TW201418333A - Heat resistance material and heat resistance component - Google Patents

Abstract

The invention provides a heat resistance material characterized in including a composite resin (A). The composite resin (A) contains a polysiloxane segment (a1) having a silanol group and/or a hydrolytic silyl group, and a vinyl polymer segment (a2). And a heat resistance material is provided, wherein in the composite resin (A), the polysiloxane segment (a1) is a segment obtained by condensing a silane compound having the silanol group and/or the hydrolytic silyl group. And in the silane compound having the silanol group and/or the hydrolytic silyl group, a silane compound containing an epoxy group ranges from 25 wt% to 90 wt%.

Description

Heat resistant material and heat resistant member

The present invention relates to a heat resistant material which is excellent in light resistance and heat resistance and which has a low coefficient of linear expansion, and a heat resistant member using the heat resistant material.

A light-resistant resin that does not deteriorate due to sunlight, fluorescent light, light-emitting diode (LED) light, or ultraviolet (UV) light, used in building materials or optical components, electrical and electronic Various uses such as components.

On the other hand, with the recent miniaturization and integration of electronic devices, there is a demand for a resin that does not deteriorate due to heat generated and has dimensional stability, that is, a low linear expansion ratio.

As a resin excellent in light resistance, for example, Patent Document 1 discloses a composite resin having a polysiloxane structure. The composite resin can form a cured coating film having excellent durability such as gloss retention and water repellency retention upon exposure, but does not reveal heat stability. In addition, as a resin film excellent in heat resistance, for example, Patent Document 2 discloses a norbornene compound polymer film. The resin film has a small coefficient of linear expansion and a film The stability is excellent, but deterioration due to light such as sunlight or fluorescent lamps, LED light, or UV lamps is not disclosed.

On the other hand, in order to impart the processability and flexibility to the organic polymer The properties such as softness and surface hardness such as heat resistance and abrasion resistance of inorganic materials have been extensively studied for the formulation of inorganic fine particles into organic polymers.

For example, in a design in which the characteristics inherent to the inorganic material are effectively utilized, a higher composite effect can be expected by blending inorganic fine particles having a very small particle diameter at a high concentration. The reason is that the smaller the particle diameter, the larger the surface area per unit weight of the inorganic fine particles becomes, and the wider the interface region between the organic polymer and the inorganic material becomes. Further, when the concentration of the inorganic fine particles is increased, the characteristics of the inorganic material are more strongly exhibited.

Such organic polymers and inorganic particles from the viewpoint of coating or handling The compounding system is generally a liquid material such as a coating material or an ink, which is a liquid organic polymer, a monomer which is a raw material of the organic polymer, or an organic solvent. However, it is also known that when such inorganic fine particles are blended at a high concentration in a dispersion medium, it is difficult to obtain a stable dispersion liquid, and various problems are caused in the production work and the value of the obtained product. That is, there is a case in which the inorganic fine particles having extremely small particle diameter are secondaryly aggregated due to high surface activity, the dispersion stability due to the secondary aggregates is lowered, or the obtained coating film properties are due to the coating film portion. The uniformity of different physical properties is lacking.

Dispersing inorganic fine particles such as cerium oxide in an organic polymer Techniques, for example, are known: dispersing inorganic microparticles by surface treatment with a coupling agent A method of using a resin (refer to Patent Document 1), a method of dispersing inorganic fine particles by using a surfactant (see Patent Document 2), or a (meth) acrylate having a lactone-modified carboxyl group and (meth) A method of dispersing inorganic fine particles in a mixture of caprolactone of acrylic acid (see Patent Document 3).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 96/035755

[Patent Document 2] International Publication No. 07/135887

[Patent Document 3] Japanese Patent Special Publication No. 7-98657

[Patent Document 4] Japanese Patent Special Publication No. 8-13938

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-281934

[Patent Document 6] International Publication No. 96/035755

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2006-328354

An object of the present invention is to provide a heat resistant material which is excellent not only in light resistance but also in heat resistance, has a low coefficient of linear expansion, and is excellent in dimensional stability with respect to heat history.

As a result of intensive studies by the inventors of the present invention, it has been found that the composite resin (A) having the specific polyoxyalkylene fragment (a1) and the ethylene-based polymer segment is excellent not only in light resistance but also in heat resistance and low in linear expansion. The ratio solves the above problems.

That is, the present invention solves the above problems by providing a heat resistant material characterized by containing a composite resin (A) which is a polyoxyxane fragment (a1) and a vinyl polymer fragment (a2). The polyoxaxane fragment (a1) has a structural unit represented by the formula (1) and/or the formula (2) and a stanol group, which is bonded by a bond represented by the formula (3). And/or hydrolyzable decyl group:

(In the general formulae (1) and (2), R ¹ , R ² and R ³ each independently represent: having a selected from -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ^{_{2, -R 4 -O-CO-}} C (CH 3) = CH 2, and ^{-R 4 -O-CO-CH =} CH group of one kind of polymerizable double bond group consisting of ₂ (wherein, R ⁴ represents a single bond or an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon atom; 7~12 aralkyl)

(In the formula (3), a carbon atom constitutes a part of the above-mentioned ethylene-based polymer fragment (a2), and only a ruthenium atom bonded to an oxygen atom constitutes a part of the above-mentioned polyoxyalkylene fragment (a1).

Further, a heat resistant material is provided, wherein in the above composite resin (A), the polyoxyalkylene fragment (a1) is a fragment obtained by condensing a decane compound having a decyl alcohol group and/or a hydrolyzable decyl group, and the above has decane. In the decane compound of the alcohol group and/or the hydrolyzable alkylene group, the epoxy group-containing decane compound is 25% by weight or more and 90% by weight.

Further, a heat resistant material is provided, which comprises the above composite resin (A) and inorganic fine particles.

Further, a heat resistant material is provided, wherein the content of the polyoxymethane fragment (a1) in the composite resin (A) is from 45% by weight to 95% by weight based on the total solid content of the composite resin (A).

Further, a heat resistant material is provided, wherein in the above composite resin (A), the polyoxyalkylene fragment (a1) is a fragment obtained by condensing a decane compound having a decyl alcohol group and/or a hydrolyzable decyl group, and the above has decane. Alcohol and/or hydrolyzable decane Among the decane compounds of the group, the trialkoxy decane is 40 mol% or more.

