tetrakis (1-methylethyl) disiloxane, 1,1,3,3-tetrakis (1) , 1-dimethylethyl) disiloxane, 1,3-bis (1,1-dimethylethyl) -1,3-dimethyldisiloxane, DMS-Hm15 (trade name, manufactured by Gelest), DMS-Hm25 (trade name, Gelest) , DMS-H03 (trade name, manufactured by Gelest), DMS-H11 (trade name, manufactured by Gelest), FM 1105 (trade name, manufactured by JNC Co., Ltd.), FM 1111 (trade name, manufactured by JNC Co., Ltd.) , 1,3-Difluoro-1,1,3,3-tetramethyldisiloxane, 1,5-difluoro-1,1,3,3,5,5-hexamethyldisiloxane, 1,1,3,3 -Tetramethyl-1,3-bis (trifluoromethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (trifluoromethyl) disiloxane, 1,3-dimethoxy- 1,1,3,3-Tetramethyldisiloxane, 1,5-dimethoxy-1,1,1,3,3,5,5-hexamethyltrisiloxane, 1,3-diethoxy-1,1,3,3- Tetramethyldisiloxane, 1,5-diethoxy-1,1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3-tetramethyl-1,3-dipropoxydisiloxane, 1,, 1,3,3,5,5-hexamethyl-1,5-di Propoxytrisiloxane 1,1,3,5,7,7-hexamethoxy-1,3,5,7-tetramethyltetrasiloxane, 3,3,11,11-tetramethoxy-6,6,8,8 -Tetramethyl-2,7,12-Trioxa-3,6,8,11-Tetrasilatridecan, 4,4,12,12-Tetraethoxy-7,7,9,9-Tetramethyl-3,8, 13-Trioxa-4,7,9,12-Tetrasilapentadecane, 1,3-dietinyl-1,1,1,3,3-tetramethyldisiloxane, 1,5-dietinyl l-1,1,3,3, 5,5-Hexamethyltrisiloxane, FM 2205 (trade name, manufactured by JNC Co., Ltd.), 1,1,3,3-tetramethyl-1,3-di-2-propane-1-yldisiloxane, 1, 1,3,3,5,5-hexamethyl-1,5-di-2-propane-1-yltrisiloxane, FM-4411 (trade name, manufactured by JNC Co., Ltd.), FM-4421 (trade name, JNC) (Product name, manufactured by JNC Co., Ltd.), FM-4425 (trade name, manufactured by JNC Co., Ltd.), DMS-C15 (trade name, manufactured by Gelest), DMS-C16 (trade name, manufactured by Gelest), DMS-C21 (trade name, manufactured by Gelest). ), DMS-CA21 (trade name, manufactured by Gelest).

Ｒ^０は式（Ａ）におけるＲ^０と同様に定義され、好ましい例も同様である。
Ｒ^１は式（Ａ）におけるＲ^１と同様に定義され、好ましい例も同様である。
式（ａ）で表される化合物は、例えば、特開２００６－０２２２０７号公報の記載を参照して合成することができ、以下に示される化合物が好ましい。この化合物において、Ｐｈはフェニルを示し、Ｃ－Ｈｅｘはシクロヘキシルを示す。 Examples of the cage-type silsesquioxane include a compound represented by the formula (a).

R ⁰ is defined in the same manner as R ⁰ in the formula (A), and so is the preferred example.
R ¹ is defined in the same manner as R ¹ in the formula (A), and so is the preferred example.
The compound represented by the formula (a) can be synthesized, for example, with reference to the description in JP-A-2006-022207, and the compounds shown below are preferable. In this compound, Ph represents phenyl and C-Hex represents cyclohexyl.

Further, in the polysiloxane copolymer obtained in the above step (ii), a compound represented by the formula (d) is added to a terminal different from the end bonded to the surface of a substance selected from the inorganic substance and the organic substance of the polysiloxane. By reacting, a terminal different from the end bonded to the surface of the substance of the polysiloxane may be modified.

式（ｄ）におけるＲ^３は、式（ｃ）におけるＲ^３と同様に定義され、好ましい基も同様である。
Ｒ^４は独立して、水素、ビニル、アリル、水酸基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、または炭素数１～４０のアルキルであり、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、および炭素数７～４０のアリールアルキル中のアリールにおいて、少なくとも１つの水素がハロゲンまたは炭素数１～２０のアルキルで置き換えられてもよく、炭素数７～４０のアリールアルキル中のアルキレンにおいて、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－、－ＣＨ＝ＣＨ－、または炭素数５～２０のシクロアルキレンで置き換えられてもよく、炭素数１～４０のアルキルは、少なくとも１つの水素がハロゲンで置き換えられてもよく、少なくとも１つの－ＣＨ_２－が、－Ｏ－または炭素数５～２０のシクロアルキレンで置き換えられてもよい。
ｎは１～３０である。
式（ｄ）で表される化合物としては、例えば、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ヘキサフェニルジシロキサン、オクタフェニルトリシロキサン、デカフェニルテトラシロキサン、Ｇｅｌｅｓｔ製 ＤＭＡ－Ｔ０７Ｒが挙げられる。 <Compound represented by the formula (d)>

R ³ in formula (d) is defined in the same way as R ³ in formula (c), as is the preferred group.
^R4 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl with 6 to 20 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, arylalkyl with 7 to 40 carbon atoms, or alkyl with 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. A cycloalkylene having 5 to 20 carbon atoms may be replaced, and an alkyl having 1 to 40 carbon atoms may have at least one hydrogen replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms.
n is 1 to 30.
Examples of the compound represented by the formula (d) include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexaphenyldisiloxane, octaphenyltrisiloxane, decaphenyltetrasiloxane, and Gelest's DMA-T07R. Can be mentioned.