Further, a heat resistant material is provided, characterized in that, in the above composite resin (A), the trialkoxysilane is a monoalkyltrialkoxydecane having 1 to 4 carbon atoms.

Further, a heat resistant member is provided which is formed by molding the above heat resistant material.

The heat-resistant material of the present invention is excellent not only in light resistance but also in heat resistance, and therefore can be preferably used for outdoor use or an optical member or electric which is prone to high temperature. Electronic components. In addition, the heat-resistant member obtained by molding the heat-resistant material has excellent linear expansion coefficient and excellent dimensional stability, and thus can be particularly preferably used as a high-precision electric. Electronic components.

[Composite Resin (A)]

The composite resin (A) used in the present invention is characterized in that it is a polymer having the structural unit represented by the above formula (1) and/or the above formula (2) and a stanol group and/or a hydrolyzable alkyl group. a siloxane derivative (a1) (hereinafter abbreviated as a polyoxyalkylene fragment (a1)), and a composite resin obtained by bonding a vinyl polymer fragment (a2) with a bond represented by the above formula (3) (A).

Dehydration of a decyl alcohol group and/or a hydrolyzable decyl group which the polyaluminoxane fragment (a1) which is described later has, and a decyl alcohol group and/or a hydrolyzable decyl group which the ethylene-based polymer fragment (a2) mentioned later has. a condensation reaction to form the above formula (3) Key. Therefore, in the above formula (3), a carbon atom constitutes a part of the above-mentioned ethylene-based polymer fragment (a2), and only a ruthenium atom bonded to an oxygen atom constitutes a part of the above-mentioned polyoxyalkylene fragment (a1).

The form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polyaluminoxane fragment (a1) is chemically bonded to the side chain of the polymer fragment (a2), or has a polymer The segment (a2) is a composite resin having a block structure chemically bonded to the above polyoxyalkylene fragment (a1).

(Composite resin (A) polyoxane fragment (a1))

The polyoxyalkylene fragment (a1) of the present invention is a fragment obtained by condensing a decane compound having a decyl alcohol group and/or a hydrolyzable decyl group, and has a formula represented by the formula (1) and/or the formula (2) The structural unit, and a stanol group and/or a hydrolyzable alkyl group.

The content of the polyaluminoxane fragment (a1) is from 45% by weight to 95% by weight based on the total solid content of the composite resin (A), whereby the heat resistance of the composite resin (A) is further improved.

(structural unit represented by the general formula (1) and/or the general formula (2))

Specifically, R ¹ , R ² and R ³ in the above formula (1) and formula (2) are each independently represented by having a group selected from -R ⁴ -CH=CH ₂ and -R ⁴ -C(CH). a group of one polymerizable double bond of the group consisting of ₃ )=CH ₂ , -R ⁴ —O—CO—C(CH ₃ )=CH ₂ , and —R ⁴ —O—CO—CH=CH ₂ a group (wherein R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group, or An aralkyl group having 7 to 12 carbon atoms.

Examples of the above-mentioned alkylene group having 1 to 6 carbon atoms in the above R ⁴ include a methylene group, an ethylidene group, a propyl group, an extended isopropyl group, a butyl group, an isobutyl group, and a stretching group. Second butyl, tert-butyl, pentyl, isoamyl, neopentyl, tert-amyl, 1-methylbutyl, 2-methylbutyl, 1,2 - dimethyl-propyl, 1-ethyl-propyl, hexyl, isohexyl, 1-methyl-amyl, 2-methyl-amyl, 3-methyl-amyl, 1,1- Dimethylbutylene, 1,2-dimethylbutylene, 2,2-dimethylbutylene, 1-ethylbutylene, 1,1,2-trimethylpropyl, 1 , 2,2-trimethyl-propyl, 1-ethyl-2-methyl-propyl, 1-ethyl-1-methyl-propyl, and the like. Among them, R ^{4 is} preferably a single bond or an alkylene group having 2 to 4 carbon atoms in terms of ease of obtaining a raw material.

Further, examples of the alkyl group having 1 to 6 carbon atoms include, for example, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, neopentyl, third amyl, 1-methyl Butyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Butyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropane Base, 1,2,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1-methylpropyl, and the like.

In addition, examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Further, examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropyl group. Phenyl and the like.

In addition, examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

Among the heat resistant materials in the present invention, a curable resin composition is preferred. The concentration of the crosslinked structure is increased to such an extent that the residual stress of the molded product is not large, and therefore it is more preferable to contain a functional group forming a crosslinked structure in the composite resin in addition to the hydrolyzable alkylene group.

As the functional group forming the crosslinked structure described above, a publicly known official can be used. Examples of the energy group include an epoxy group, a carboxyl group, an amine group, an isocyanate, an acid anhydride, a phenolic hydroxyl group, an alcoholic hydroxyl group, and a thiol group.

Among them, in consideration of the application to the electronic device, it is more preferable to appropriately contain a crosslinked structure using an epoxy group.

Further, examples of the functional group forming the crosslinked structure include a group having a polymerizable double bond. When at least one of R ¹ , R ² and R ³ is a group having the above polymerizable double bond, it can be easily cured by an active energy ray, a thermal radical generator or the like. Further, by the two curing mechanisms of the active energy ray and the condensation reaction of the stanol group and/or the hydrolyzable decyl group, the obtained cured product has a high crosslinking density, and can be formed to have more excellent heat resistance and low. A molded product having a linear expansion ratio.

The group having the above polymerizable double bond preferably has 2 or more, more preferably 3 to 200, more preferably 3 to 50, in the polyoxyalkylene fragment (a1), and is preferably available. A molded product having a lower coefficient of linear expansion. Specifically, when the content of the polymerizable double bond in the polyaluminoxane fragment (a1) is from 3% by weight to 35% by weight, a desired linear expansion ratio can be obtained. Further, the polymerizable double bond herein is a general term for a group which can be grown by a radical in a vinyl group, a vinylidene group or a vinyl group. Further, the content ratio of the polymerizable double bond means the weight % of the vinyl group, the vinylidene group or the vinyl group in the polyoxyalkylene fragment.

As the group having a polymerizable double bond, all of the known functional groups including the vinyl group, the vinylidene group, and the vinyl group may be used, wherein -R ⁴ -C(CH ₃ )=CH ₂ or - The (meth) acrylonitrile group represented by R ⁴ -O-CO-C(CH ₃ )=CH ₂ is reactive at the time of ultraviolet curing, or has good compatibility with the ethylene-based polymer fragment (a2) described later. .