In the above steps (i) and (ii), equilibrium polymerization can be adopted.
The equilibrium polymerization can be carried out, for example, with reference to the method described in JP-A-2017-014320. It is preferable to use the following solvent and acid catalyst for the reaction. Further, it is preferable to carry out the reaction in an inert atmosphere such as nitrogen (N ₂ ). Further, it is preferable to carry out the reaction while stirring. The reaction temperature is, for example, 25 to 120 ° C.

<Solvent>
The solvent used in the reaction is not particularly limited as long as it can dissolve the raw material compounds (a), (b) and / or (c). Preferred solvents are hydrocarbon solvents such as butane, hexane, heptane, octane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylen, anisole; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane. , Ether solvent such as tetrahydrofuran (THF), dioxane, halogenated hydrocarbon solvent such as methylene chloride, carbon tetrachloride; ester solvent such as ethyl acetate; glycol ester solvent such as propylene glycol monomethyl ether acetate (PGMEA). Nitrogen-containing solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), pyridine; alcohol solvents such as methanol, ethanol, isopropanol, butanol; acetone, It is a ketone solvent such as methyl ethyl ketone. Preferred are toluene, mesityrene, anisole, tetrahydrofuran, cyclopentylmethyl ether, propylene glycol monomethyl ether acetate and 2- (2-ethoxyethoxy) ethyl acetate, and more preferably toluene and propylene glycol monomethyl ether acetate (PGMEA). One type of solvent may be used, or two or more types may be used. Further, the solvent may be dehydrated before use. The amount of the solvent used is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, and usually 1000% by mass or less, preferably 500% by mass or less, based on the raw material compound. ..

<Catalyst>
It is preferable to use an acid catalyst for the equilibrium polymerization.
Examples of the acid catalyst include phosphoric acid, toluene sulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, sulfuric acid, nitric acid, acetic acid and benzoic acid, and DIAION ™ RCP-160M (strongly acidic ion exchange). Resin, manufactured by Mitsubishi Chemical Co., Ltd.) can be mentioned.
The amount of the catalyst added is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and usually 10% by mass or less, preferably preferably 10% by mass or more, based on the polysiloxane. It is 5% by mass or less, more preferably 3% by mass or less. When two or more kinds of catalysts are used, it is preferable that the total content is within the above range.

<Thermal conductive inorganic filler>
The thermally conductive inorganic filler is an inorganic filler having a thermal conductivity of 1 W / m · K or more.
Examples of the thermally conductive inorganic filler, the thermally conductive first inorganic filler, and the thermally conductive second inorganic filler include nitrides, metals, metal oxides, silicate compounds, carbon materials, and the like. Can be done. The thermally conductive first inorganic filler and the thermally conductive second inorganic filler may be the same or different.
Specifically, the first inorganic filler having thermal conductivity and the second inorganic filler having thermal conductivity have high thermal conductivity and a very small or negative thermal expansion rate as thermally conductive inorganic fillers. Examples thereof include boron nitride, aluminum nitride, boron carbide, carbon nitride carbon, graphite, carbon fibers, carbon nanotubes, and alumina. Alternatively, silica, magnesium oxide, zinc oxide, gold, silver, iron oxide, ferrite, mullite, cordierite, silicon nitride, and silicon carbide can be mentioned.
Alternatively, the following thermally conductive inorganic filler having a high thermal conductivity and a positive thermal expansion rate may be used for either the first thermal conductive or the second thermally conductive inorganic filler.
The third filler includes alumina, silica, silicon carbide, aluminum nitride, and nitride, which has high thermal conductivity, positive thermal expansion rate, or smaller size than the first and second inorganic fillers having thermal conductivity. Silicon, diamond, carbon nanotube, graphite, graphene, silicon, verilia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, forminium oxide, bismuth oxide, cobalt oxide , Inorganic and metal fillers such as calcium oxide, magnesium oxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, stainless steel. can.
It is desirable that the structure of the polysiloxane copolymer has a shape and length that can efficiently bond between these thermally conductive inorganic fillers. The type, shape, size, addition amount, etc. of the thermally conductive inorganic filler can be appropriately selected according to the purpose. When the obtained heat radiating member requires insulation, a heat-conducting inorganic filler having conductivity may be used as long as the desired insulation is maintained. Examples of the shape of the thermally conductive inorganic filler include a plate shape, a spherical shape, an amorphous shape, a fibrous shape, a rod shape, and a tubular shape.

Preferred are boron nitride, aluminum nitride, boron carbide, carbon nitride, graphite, carbon fiber, carbon nanotubes, alumina, zinc oxide, gold, silver and cordierite. In particular, alumina, hexagonal boron nitride (h-BN), and graphite are preferable. Boron nitride and graphite are preferable because they have a very high thermal conductivity in the plane direction, and boron nitride has a low dielectric constant and high insulating properties. For example, it is preferable to use boron nitride as a plate-like crystal because the plate-like structure is easily oriented along the mold due to the flow and pressure of the raw material during molding and curing. Alumina is preferable because it has good packing when forming a further complex with the polysiloxane copolymer.

The average particle size of the thermally conductive inorganic filler is preferably 0.1 to 500 μm. More preferably, it is 1 to 100 μm. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 500 μm or less, the filling rate can be increased.
In the present specification, the average particle size is based on the particle size distribution measurement by the laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle size by the wet method using the analysis by Franhofer diffraction theory and Mie's scattering theory, the diameter on the large side and the small side are equal (volume basis). Was taken as the median diameter.

<Coupling agent>
When the functional group of the bifunctional or higher functional silsesquioxane is oxylanyl, acid anhydride, or the like, the coupling agent to be bonded to the thermally conductive inorganic filler preferably reacts with those functional groups. Those having an amine-based reactive group at the end are preferable. For example, Sila Ace (registered trademark) S310, S320, S330, S360 manufactured by JNC Co., Ltd., KBM903, KBE903 manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be mentioned.
When the terminal of the bifunctional or higher silsesquioxane is an amine, a coupling agent having an oxylanyl group or the like at the terminal is preferable. For example, in the case of JNC Co., Ltd., Sila Ace (registered trademark) S510, S530 and the like can be mentioned. It should be noted that the modification of the thermally conductive inorganic filler with the coupling agent is preferable because the more the coupling agent is, the more the bonds are formed.
The first coupling agent and the second coupling agent may be the same or different.

<siloxane>
Examples of the surface treatment agent include siloxane. Siloxane is a compound having a main skeleton of —Si—O— (Si—O) n—Si—, and is capable of forming a covalent bond with a thermally conductive inorganic filler or silsesquioxane, Si—O—. It is preferably a compound having a group such as R. n is 0 to 40, preferably 1 to 30, and more preferably 2 to 15. When n is in this range, the siloxane is difficult to volatilize and easily reacts with a thermally conductive inorganic filler. As long as the effect of the present invention is exhibited, the first siloxane to the third siloxane may contain Si having a structure other than the alkoxy group "-OR". The first siloxane to the third siloxane have a plurality of functional groups, and examples of the functional group include (Si—OR). R is alkyl, and examples thereof include groups such as methyl, ethyl, and propyl. Specific examples thereof include methyl silicate (manufactured by Mitsubishi Chemical Corporation, (trade name) M / KC silicate MS51), polydiethoxysiloxane (manufactured by Gelest, (commodity code) PSI-021) and the like. The structure of methyl silicate is as follows.

The proportion of siloxane that binds directly to the thermally conductive inorganic filler depends on the type of thermally conductive inorganic filler used and the amount of siloxane that binds. For example, when boron nitride is used as a thermally conductive inorganic filler, as described above, boron nitride has no reactive group on a flat surface and has a reactive group only on the side surface. As many siloxanes as possible are directly attached to the few reactive groups.
The amount of siloxane reacting to the thermally conductive inorganic filler mainly varies depending on the size of the thermally conductive inorganic filler and the reactivity of the siloxane. For example, as the boron nitride becomes larger, the area ratio of the side surface of the boron nitride decreases, so that the bond amount (modification amount) is small. We want to react an appropriate amount of siloxane, but it is preferable to balance it because the thermal conductivity of the product decreases when the particles are made smaller.
When the thermally conductive inorganic filler is boron nitride, the reaction amount of the siloxane directly bonded to the thermally conductive inorganic filler can be, for example, 0.5 to 5%, preferably 1 to 3% by weight. .. When the thermally conductive inorganic filler is titanium oxide, for example, the weight ratio can be 0.5 to 15%, preferably 1 to 10%.

<Other components>
The composition for the heat dissipation member is further not bound to, or contributes to, the thermally conductive inorganic filler, or the thermally conductive first inorganic filler and the thermally conductive second inorganic filler. It may contain a compound (for example, a polymerizable compound or a polymer compound), and may contain a polymerization initiator, a solvent, or the like.

<Non-bonded polymerizable compound>
The composition for a heat radiating member may contain a polysiloxane copolymer or a cross-linking agent that is not bonded to a thermally conductive inorganic filler as a component. As such silsesquioxane, those that do not interfere with the thermal curing of the thermally conductive inorganic filler and do not evaporate or bleed out by heating are preferable. Alternatively, other polymerizable compounds not bonded to the thermally conductive inorganic filler may be used as a component. This polymerizable compound is classified into a compound having no liquid crystal property and a compound having a liquid crystal property. Examples of the polymerizable compound having no liquid crystal property include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives and the like. As for the content, it is desirable to first prepare a composition for a heat radiating member that does not contain a compound that is not bonded, measure the porosity, and add an amount of the compound that can fill the porosity.

<Unbound polymer compound>
The composition for a heat radiating member may contain a polymer compound that is not bonded to a thermally conductive inorganic filler as a constituent element. As such a polymer compound, a compound that does not reduce the film-forming property and the mechanical strength is preferable. The polymer compound may be a thermally conductive inorganic filler, a surface treatment agent, and a polymer compound that does not react with a siloxane complex or a cross-linking agent. For example, silsesquioxane is an oxylanyl group and a silane coupling agent is amino. When it has a group, examples thereof include a polyolefin resin, a polyvinyl resin, a silicone resin, and a wax. As for the content, it is desirable to first prepare a composition for a heat radiating member that does not contain a non-bonded polymerizable compound, measure the porosity, and add an amount of the polymer compound that can fill the porosity. ..

<Solvent>
The composition for a heat radiating member may contain a solvent. When the component to be polymerized is contained in the composition, the polymerization may be carried out in a solvent or in the absence of a solvent. The composition containing the solvent may be applied onto a substrate by, for example, a spin coating method, and then the solvent may be removed before photopolymerization. Further, after photo-curing, it may be heated to an appropriate temperature and post-treated by thermosetting.
Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , Cyclohexanone, PGMEA and the like. The above solvent may be used alone or in combination of two or more.
It is not so meaningful to limit the ratio of the solvent used at the time of polymerization, and it may be determined for each individual case in consideration of polymerization efficiency, solvent cost, energy cost and the like.