The structural unit represented by the above formula (1) and/or the above formula (2) is 矽 Two or three of the binding bonds participate in the cross-linked three-dimensional network polyoxyalkylene structural unit. Although a three-dimensional network structure is formed but a dense network structure is not formed, gelation or the like does not occur, and storage stability is also good.

(stanol-based and/or hydrolyzable decyl)

The stanol group in the present invention is a ruthenium-containing group having a hydroxyl group directly bonded to a ruthenium atom. Specifically, the stanol group is preferably a stanol group formed by bonding an oxygen atom having a bond to a hydrogen atom in the structural unit represented by the above formula (1) and/or the formula (2).

Further, the hydrolyzable alkylene group in the present invention has a direct Specific examples of the hydrazine-containing group of the hydrolyzable group to be bonded are, for example, a group represented by the formula (4).

(In the formula (4), R ⁵ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁶ is selected from a halogen atom, an alkoxy group, a decyloxy group, a phenoxy group, an aryloxy group, a hydrolyzable group of a group consisting of a mercapto group, an amine group, a decylamino group, an aminooxy group, an imidooxy group, and an alkenyloxy group. Further, b is an integer of 0 to 2.) In the above R ⁵ , Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like. Tripentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1-ethylbutyl, 1, 1,2-Trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-1-methylpropyl, and the like.

Further, examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylbenzene group. Base.

Further, examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In the above R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.

Further, examples of the decyloxy group include a methyl methoxy group, an ethyl methoxy group, a propyl methoxy group, a butoxy group, a p-pentyloxy group, a pentyloxy group, and a phenylacetoxy group. ), ethyl hydrazine, benzyl methoxy, naphthyl methoxy, and the like.

Further, examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

Examples of the alkenyloxy group include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, and a 2- A group, a 3-methyl-3-butenyloxy group, a 2-hexenyloxy group, or the like.

The hydrolyzable group represented by the above R ^{6 is} hydrolyzed, and the hydrolyzable decyl group represented by the formula (4) is a stanol group. Among the aspects excellent in hydrolyzability, among them, a methoxy group and an ethoxy group are preferable.

Further, in particular, the hydrolyzable alkylene group is preferably an oxygen atom having a bonding bond of a structural unit represented by the above formula (1) and/or the above formula (2) bonded to the hydrolyzable group or A hydrolyzable alkylene group substituted.

The hydroxy group of the above stanol group or the above hydrolyzable decyl group in the stanol group Since the hydrolysis-condensation reaction is carried out between the above-mentioned hydrolyzable groups in the hydrolyzable alkylene group, the crosslinking density of the polyoxymethane structure is improved, and a molded article having a low linear expansion ratio can be formed.

In addition, when bonding is carried out via a bond represented by the above formula (3), a polyoxyalkylene fragment (a1) containing the above decyl alcohol group or the above hydrolyzable alkylene group and a vinyl polymer fragment (a2 described later) are used. ).

The polyoxyalkylene fragment (a1) has a structural unit represented by the above formula (1) and/or the above formula (2), and a stanol group and/or a hydrolyzable alkylene group, and is not particularly limited. It may contain other groups. E.g

In the above formula (1), R ¹ is a structural unit having a group having the above polymerizable double bond, and a polymer having coexistence with a structural unit in which R ¹ in the above formula (1) is an alkyl group such as a methyl group. silicon siloxane segment (A1); may also be: the above general formula (1) R ¹ in the structural unit having a group having the polymerizable double bond, with the general formula R (1) is ^a methyl group a structural unit of an alkyl group, and a polyoxyalkylene fragment (a1) in which R ² and R ³ in the above formula (2) are a structural unit of an alkyl group such as a methyl group; or the above formula (1) In the above, R ¹ is a structural unit having a group having the above polymerizable double bond, and a polyoxyxane fragment having a structural unit in which R ² and R ³ in the above formula (2) are an alkyl group such as a methyl group ( A1) is not particularly limited.

Specifically, examples of the polyoxyalkylene fragment (a1) include those having the following structures.

[Chemistry 13]

In the present invention, when the content of the polyaluminoxane fragment (a1) is 45% by weight to 95% by weight based on the total solid content of the composite resin (A), the heat resistance, the light resistance, and the low linear expansion ratio are excellent. .

(Composite resin (A) ethylene-based polymer fragment (a2))

The ethylene-based polymer fragment (a2) in the present invention is an ethylene polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer or a polyolefin polymer. These are preferably appropriately selected depending on the use.

For example, the acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth)acrylic monomer. The (meth)acrylic monomer is not particularly limited, and the vinyl monomer may be copolymerized. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms such as tert-butyl acrylate, 2-ethylhexyl (meth)acrylate or lauryl (meth)acrylate; Benzyl (meth) acrylate, 2- benzene (meth) acrylate (A) arylalkyl (meth)acrylates; cyclohexyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; (meth)acrylic acid 2 -Omega-alkoxyalkyl (meth)acrylates such as methoxyethyl ester and 4-methoxybutyl (meth)acrylate; vinyl acetate, vinyl propionate, vinyl pivalate, Vinyl carboxylic acid esters such as vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethylmalate, di-n-butyl malate, and anti-butyl a dialkyl ester of an unsaturated dibasic acid such as dimethyl enedionate or dimethyl itaconate; an α-olefin such as ethylene or propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene or chlorotrimide; Fluoroolefins such as vinyl fluoride; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N,N-dimethyl ( Methyl) acrylamide, N-(methyl) propylene decylmorpholine, N-(methyl) propylene decyl pyrrolidine, N-vinyl pyrrolidone, and the like, which contain a tertiary amide group.

a polymerization method, a solvent, or a polymerization initiation when the above monomers are copolymerized The agent is not particularly limited, and the ethylene-based polymer fragment (a2) can be obtained by a known method. For example, 2,2'-azobis(isobutyronitrile) and 2,2'-even can be used by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Nitrogen bis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, a polymerization initiator such as tert-butyl peroxy 2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide or diisopropyl peroxycarbonate to obtain a vinyl polymer fragment (a2) .

The number average molecular weight of the ethylene-based polymer fragment (a2) is preferably 500 to 500 in terms of a number average molecular weight (hereinafter abbreviated as Mn). In the range of 200,000, it is possible to prevent sticking or gelation when the above composite resin (A) is produced, and it is excellent in durability. In particular, Mn is preferably in the range of 700 to 100,000, and Mn is preferably in the range of 1,000 to 50,000 in order to obtain a good molded body which does not cause cracks or the like.

Further, the above vinyl polymer segment (a2) is formed in order to form the above The oxirane fragment (a1) has a composite resin (A) bonded by a bond represented by the formula (3), and has a decane directly bonded to a carbon atom in the ethylene-based polymer fragment (a2). Alcohol group and/or hydrolyzable decyl group. These stanol groups and/or hydrolyzable decyl groups are a bond represented by the formula (3) in the production of the composite resin (A) to be described later, and are hardly present in the composite resin (A) as a final product. In the vinyl polymer fragment (a2). However, there is no problem even if the stanol group and/or the hydrolyzable decyl group remain in the ethylene-based polymer fragment (a2), and when the heat-resistant material containing the composite resin (A) is hardened, it is in the stanol group. Since the hydrolysis-condensation reaction is carried out between the hydrolyzable groups in the hydroxy group or the hydrolyzable decyl group, the cross-linking density of the polysiloxane structure of the obtained cured product is improved, and a molded article excellent in heat resistance can be formed.

a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon atom Specifically, the ethylene-based polymer fragment (a2) can be obtained by copolymerizing the above-mentioned general-purpose monomer and a vinyl-based monomer containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon bond.

Examples of the vinyl monomer containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon atom include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl methyl dimethyl hydride. Oxydecane, vinyl tris(2-methoxyethoxy) Decane, vinyltriethoxydecane, vinyltrichlorodecane, 2-trimethoxydecylethylvinylether, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(A Base) propylene methoxy propyl triethoxy decane, 3-(methyl) propylene methoxy propyl methyl dimethoxy decane, 3- (meth) propylene methoxy propyl trichloro decane, etc. . Among them, vinyl trimethoxydecane and 3-(meth)acryloxypropyltrimethoxy group are preferred in that the hydrolysis reaction can be easily carried out and the by-product after the reaction can be easily removed. Decane.

The vinyl polymer segment (a2) of the present invention may have various functional groups. For example, a group having a polymerizable unsaturated double bond, an epoxy group, an alcoholic hydroxyl group, or the like may be added at the time of introduction as long as a vinyl monomer having a corresponding functional group is prepared during the polymerization.

Examples of the vinyl monomer having an epoxy group include (meth) propyl group. Glycidyl acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, vinyl epoxidized cyclohexane, glycidyl vinyl ether, methyl shrinkage Glyceryl vinyl ether or allyl glycidyl ether and the like.

Examples of the vinyl monomer having an alcoholic hydroxyl group include (meth) propyl group. 2-hydroxyethyl enoate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy butyl (meth) acrylate Ester, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, fumaric acid mono-2- Hydroxyethyl monobutyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, "PLACCEL FM or PLACCEL FA" [Daicel Chemical (shares) a lactone addition monomer] and various α-ethylenically unsaturated carboxylic acids, β-ethylenically unsaturated carboxylic acids a hydroxyalkyl ester or an adduct of these with ε-caprolactone.

(Manufacturing method of composite resin (A))

The composite resin (A) used in the present invention is specifically produced by the methods shown in the following (Method 1) to (Method 3).

(Method 1) The above-mentioned general (meth)acrylic monomer, etc. The vinyl monomer containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon bond is copolymerized to obtain a vinyl group containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon bond. Polymer fragment (a2). This is mixed with a decane compound containing a stanol group and/or a hydrolyzable decyl group to carry out a hydrolysis condensation reaction. In this case, in order to introduce an epoxy group into the produced polyoxyalkylene, an epoxy group-containing decane compound having a stanol group and/or a hydrolyzable decyl group may be used at the same time. Further, in the presence of other groups to be introduced, a decane compound having a group to be introduced is used in combination. For example, when an aryl group is introduced, a decane compound having an aryl group and a stanol group and/or a hydrolyzable decyl group may be used in combination. In addition, when a group having a polymerizable double bond is introduced, a decane compound having a group containing a polymerizable double bond and a stanol group and/or a hydrolyzable decyl group may be used in combination.

In the method, a stanol group or a hydrolyzable alkylene group of a decane compound, and a stanol group having a vinyl polymer segment (a2) containing a stanol group directly bonded to a carbon bond and/or a hydrolyzable decyl group And/or a hydrolyzable decyl group undergoes a hydrolysis condensation reaction to form the above polyoxane fragment (a1), and The fragment (a1) and the ethylene-based polymer fragment (a2) are obtained by the bond represented by the above formula (3) to obtain a composite composite resin (A).

(Method 2) In the same manner as in Process 1, a vinyl polymer segment (a2) containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon bond is obtained.

On the other hand, a decane compound containing a decyl alcohol group and/or a hydrolyzable decyl group (for the introduction of an epoxy group, an epoxy group-containing decane compound having a stanol group and/or a hydrolyzable decyl group) is used. In the presence of other groups to be introduced, a hydrolytic condensation reaction is carried out using a decane compound having a group to be introduced, to obtain a polyoxyalkylene fragment (a1). Next, the stanol group and/or the hydrolyzable alkylene group of the ethylene-based polymer fragment (a2) and the decyl alcohol group and/or hydrolyzability of the epoxy group-containing polyoxyalkylene fragment (a1) The decyl group undergoes a hydrolysis condensation reaction.

(Method 3) In the same manner as in Process 1, a vinyl polymer fragment (a2) containing a stanol group and/or a hydrolyzable decyl group directly bonded to a carbon bond is obtained. On the other hand, in the same manner as in Process 2, a polyoxyalkylene fragment (a1) was obtained. Further, when an epoxy group is introduced into the polyoxyalkylene fragment (a1), an epoxy group-containing decane compound having a decyl alcohol group and/or a hydrolyzable decyl group and other groups to be introduced are present. The group is mixed with a decane compound or the like having a group to be introduced, and a hydrolysis condensation reaction is carried out.