<Others>
A stabilizer may be added to the composition for the heat radiating member for ease of handling. As such stabilizers, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
Further, an additive (oxide or the like) may be added to adjust the viscosity and color of the composition for a heat radiating member. For example, titanium oxide for whitening, carbon black for blackening, and fine powder of silica for adjusting the viscosity can be mentioned. In addition, additives may be added to further increase the mechanical strength. For example, inorganic fibers and cloths such as glass fibers, carbon fibers and carbon nanotubes, or as polymer additives, fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide and polyimide can be mentioned.

<Manufacturing method>
Hereinafter, a method for producing a composition for a heat radiating member and a method for producing a heat radiating member from the composition will be specifically described.
(1) Coupling treatment A heat-conducting inorganic filler is subjected to a coupling treatment, and one end of the coupling agent and the heat-conducting inorganic filler are bonded to form a second heat-conducting inorganic filler. .. A known method can be used for the coupling treatment.
As an example, first, a thermally conductive inorganic filler and a coupling agent are added to the solvent. After stirring with a stirrer or the like, it is dried. After the solvent is dried, heat treatment is performed under vacuum conditions using a vacuum dryer or the like. A solvent is added to this thermally conductive inorganic filler, and the mixture is pulverized by ultrasonic treatment. The solution is separated and purified using a centrifuge. After discarding the supernatant, add a solvent and perform the same operation several times. The heat-conducting inorganic filler that has been subjected to the coupling treatment after purification is dried using an oven.
(2) A thermally conductive inorganic filler modified with a siloxane composite or a cross-linking agent (which may be the same as or different from the above-mentioned thermally conductive second inorganic filler). , A siloxane complex or cross-linking agent is attached to the other end of the coupling agent. The thermally conductive inorganic filler modified with the siloxane composite or the cross-linking agent as described above is used as the first thermally conductive inorganic filler.
As an example, the coupled thermally conductive inorganic filler and the siloxane composite or the cross-linking agent are mixed using an agate mortar or the like, and then kneaded using a biaxial roll or the like. Then, it is separated and purified by sonication and centrifugation.
(3) As an example of manufacturing a heat-dissipating member, a method of manufacturing a film as a heat-dissipating member by using a composition for a heat-dissipating member will be described. The composition for a heat radiating member is sandwiched in a heating plate using a compression molding machine, and is oriented and cured by compression molding. Further, post-curing is performed using an oven or the like to obtain the heat dissipation member of the present invention. The pressure during compression molding is preferably 50 to 200 kgf / cm ² , more preferably 70 to 180 kgf / cm ² . Basically, it is preferable that the pressure at the time of curing is high. However, it is preferable to appropriately change the fluidity in the mold and the desired physical properties (which direction the thermal conductivity is emphasized, etc.) and apply an appropriate pressure.

Hereinafter, a method for producing a film as a heat radiating member by using a composition for a heat radiating member containing a solvent will be specifically described.
First, the composition is applied onto a substrate, and the solvent is dried and removed to form a coating film layer having a uniform film thickness. Examples of the coating method include spin coating, roll coating, cutane coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating method and the like.
The solvent can be removed by drying, for example, by air-drying at room temperature, drying on a hot plate, drying in a drying oven, blowing warm air or hot air, or the like. The conditions for removing the solvent are not particularly limited, and the solvent may be generally removed and dried until the coating film layer loses its fluidity.

Examples of the substrate include metal substrates such as copper, aluminum, and iron; inorganic semiconductor substrates such as silicon, silicon nitride, gallium nitride, and zinc oxide; glass substrates such as alkali glass, borosilicate glass, and flint glass, alumina, and nitride. Inorganic insulating substrate such as aluminum; polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polycarbonate sulphide, polyethersulphon, polysulphon, polyphenylene sulphide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, Examples thereof include plastic film substrates such as polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose or a partially saponified product thereof, epoxy resin, phenol resin, and norbornene resin.

The film substrate may be a uniaxially stretched film or a biaxially stretched film. The film substrate may be subjected to surface treatment such as saponification treatment, corona treatment, and plasma treatment in advance. A protective layer may be formed on these film substrates so as not to be attacked by the solvent contained in the composition for heat dissipation member. Examples of the material used as the protective layer include polyvinyl alcohol. Further, an anchor coat layer may be formed in order to improve the adhesion between the protective layer and the substrate. Such an anchor coat layer may be either an inorganic material or an organic material as long as it enhances the adhesion between the protective layer and the substrate.

As described above, the bond between the thermally conductive inorganic fillers is surface-treated with the surface-treated thermally conductive inorganic filler including the coupling treatment, and further modified with the siloxane composite or the cross-linking agent. The case of being composed of a filler has been described.

[Heat dissipation member]
The heat radiating member according to the second embodiment of the present invention is obtained by curing a composition for a heat radiating member and molding it according to the intended use. This cured product has high thermal conductivity and can be positive with a negative or very small thermal expansion rate, and is excellent in heat resistance, chemical stability, hardness, mechanical strength and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, flexural modulus, impact strength, and the like. The heat radiating member is useful for a heat radiating plate, a heat radiating sheet, a heat radiating film, a heat radiating adhesive, a heat radiating molded product, and the like.

As a pre-curing condition for curing the composition for a heat-dissipating member by thermal polymerization, the thermosetting temperature is in the range of room temperature to 350 ° C., preferably room temperature to 250 ° C., more preferably 120 ° C. to 220 ° C. The curing time is in the range of 5 seconds to 10 hours, preferably 1 minute to 8 hours, and more preferably 5 minutes to 5 hours. After the polymerization, it is preferable to slowly cool the mixture in order to suppress stress-strain and the like. Further, the strain may be relaxed by performing a reheat treatment.

The heat radiating member is used in the form of a sheet, a film, a thin film, a fiber, a molded body, or the like. Preferred shapes are plates, sheets, films and thin films. The film thickness of the sheet in the present specification is 1 mm or more, the film thickness is 3 μm or more, preferably 5 to 999 μm, more preferably 20 to 300 μm, and the film thickness of the thin film is less than 3 μm. The film thickness may be appropriately changed according to the intended use. The composition for a heat radiating member can be used as it is as an adhesive or a filler.

[Electronics]
The electronic device according to the third embodiment of the present invention includes a heat radiating member according to the second embodiment and an electronic device having a heat generating portion or a cooling portion. The heat radiating member is arranged on the electronic device so as to come into contact with the heat generating portion. The shape of the heat radiating member may be any of a heat radiating electronic substrate, a heat radiating plate, a heat radiating sheet, a heat radiating film, a heat radiating adhesive, a heat radiating molded product, and the like.
For example, a semiconductor module can be mentioned as an electronic device. The low thermal expansion member has high thermal conductivity, high heat resistance, and high insulation in addition to low thermal expansion. Therefore, it is particularly effective for an insulated gate bipolar transistor (IGBT), which requires a more efficient heat dissipation mechanism due to its high power among semiconductor elements. An IGBT is one of the semiconductor elements, which is a bipolar transistor in which a MOSFET is incorporated in a gate portion, and is used for power control. Electronic devices equipped with IGBTs include main conversion elements for high-power inverters, non-disruptive power supply devices, variable voltage variable frequency control devices for AC motors, control devices for railway vehicles, electric transport equipment such as hybrid cars and electric cars, and IH. Examples include cookers.

Although the present invention has been described above as describing that the present invention is formed by a heat conductive inorganic filler and a polysiloxane copolymer to obtain a heat radiating member having high heat conductivity and high heat resistance, the present invention is not limited to this. ..
That is, in the present invention, in the compounding of an inorganic material and an organic compound, a bond is formed between the inorganic materials by the organic compound, the thermal conductivity is remarkably improved, and the heat resistance is further improved.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the following examples.

The materials constituting the heat radiating member used in the examples of the present invention are as follows.

<Polysiloxane copolymer>
[Synthesis Example 1]
Preparation of Silicon Compound 1 A cooling tube, a magnetic stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. Compound in formula (A) where R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 2.3 g, methanesulfonic acid 0.47 g, dehydrated toluene 10.2 g, 4-methyl 2.6 g of tetrahydropyran was placed in a flask. After stirring at 80 ° C. for 7 hours, 30.0 g of water and 56.3 g of ethyl acetate were added, and the aqueous layer was extracted. After washing the organic layer with brine three times, 5.0 g of sodium sulfate and 4.2 g of Kyoward 500 were added, and the mixture was stirred overnight. The solid was filtered off by vacuum filtration and the filtrate was concentrated. Heptane and methanol were added to the concentrate, and the obtained precipitate was dried under reduced pressure at 80 ° C. to obtain 9.9 g of a white solid. ¹ The white solid obtained by H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1'). It was found that the polymer was formed by alternately bonding, and the number n of DMS units was 2.7 on average. From GPC analysis, the number average molecular weight of silicon compound 1 was Mn = 45,300, and the weight average molecular weight was Mw = 110,000.

[Synthesis Example 2]
Preparation of Silicon Compound 2 A cooling tube, a mechanical stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. Compound in formula (A) where R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 4.50 g, methanesulfonic acid 0.681 g, dehydrated toluene 12.1 g, 4-methyl 3.04 g of tetrahydropyran was placed in a flask. The mixture was stirred at 80 ° C. for 5 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water, anhydrous sodium sulfate and Kyoward 500 were added, and the mixture was stirred. Anhydrous sodium sulfate and Kyoward 500 were separated by filtration, and the obtained solution was concentrated under reduced pressure. The obtained crude product was reprecipitated with heptane and purified. The obtained white solid was vacuum dried at 80 ° C. to obtain 9.53 g of the white solid. ¹ The white solid obtained by H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1'). It was found that the polymer was formed by alternately binding and the number n of DMS units was 3.8 on average. From GPC analysis, the number average molecular weight of silicon compound 2 was Mn = 40,000, and the weight average molecular weight was Mw = 93,500.

[Synthesis Example 3]
Preparation of Silicon Compound 3 A cooling tube, a magnetic stirrer, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. Compound in formula (A) where R ⁰ is phenyl and R ¹ is methyl 10.0 g, octamethylcyclotetrasiloxane (D4) 2.3 g, methanesulfonic acid 3.2 g, dehydrated toluene 12.6 g, 4-methyl 3.2 g of tetrahydropyran was placed in a flask. After stirring at 80 ° C. for 2 hours, the mixture was refluxed for 5 hours. 30.0 g of water and 46.6 g of ethyl acetate were added, and the aqueous layer was extracted. After washing the organic layer twice with brine, 5.0 g of sodium sulfate and 32.0 g of Kyoward 500 were added, and the mixture was stirred overnight. The solid was filtered off by vacuum filtration and the filtrate was concentrated. Heptane and methanol were added to the concentrate, and the obtained precipitate was dried under reduced pressure at 80 ° C. to obtain 9.5 g of a white solid. The white solid obtained by ¹ H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and the white solid obtained by ¹ H-NMR and GPC analysis is represented by the formula (1'). It is a silicon compound represented by a polymer in which each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1') is alternately bonded, and the number n of DMS units is 3.2 on average. It turned out that there was. From GPC analysis, the number average molecular weight of the silicon compound 3 was Mn = 10,300, and the weight average molecular weight was Mw = 15,100.