In addition, as a decane compound having a polymerizable double bond group and a decyl alcohol group and/or a hydrolyzable decyl group, which are used together with a group having a polymerizable double bond, for example, a vinyl trimethoxy group is used in combination. Decane, vinyltriethoxydecane, vinylmethyldimethoxydecane, vinyltris(2-methoxyethoxy)decane, vinyltriethoxydecane, vinyltrichloromethane, 2-trimethoxydecylethylethyl vinyl ether, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxy Propyltriethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(meth)acryloxypropyltrichlorodecane, and the like. Among them, vinyl trimethoxydecane and 3-(meth)acryloxypropyltrimethoxy group are preferred in that the hydrolysis reaction can be easily carried out and the by-product after the reaction can be easily removed. Decane.

In addition, as used in the above (Method 1) to (Method 3) Examples of the general decane compound include methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-butoxydecane, ethyltrimethoxydecane, n-propyltrimethoxydecane, and the like. Various organic trialkoxy decanes such as butyltrimethoxydecane, cyclohexyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane; Dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldi-n-butoxydecane, diethyldimethoxydecane, methylcyclohexyldimethoxydecane, 3-shrinkage Various diorganodialkoxydecanes such as glyceryloxypropylmethyldimethoxydecane and 3-glycidoxypropylmethyldiethoxydecane; methyltrichlorodecane, ethyltrichloromethane , chlorodecane such as vinyltrichloromethane, dimethyldichlorodecane or diethyldichlorodecane.

In addition, tetramethoxy can also be used in combination within a range that does not impair the effects of the present invention. A tetrafunctional alkoxydecane compound such as a decane, tetraethoxydecane or tetra-n-propoxydecane or a partially hydrolyzed condensate of the tetrafunctional alkoxydecane compound. When the above-mentioned tetrafunctional alkoxydecane compound or a partially hydrolyzed condensate thereof is used in combination, it is preferred that all of the ruthenium atoms constituting the polyazepine fragment (a1) have a tetrafunctional alkoxydecane compound. The method in which the cesium atom does not exceed the range of 20 mol% is used in combination.

In addition, in the above decane compound, the effect of the present invention may not be impaired. Within the range of the fruit, a metal alkoxide compound other than a ruthenium atom such as boron, titanium, zirconium or aluminum is used in combination. For example, it is preferable to use all of the ruthenium atoms constituting the polyaluminoxane fragment (a1) in a range in which the metal atom of the metal alkoxide compound does not exceed 25 mol%.

In the present invention, when the polyaoxane fragment (a1) is formed, it is used Among the decane compounds containing a stanol group and/or a hydrolyzable decyl group, the trialkoxy decane is preferably 40 mol% or more. When the trialkoxy decane is 40 mol% or more, the reactive group of the hydrolytic condensation of the three polyoxoxane fragments (a1) exists in one molecule, so that the crosslinking density is increased and the bonding becomes stronger. Therefore, the linear expansion ratio of the obtained heat resistant material and heat resistant member becomes low.

Further, the above trialkoxydecane is preferably a monoalkyltrialkoxydecane. The reason is that, in the case of monoalkyltrialkoxydecane, the hydrolysis condensation of the polyoxyalkylene fragment (a1) is more easily carried out, and the crosslinking density of the cured product is further improved. In the monoalkyltrialkoxydecane, the alkoxy group preferably has 1 to 4 carbon atoms, more preferably the alkyl group has 1 to 2 carbon atoms.

As a monoalkyltrialkoxyquinone having an alkyl group having 1 to 4 carbon atoms Specific examples of the alkane include methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-butoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and ethyltri-n-butylene. Oxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane or butyltriethoxydecane, etc., preferably methyltrimethoxydecane.

In addition, if the epoxy resin is used as the starting point in the composite resin (A) In the joint structure, the heat resistance is further improved, and therefore it is preferably used in the use of an electronic device. When the epoxy group is introduced into the composite resin (A), the polyoxonane fragment (a1) is preferably a decane compound as long as it contains a decane compound having a stanol group and/or a hydrolyzable decyl group. The epoxy group-containing decane compound is 25 wt% or more and 90 wt% or less.

Examples of the epoxy group-containing decane compound include 3-condensed sugar. Oloxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, polyfunctional epoxydecane (for example, X-12-981, X- manufactured by Shin-Etsu Silicone) 12-984), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyl Diethoxydecane, etc.

(inorganic particles)

The heat resistant material of the present invention contains the above composite resin (A), and the heat resistance is further improved by containing inorganic fine particles.

The inorganic fine particles used in the present invention are not particularly limited as long as the effects of the present invention are not impaired.

Since the composite resin (A) used in the present invention has a polyoxyalkylene fragment (a1), it is excellent in fusion with an inorganic component, and even if it is added in an amount exceeding 50% by weight, it can be dispersed without any problem. Further, after the dispersion, the inorganic fine particles are not precipitated or solidified, and have long-term storage stability. On the other hand, since the ethylene-based polymerizable segment and the reactive compound have good phase properties, they contain the above-mentioned composite resin (A) and inorganic fine particles. Since the thermal material is well dispersed with the reactive compound, a heat-resistant material containing inorganic fine particles having excellent dispersion stability can be obtained.

The inorganic fine particles are not particularly limited, and may be appropriately selected depending on the application.

For example, as an excellent heat resistance, it is alumina, magnesia, titania, zirconia, cerium oxide (quartz, smoked sputum, precipitated cerium oxide, anhydrous ceric acid, molten cerium oxide, crystalline cerium oxide (crystalline silica) ), ultrafine powder, amorphous cerium oxide, etc.).

These inorganic fine particles may be used as appropriate depending on the application, and may be used singly or in combination of two or more. Further, the inorganic fine particles have various characteristics in addition to the properties exemplified in the examples, and therefore may be appropriately selected depending on the application.

For example, when cerium oxide is used as the inorganic fine particles, it is not particularly limited, and known cerium oxide fine particles such as powdered cerium oxide or colloidal cerium oxide can be used. Examples of commercially available powdered cerium oxide microparticles include, for example, Aerosil 50 manufactured by Aerosil Co., Ltd., Aerosil 200, and SILDEX H31, SILDEX H32, SILDEX H51, and SILDEX H52 manufactured by Asahi Glass Co., Ltd. SILDEX H121, SILDEX H122, E220A and E220 manufactured by Nippon Silica Kogyo Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Co., Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

Further, examples of commercially available colloidal cerium oxide include methanol oxime sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, and ST-UP manufactured by Nissan Chemical Industries Co., Ltd. , ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc.