[Synthesis Example 4]
Preparation of Silicon Compound 4 A cooling tube, a mechanical stirrer, and a thermometer protection tube were attached to a 1000 mL flask, and the inside of the flask was replaced with nitrogen. 100 g of the compound in which R ⁰ is phenyl and R ¹ is methyl in the formula (A), 30.0 g of octamethylcyclotetrasiloxane (D4), 5.35 g of methanesulfonic acid, 108 g of dehydrated toluene, 4-methyltetrahydropyran 27. 1 g was placed in a flask. The mixture was stirred at 80 ° C. for 5 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water, anhydrous sodium sulfate and Kyoward 500 were added, and the mixture was stirred. Anhydrous sodium sulfate and Kyoward 500 were separated by filtration, and the obtained solution was concentrated under reduced pressure. The obtained crude product was reprecipitated with heptane and purified. The obtained white solid was vacuum dried at 80 ° C. to obtain 107 g of the white solid. ¹ The white solid obtained by H-NMR and GPC analysis is a silicon compound represented by the formula (1'), and each structural unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1'). It was found that the polymer was formed by alternately binding and the number n of DMS units was 2.6 on average. From the GPC analysis, the number average molecular weight of the silicon compound 4 was Mn = 43,600, and the weight average molecular weight was Mw = 141,400.

The measurement conditions for GPC measurement are shown below.
<Measurement conditions>
Column: Shodex KF-804L 300 x 8.0 mm
Chromatography KF-805L 300 × 8.0mm 2 series Mobile phase: THF
Flow velocity: 1.0 ml / min
Temperature: 40 ° C
Detector: RI
Molecular Weight Standard Sample: PMMA with Known Molecular Weight

<Thermal conductive inorganic filler>
-Boron Nitride: h-BN particles (manufactured by Momentive Performance Materials Japan (combination), (trade name) PolarTherm PTX-25) (PTX-25)
-Alumina: DAW-20 (Denka)

<Silane coupling agent 1>
・ Decyltriethoxysilane, (DTES) manufactured by Tokyo Chemical Industry Co., Ltd.
<Silane coupling agent 2>
-Made by Tokyo Chemical Industry Co., Ltd., Phenyltriethoxysilane, (PhTES)

・１，４－ビス（トリエトキシシリル）ベンゼン、Ｇｅｌｅｓｔ製、（１，４－ＢＴＥＳＢ）

<Crosslinking agent compound>
・ Methyl silicate, manufactured by Mitsubishi Chemical Corporation, (trade name) MS-51

1,4-Bis (triethoxysilyl) benzene, manufactured by Gelest, (1,4-BTESB)

<Catalyst>
・ Dibutyl phthalate tin (manufactured by Tokyo Chemical Industry Co., Ltd.) (DBTDL)

<Solvent>
・ Methanol (manufactured by Wako Pure Chemical Industries, Ltd.)
・ 1-Methyl-2-pyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Treatment of coupling agent 1>
20.0 g of boron nitride (PTX-25), 70.0 g of methanol and 2.0 g of DTES were placed in a glass container and stirred, then 17.5 g of ultrapure water was added and the mixture was stirred at room temperature for 12 hours. This was filtered under reduced pressure to obtain a solid content. To wash the filler, it was placed in a glass container, 100 g of methanol was added, and the mixture was stirred for several minutes. The step of filtering under reduced pressure and cleaning the filler was performed three times. The washed solid content was filtered under reduced pressure, placed in a glass container, and dried in a vacuum dryer at 120 ° C. for 5 hours to obtain a powdery <filler 1>.

<Treatment of coupling agent 2>
A powdery <filler 2> was prepared by using PhTES instead of DTES in the same manner as in <Coupling Agent Treatment 1>.

[Example 1]
<Preparation of heat dissipation member>
An example of preparing a heat radiating member is shown below.
1 g of <silicon compound 1> was added to 1 mL of NMP, and the mixture was stirred overnight. After that, 2 g of DAW-20 was added, and the rotation treatment was carried out at 2000 rpm for 1 minute under no pressure conditions and then at 2000 rpm under the condition of reduced pressure to 100.3 kPa using vacuum foam training Taro for 1 minute. went.

A 3 mm-thick stainless steel plate with a φ2.5 cm hole was pressed and fixed with a 1 mm PTFE plate processed to φ2.5 cm, and the above composition was filled into the plate. This was heated at 70 ° C. for 30 minutes, then at 110 ° C. for 30 minutes and at 220 ° C. for 4 hours. Then, a circular piece having a thickness of 602 μm as a heat radiating member was taken out.

Thermal conductivity evaluation The thermal conductivity is determined in advance by the specific heat of the heat dissipation member at 25 ° C (measured with a DSC type high-sensitivity differential scanning calorimeter manufactured by Rigaku Co., Ltd., Thermo Plus EVO2 DSC-8231) and the specific gravity at 25 ° C (new photoelectrons (new photoelectrons). (Measured by DME-220, a specific electron scale type gravity meter manufactured by Co., Ltd.), and the value was determined by the ai-Phase Mobile 1u heat diffusivity measuring device manufactured by iPhase Co., Ltd. The thermal conductivity in the thickness direction was obtained by multiplying.

<Evaluation>
Thermogravimetric (TG) measurement The amount of silane coupling agent coated on the heat conductive inorganic filler of the heat dissipation member is 901 ° C. using a thermogravimetric / differential thermal measuring device (TG-8121 manufactured by Rigaku Co., Ltd.). Calculated from heat loss.
Further, the 5% weight reduction temperature of the heat radiating member was calculated from the temperature when the weight was reduced by 5% by weight when the amount of reduction from 140 ° C. to 900 ° C. was 100% by weight using the above measuring device.

[Example 2]
A sample was prepared and measured in the same manner as in Example 1 except that <filler 2> was used instead of DAW-20 as the thermally conductive inorganic filler.

[Example 3]
<Silicon compound 2> 1 g was added to 4 mL of NMP, and the mixture was stirred overnight. Then, a sample was prepared and measured in the same manner as in Example 1 except that 36 mg of MS-51, 1.26 mg of DBTDL, and 2 g of DAW-20 were added.

[Example 4]
<Silicon compound 1> 1 g was added to 4 mL of NMP, and the mixture was stirred overnight. Then, a sample was prepared and measured in the same manner as in Example 1 except that 32 mg of MS-51, 1.12 mg of DBTDL, and 2 g of DAW-20 were added.

[Example 5]
1 g of <silicon compound 3> was added to 4 mL of NMP, and the mixture was stirred overnight. Then, a sample was prepared and measured in the same manner as in Example 1 except that 140 mg of MS-51, 4.91 mg of DBTDL, and 2 g of DAW-20 were added.

[Example 6]
1 g of <silicon compound 4> was added to 1 mL of NMP, and the mixture was stirred overnight. Then, a sample was prepared and measured in the same manner as in Example 1 except that 33 mg of MS-51, 1.15 mg of DBTDL, and 1 g of DAW-20 were added.

[Example 7]
A sample was prepared and measured in the same manner as in Example 6 except that 2 g of DAW-20 was used.

[Example 8]
A sample was prepared and measured in the same manner as in Example 6 except that 5 g of DAW-20 was used.

[Example 9]
A sample was prepared and measured in the same manner as in Example 6 except that 10 g of DAW-20 was used.

[Example 10]
A sample was prepared and measured in the same manner as in Example 6 except that 2 g of <filler 1> was used instead of DAW-20 as the thermally conductive inorganic filler.

[Example 11]
A sample was prepared and measured in the same manner as in Example 6 except that 2 g of <filler 2> was used instead of DAW-20 as the thermally conductive inorganic filler.

[Example 12]
As a heat-conducting inorganic filler, a sample was prepared and measured in the same manner as in Example 6 except that a mixture of 2 g of <filler 1> and 13 g of DAW-20 was used instead of DAW-20.

[Example 13]
As a heat-conducting inorganic filler, a sample was prepared and measured in the same manner as in Example 6 except that a mixture of 2 g of <filler 2> and 13 g of DAW-20 was used instead of DAW-20.

[Example 14]
A sample was prepared and measured in the same manner as in Example 5 except that 1,4-BTESB 44 mg was used as a cross-linking agent.

[Comparative Example 1]
1 g of KR-515 and 1 mL of NMP were added, and the mixture was stirred overnight. Then, a sample was prepared and measured in the same manner as in Example 1 except that 33 mg of MS-51, 1.15 mg of DBTDL, and 2 g of DAW-20 were added.

[Comparative Example 2]
A sample was prepared and measured in the same manner as in Comparative Example 1 except that 5 g of DAW-20 was used.

[Comparative Example 3]
A sample was prepared in the same manner as in Comparative Example 1 except that 2 g of <filler 1> was used as the heat conductive inorganic filler, but the cured product was not strong enough to measure the thermal diffusivity.

[Comparative Example 4]
A sample was prepared in the same manner as in Comparative Example 1 except that 2 g of <filler 2> was used as the heat conductive inorganic filler, but the cured product was not strong enough to measure the thermal diffusivity.

Table 1

From Table 1, when comparing the polysiloxane copolymer and the general-purpose silicone material, when the polysiloxane copolymer uses the same alumina, the thermal conductivity is slightly inferior, but the 5% weight loss temperature is remarkable. It turns out to be expensive. Further, general-purpose silicone cannot be cured by using boron nitride, but the polysiloxane copolymer can be cured and has high thermal conductivity. General-purpose silicone has poor compatibility with boron nitride, has no effect on surface-treated silicones, and does not cure because the site that becomes the reaction group has entered the inside of the boron nitride aggregate. On the other hand, the structure of the polysiloxane copolymer seems to have become stronger in curing because the compatibility is increased to some extent when boron nitride is surface-treated. In addition, there was not much difference in thermal conductivity and 5% weight loss temperature depending on the molecular weight of the silicon compound. It can be seen that the composition for a heat dissipation member of the present invention, which is an organic-inorganic hybrid material, is a material having high heat resistance and high thermal conductivity.

The composition for a heat radiating member of the present invention has both the workability of the resin and extremely high heat resistance, and can dissipate heat by efficiently conducting and transmitting the heat generated inside the electronic device. Can be used for.

1 Thermally conductive first inorganic filler 2 Thermally conductive second inorganic filler 11 First surface treatment agent 12 Second surface treatment agent 21 Polysiloxane copolymer

Claims (18)

With thermally conductive inorganic fillers;
A polysiloxane copolymer consisting of a cage-type silsesquioxane repeating unit represented by the formula (A) and a chain siloxane repeating unit represented by the formula (B);
A composition for a heat radiating member, including.