Further, cerium oxide microparticles having improved dispersibility by a known method can be used. Examples of such a dispersible cerium oxide fine particle include a surface treatment of the cerium oxide fine particles by a reactive decane coupling agent having a hydrophobic group, or a (meth) acrylonitrile hydride. The compound of the base is modified. As a commercially available powdered cerium oxide modified by a compound having a (meth) acryl fluorenyl group, Aerosil RM50, Aerosil R711, etc., manufactured by Ai Luo Technology Co., Ltd., Japan, as The commercially available colloidal cerium oxide in which the acryl oxime compound is modified includes MIBK-SD manufactured by Nissan Chemical Industries Co., Ltd., and the like.

The shape of the above-mentioned ceria microparticles is not particularly limited, and a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an irregular shape can be used. For example, as commercially available hollow cerium oxide fine particles, SiliNax manufactured by Nippon Steel Mining Co., Ltd. or the like can be used.

Further, the primary particle diameter is preferably in the range of 5 nm to 200 nm. When the primary particle diameter is less than 5 nm, the dispersion of the inorganic fine particles in the dispersion may be insufficient. When the particle diameter exceeds 200 nm, the sufficient strength of the cured product may not be maintained.

(composition)

As a heat resistant material of the present invention, a method for producing a dispersion in which inorganic fine particles and a composite resin (A) are used as constituent components will be described.

The method of dispersing the inorganic fine particles in the above composition is not particularly limited, and a known dispersion method can be used. As a mechanical device, for example, A disperser, a disperser having a stirring blade such as a turbine wing, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, and the like. In the production of the inorganic fine particle dispersion, when the obtained dispersion is used for a coating agent or the like, it is preferred to use glass beads in terms of coatability, paint stability, transparency of the cured product, and the like. Dispersion of a bead mill of a dispersion medium such as zirconia beads.

As the bead mill described above, for example, Luze Fine Technology (Ashizawa) STARMILL manufactured by Finetech); MSC-MILL, SC-MILL, grinder MA01SC manufactured by Mitsui Mining Co., Ltd.; Nano Grain Mill, Pico Grain Mill, Pure Grain Mill, Mechagper Grain of Asada Iron Works Mill, Cerapower Grain Mill, Dual Grain Mill, AD Mill, Twin AD MILL, Basket Mill, Twin Basket Mill; Apex Mill, Ultra Apex Mill, Super Apex Mill, etc. manufactured by Shou Industrial Co., Ltd. Among them, Ultra Apex Mill is preferred.

[Heat-resistant material containing inorganic microparticles]

When the composite resin (A) and the inorganic fine particles used in the present invention are mixed, they may be dispersed by a bead mill, a roll mill or the like. When mixing with other preparations, the other preparations are previously dispersed by a method such as a bead mill or a roll mill, and a composition obtained by mixing inorganic fine particles at a high concentration is prepared in advance, by blending the composition with others. The formulation can be made into a heat resistant material containing inorganic fine particles.

In particular, by making a heat-resistant material dispersed in a reactive diluent such as a reactive compound such as a polyisocyanate or an active energy ray-curable monomer, efficiency can be achieved. It is good, and it does not have to be hardened when it is gelled. When the dispersion concentration of the inorganic fine particles at this time is in the range of 5% by weight to 90% by weight based on the total amount of the solid content of the heat-resistant material, it is possible to obtain a dispersion excellent in storage stability without fear of precipitation or solidification of the inorganic fine particles. liquid.

[heat resistant material]

The heat resistant material of the present invention is one containing the above composite resin (A), and a heat resistant member is obtained by molding the heat resistant material. The molding method may be a conventionally known method, or may be formed by hardening, and may be molded by blending a thermoplastic resin, but in terms of heat resistance, if it is molded by heat hardening, the composite resin is used. (A) Since the bond by hydrolysis and condensation of the polyoxyalkylene fragment (a1) is stronger, the linear expansion ratio of the obtained heat resistant material and heat resistant member becomes low.

The heat resistant material of the present invention may contain a composite resin (A) or inorganic fine particles Formulations other than those. For example: various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow adjustment Agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, and the like.

When the composite resin (A) of the present invention has a functional group, by heat resistance In the material, a reactive compound having a functional group reactive with a functional group of the composite resin (A) is blended, and the hardening density is further increased, so that the heat resistance of the obtained heat-resistant member is improved, which is preferable.

For example, when the composite resin (A) has an alcoholic hydroxyl group, it may be mentioned that it contains isocyanic acid. In the case of having an epoxy group, various curing agents such as a phenol-based cured product, an acid anhydride-based compound, a guanamine-based compound, and an amine-based compound may be mentioned.

As the compound containing an isocyanate group, for example, it is exemplified by toluene An aromatic diisocyanate such as cyanate or diphenylmethane-4,4'-diisocyanate, or m-xylene diisocyanate, α,α,α',α'-tetramethyl-m-xylene Polyisocyanate such as aralkyl diisocyanate such as isocyanate as main raw material; tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- (or 2,4,4-) trimethyl-1,6-hexamethylene diisocyanate, isocyanate isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-Diisocyanatocyclohexane, 1,3-bis(diisocyanatomethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, allophanate type polymerization Isocyanate, biuret type polyisocyanate, adduct type polyisocyanate and isomeric cyanate type polyisocyanate.

As the hardener of the epoxy group, for example, a phenol novolac tree can be cited. Grease, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition molding resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane Resin, phenylol ethane resin, naphthol novolac resin, naphthol-phenol copolyphenolic varnish resin, naphthol-cresol copolyphenolic varnish resin, biphenyl modified phenol resin (by double sub a polyphenol compound in which a methyl group is bonded to a phenol nucleus), a biphenyl-modified naphthol resin (a poly-naphthol compound obtained by bonding a phenol nucleus with a bismethylene group), and an aminotriazine-modified phenol resin (by Polyphenolization of phenolic nucleus such as melamine or benzoguanamine a compound or a phenolic compound such as an alkoxy-containing aromatic ring-modified novolac resin (a polyphenol compound obtained by linking a phenol nucleus and an alkoxy-containing aromatic ring with formaldehyde); phthalic anhydride; Benzoic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl An acid anhydride compound such as hexahydrophthalic anhydride; dicyandiamide; a guanamine compound such as a polyamine resin synthesized from a dimer of linoleic acid and ethylenediamine; diaminobiphenyl An amine compound such as a methane, a diethylenetriamine, a triethylenetetramine, a diaminodiphenylphosphonium, an isophorone diamine, an imidazole, a BF3-amine complex, or an anthracene derivative.