In formula (A),
^R0 is independently an aryl with 6 to 20 carbon atoms or a cycloalkyl with 5 to 6 carbon atoms, and in the aryl with 6 to 20 carbon atoms and the cycloalkyl with 5 to 6 carbon atoms, at least one hydrogen is contained. It may be replaced with a halogen or an alkyl having 1 to 20 carbon atoms;
^R1 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. An alkyl having 5 to 20 carbon atoms may be replaced with a cycloalkylene having 1 to 40 carbon atoms, and at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms;
x is greater than or equal to 1;
In formula (B),
^R2 is independently composed of hydrogen, vinyl, allyl, hydroxyl group, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. At least one hydrogen is replaced by a halogen or an alkyl having 1 to 20 carbon atoms in the aryl in the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the aryl alkyl having 7 to 40 carbon atoms. Alternatively, in the alkylene in the arylalkyl having 7 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- is -O-, -CH = CH-, or. It may be replaced with a cycloalkylene having 5 to 20 carbon atoms, or in an alkyl having 1 to 40 carbon atoms, at least one hydrogen may be replaced with a halogen, and at least one -CH _2- may be replaced with -O- or carbon. May be replaced with the number 5-20 cycloalkylene;
y is 1 or more. The composition for a heat dissipation member according to claim 1, wherein the heat conductive inorganic filler is surface-treated with a surface treatment agent. The thermally conductive inorganic filler consists of a thermally conductive first inorganic filler and a thermally conductive second inorganic filler.
The first inorganic filler of thermal conductivity is bonded to one end of the first surface treatment agent.
The second inorganic filler of thermal conductivity is bonded to one end of the second surface treatment agent.
By hardening treatment
The other end of the first surface treatment agent and the other end of the second surface treatment agent are bonded to the polysiloxane copolymer polysiloxane copolymer, or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer in its structure, and the other end of the first surface treatment agent and the second surface treatment agent. The other ends join each other,
The composition for a heat dissipation member according to claim 1. The composition for a heat dissipation member according to claim 1, further comprising a cross-linking agent or a transition metal catalyst. The composition for a heat dissipation member according to claim 4, wherein the cross-linking agent is a compound represented by the formula (2-1) or the formula (2-2).

R ³ O- [Si (OR ³ ) ₂ -O-] _m -R ³ (2-1)

R ³ O- [Si (OR ³ ) ₂ ] -A ^1- [Z] _n -A ^2- [Si (OR ³ ) ₂ ] -OR ³ (2-2)

In equations (2-1) and (2-2),
^R3 is independently methyl or ethyl;
A ¹ and A ² are independently single-bonded or alkyl having 1 to 10 carbon atoms, in which at least one hydrogen may be replaced by fluorine and at least one -CH. _2- May be replaced with -O- or -CH = CH-;
Z is an independently aryl with 6 to 20 carbon atoms;
m is 1 to 10;
n is 1 to 4. The composition for a heat dissipation member according to claim 5, wherein the thermally conductive inorganic filler is surface-treated with a surface treatment agent. The thermally conductive inorganic filler consists of a thermally conductive first inorganic filler and a thermally conductive second inorganic filler.
With a thermally conductive first inorganic filler bonded to one end of the first surface treatment agent;
Containing; with a thermally conductive second inorganic filler coupled to one end of the second surface treatment agent;
By hardening treatment
The other end of the first surface treatment agent and the other end of the second surface treatment agent bind to the polysiloxane copolymer and the cross-linking agent, respectively, or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer or a cross-linking agent, and the other end of the first surface treatment agent and the other of the second surface treatment agent. The ends join each other,
The composition for a heat dissipation member according to claim 6. The composition for a heat dissipation member according to any one of claims 2, 3, 6, and 7, wherein the surface treatment agent is a coupling agent. The composition for a heat dissipation member according to any one of claims 2, 3, 6, and 7, wherein the surface treatment agent is a siloxane compound. The composition for a heat dissipation member according to any one of claims 1 to 9, wherein the weight average molecular weight of the polysiloxane copolymer is in the range of 2,000 to 10,000,000. In the formulas (A) and (B) according to claim 1, R ⁰ is independently phenyl or cyclohexyl, and R ¹ and R ² are independently methyl or phenyl. 10. The composition for a heat radiating member according to any one of 10. The thermally conductive inorganic filler, or the thermally conductive first inorganic filler and the thermally conductive second inorganic filler, are nitrides, metals, metal oxides, silicate compounds, or carbon materials.
The composition for a heat radiating member according to any one of claims 1 to 11. The thermally conductive inorganic filler, or the thermally conductive first inorganic filler and the thermally conductive second inorganic filler, are boron nitride, aluminum nitride, boron carbide, carbon nitride carbon, graphite, carbon fibers, carbon nanotubes, etc. At least one selected from alumina, zinc oxide, gold, silver and cordierite,
The composition for a heat radiating member according to any one of claims 1 to 12. Further comprising a thermally conductive inorganic filler, or a polymerizable or polymer compound that is not bound to a thermally conductive first inorganic filler and a thermally conductive second inorganic filler.
The composition for a heat radiating member according to any one of claims 1 to 13. A heat radiating member obtained by curing the heat radiating member composition according to any one of claims 1 to 14. With the heat dissipation member according to claim 15.
With an electronic device having a heating part;
The heat radiating member is arranged in the electronic device so as to come into contact with the heat generating portion.
Electronics. With the step of binding the first inorganic filler of thermal conductivity to one end of the first surface treatment agent;
It comprises a step of binding the second inorganic filler of thermal conductivity to one end of the second surface treatment agent;
A step of binding the other end of the first surface treatment agent and the other end of the second surface treatment agent to the polysiloxane copolymer; or
At least one of the first surface treatment agent and the second surface treatment agent contains a polysiloxane copolymer in its structure, and the other end of the first surface treatment agent and the second surface treatment agent. A step of joining the other ends to each other;
A method for manufacturing a composition for a heat radiating member. With the step of binding the first inorganic filler of thermal conductivity to one end of the first surface treatment agent;
It comprises a step of binding the second inorganic filler of thermal conductivity to one end of the second surface treatment agent;
A step of binding the other end of the first surface treatment agent and the other end of the second surface treatment agent to the first polysiloxane copolymer and the second polysiloxane copolymer; or
At least one of the first surface treatment agent and the second surface treatment agent contains a first polysiloxane copolymer or a second polysiloxane copolymer in its structure, and the first surface treatment agent. The other end of the second surface treatment agent and the other end of the second surface treatment agent are bonded to each other;
A method for manufacturing a composition for a heat radiating member.

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