Further, if necessary, in addition to the above-mentioned curing agent, a curing accelerator may be used in combination. Various types of hardening accelerators can be used, and examples thereof include a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, and an amine salt. In particular, in terms of excellent properties such as hardenability, heat resistance, electrical properties, moisture resistance reliability, etc., 2-ethyl-4-methylimidazole is preferred among the imidazole compounds, and preferably three in the phosphorus compound. Phenylphosphine, preferably 1,8-diazabicyclo-[5.4.0]-undecene-7 (DBU) in the tertiary amine.

[thermosetting]

When the decyl alcohol group and/or the hydrolyzable alkylene group which the polyaluminoxane fragment (a1) which the composite resin (A) of the present invention has is hardened, it is good to heat-harden. In the thermal curing, it may be separately heated and hardened, and a known curing catalyst such as the following may be used in combination. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; sodium hydroxide or Inorganic bases such as potassium hydroxide; titanates such as tetraisopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethyl Various compounds containing a basic nitrogen atom such as benzylamine, monoethanolamine, imidazole or 1-methylimidazole; and various four grades such as tetramethylammonium salt, tetrabutylammonium salt and dilauryldimethylammonium salt a quaternary ammonium salt having an ammonium salt and having a chloride, a bromide, a carboxylate or a hydroxide as a counter anion; tin dibutyl diacetate, tin dibutyl dioctoate, dibutyl dilaurate A tin carboxylate such as tin, dibutyldiethylpyruvium pyruvate, tin octylate or tin stearate. The catalyst may be used singly or in combination of two or more.

Further, when the ethylene-based polymer fragment (a2) contains an alcoholic hydroxyl group and the heat-resistant material contains a compound containing an isocyanate group, the urethanization reaction can be caused by the addition of a catalyst.

Further, when the vinyl polymer fragment (a2) or the polyoxyalkylene fragment (a1) has a polymerizable unsaturated group, it can be reacted by using a thermal polymerization initiator.

Further, when the vinyl polymer fragment (a2) or the polyoxyalkylene fragment (a1) has an epoxy group, it can be prepared by formulating a compound having an epoxy group, a hydroxyl group, a carboxyl group or an acid anhydride, or a guanamine group. The reaction can be carried out using a general hardener for epoxy resins.

Further, a thermosetting resin may also be used in combination. As a thermosetting resin, Listed: vinyl resin, unsaturated polyester resin, polyurethane resin, epoxy resin, epoxy ester resin, acrylic resin, phenol resin, petroleum resin, ketone resin, oxime resin or modified resin of these Wait.

[Photohardening]

When the vinyl polymer fragment (a2) or the polyoxyalkylene fragment (a1) contains a group having a polymerizable double bond, photohardening can be carried out by blending a photopolymerization initiator in a heat resistant material. As photocuring, ultraviolet curing is preferred.

As the photopolymerization initiator, a known one may be used. For example, a group selected from the group consisting of acetophenones, benzil ketals, and benzophenones can be preferably used. the above. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-(4-isopropylphenyl)-2. - hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, and the like. Examples of the benzoin ketal include 1-hydroxycyclohexyl-phenyl ketone and benzoin dimethyl ketal. Examples of the benzophenones include benzophenone and methyl benzylidenebenzoate. Examples of the benzoin or the like include benzoin, benzoin methyl ether, and benzoin isopropyl ether. The photopolymerization initiator (B) may be used singly or in combination of two or more.

When ultraviolet curing is performed, a polyfunctional (meth)acrylate can be blended as needed, and since the hardening density is improved, heat resistance is improved. Further, a monofunctional (meth) acrylate can also be used.

For the light used for ultraviolet curing, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium-cadmium laser, an ultraviolet light emitting diode, or the like can be used.

[heat-resistant member]

The heat resistant structure of the present invention can be obtained by molding the heat resistant material of the present invention. Pieces. The shape of the heat-resistant member is not particularly limited, and may be, for example, a sheet shape, a plate shape, a spherical shape, a film shape, a large-sized structure, or an assembly or a molded product having a complicated shape, and may be selected according to the use.

The method for producing the heat-resistant member is not particularly limited, and for example, it may be The molding method of the mold can also be adjusted to adjust the viscosity to form a coating film. Alternatively, as in the case of an adhesive or a sealing material, it is hardened in a state in which another member is filled or covered, whereby a heat-resistant member can be produced.

[use]

Since the heat resistant material and the heat resistant member of the present invention are excellent in light resistance and heat resistance and have a low coefficient of linear expansion, they can be used in various applications. For example, it can be used for a sealing material for power semiconductors, a sealing material for high-brightness LEDs, a heat-resistant coating material, a copper clad laminate, and the like. In particular, by using as a sealing material for an optical semiconductor, deterioration due to light and dimensional change due to heat can be suppressed, and the performance of the semiconductor can be maintained at a high level.

[Examples]

Next, the present invention will be specifically described by way of examples and comparative examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

(Preparation example of polyoxyalkylene (a1-1))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen inlet, 415 parts of methyltrimethoxydecane (MTMS) and 3-methylpropenyloxypropyltrimethoxydecane (MPTS) were charged. 756 parts were heated to 60 ° C while stirring under a nitrogen atmosphere. Then, it took 5 minutes to add "Phoslex." A-4" [N-butyl acid phosphate produced by 堺Chemical Co., Ltd.] (A-4) A mixture of 0.1 parts with 121 parts of deionized water. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours to carry out a hydrolysis condensation reaction to obtain a reaction product.

The methanol and water contained in the obtained reaction product are removed under reduced pressure of 1 kPa to 30 kPa (kPa) at 40 ° C to 60 ° C to obtain a number average molecular weight of 1,000 and an active ingredient of 75.0% of polyoxyalkylene (a1-1) 1000 parts.

In addition, the "active ingredient" is a value obtained by dividing the theoretical yield (parts by weight) of the methoxy group of the decane monomer used by the hydrolysis and condensation reaction by the actual yield (parts by weight) after the hydrolysis condensation reaction. That is, it is calculated based on the equation [the theoretical yield (parts by weight) when the methoxy group of the decane monomer is subjected to the hydrolysis condensation reaction/the actual yield (parts by weight after the hydrolysis condensation reaction).

(Preparation example of polyoxyalkylene (a1-2))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen inlet, 642 parts of methyltrimethoxydecane (MTMS) and 3-glycidoxypropyltrimethoxydecane (GPTS) 62 were charged. The mixture was heated to 60 ° C while stirring under a nitrogen atmosphere. Next, a mixture containing 0.1 parts of "Phoslex A-4" [n-butyl acid phosphate (A-4) manufactured by Sigma Chemical Co., Ltd.] and 98.6 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours, whereby a hydrolysis condensation reaction was carried out to obtain a reaction product.

(Preparation example of polyoxyalkylene (a1-9))

In the same reaction vessel as in the above synthesis example, 231.9 parts of phenyltrimethoxydecane (PTMS) and 26.6 parts of dimethyldimethoxydecane (DMDMS) were charged. 114.5 parts of MTMS was heated to 60 ° C while stirring under a nitrogen atmosphere. Next, a mixture containing 0.1 part of "A-4" and 44.2 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours, whereby a hydrolysis condensation reaction was carried out to obtain a reaction product.

The methanol and water contained in the obtained reaction product are removed under reduced pressure of 1 kPa to 30 kPa (kPa) at 40 ° C to 60 ° C to obtain a number average molecular weight of 1,000 and an active ingredient of 75.0% of polyoxane (a1-9) 298.5 parts.

(Preparation example of polyoxyalkylene (a1-10))

In the same reaction vessel as in the above synthesis example, 151.7 parts of PTMS, 27.2 parts of DMDMS, 117.9 parts of MTMS, 35.0 parts of MPTS, and 35.2 parts of 3-glycidoxypropyltrimethoxydecane (GPTS) were placed in a nitrogen atmosphere. The temperature was raised to 60 ° C while stirring. Next, a mixture containing 0.1 part of "A-4" and 42.6 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours, whereby a hydrolysis condensation reaction was carried out to obtain a reaction product.

The methanol and water contained in the obtained reaction product are removed under reduced pressure of 1 kPa to 30 kPa (kPa) at 40 ° C to 60 ° C to obtain a number average molecular weight of 1,000 and an active ingredient of 74.8% of the polyoxyalkylene (a1-10) was 302 parts.

(Preparation example of polyoxyalkylene (a11-1))

In the same reaction vessel as in the above-mentioned synthesis example, 143.06 parts of MTMS was charged, and the temperature was raised to 60 ° C while stirring under a nitrogen atmosphere. Next, a mixture containing 0.1 part of "A-4" and 45 parts of deionized water was added dropwise over 5 minutes. End of drop Thereafter, the temperature of the reaction vessel was raised to 80 ° C and stirred for 4 hours, whereby a hydrolysis condensation reaction was carried out to obtain a reaction product.

The methanol and water contained in the obtained reaction product are removed under reduced pressure of 1 kPa to 30 kPa (kPa) at 40 ° C to 60 ° C to obtain a number average molecular weight of 1,000 and an active ingredient of 120 parts of 75.0% polyoxyalkylene (a11-1).

(Preparation of polyoxyalkylene (a11-2~a11-4, a11-6~a11-10))

Using the same apparatus as in the above-mentioned synthesis example, the oxirane monomer was charged at the mixing ratio shown in Table 1, and the temperature was raised to 60 ° C while stirring under a nitrogen atmosphere. Next, a mixture containing 0.1 part of "A-4" and 45 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 4 hours, whereby a hydrolysis condensation reaction was carried out to obtain a reaction product.

The methanol and water contained in the obtained reaction product are removed under reduced pressure of 1 kPa to 30 kPa (kPa) at 40 ° C to 60 ° C to obtain a polyoxane (a11-2~). Each sample of a11-4, a11-6, a11-7, a11-8).

The amount of the oxoxane monomer (unit: parts by weight) in the above polyoxane synthesis examples (a11-1 to a11-10) is shown in Table 1.

(Preparation example of vinyl polymer (a2-3))

In the same reaction vessel as in the above-mentioned synthesis example, 120 parts of PTMS and 322.5 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C while stirring under a nitrogen atmosphere. Next, at this temperature, while stirring under a nitrogen atmosphere, 263.3 parts of methyl methacrylate (MMA) and glycidyl methacrylate (GMA) 189.0 were added dropwise to the reaction container over 4 hours while stirring. Parts, 3.2 parts of styrene (St), 6.3 parts of butyl acrylate (BA), 37.8 parts of MPTS, 157.5 parts of 2-hydroxyethyl methacrylate (HEMA), 45 parts of n-butyl acetate, 2-ethyl peroxide A mixture of 25.2 parts of tert-butyl hexanoate (TBPEH). Then, the mixture was stirred at this temperature for 10 hours to obtain a vinyl polymer (a2-3) which is a reaction product in which the residual amount of TBPEH was 0.1% or less.

(Preparation Example of Vinyl Polymer (a21-1))

In the same reaction vessel as in the above-mentioned synthesis example, 27.58 parts of 3-glycidoxypropyltrimethoxydecane (GPTS) and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 while stirring under a nitrogen atmosphere. °C. Next, 26.9 parts of methyl methacrylate (MMA) and n-butyl methacrylate (BMA) 3.2 were added dropwise to the reaction container at this temperature under aeration of nitrogen gas under aeration for 4 hours. Parts, 75 parts of cyclohexyl methacrylate (CHMA), 2.0 parts of acrylic acid (AA), 2.0 parts of butyl acrylate (BA), 3.0 parts of MPTS, 37.5 parts of 2-hydroxyethyl methacrylate (HEMA), acetic acid A mixture of 15 parts of butyl ester and 6 parts of perbutyl 2-ethylhexanoate (TBPEH). Then, after stirring at this temperature for 2 hours, "A-4" was added dropwise over 5 minutes in the above reaction vessel. A mixture of 0.07 parts and 17.1 parts of deionized water was stirred at this temperature for 5 hours to carry out a hydrolysis condensation reaction of PTMS, DMDMS, and MPTS. The reaction product was analyzed by 1 H-NMR, and as a result, almost 100% of the trimethoxydecyl group of the decane monomer in the above reaction vessel was hydrolyzed. Then, the mixture was stirred at this temperature for 10 hours to obtain a vinyl polymer (a21-1) which is a reaction product having a residual amount of TBPEH of 0.1% or less.

(Preparation Example of Vinyl Polymer (a21-2~a21-4, a21-6~a21-12))

In the same reaction vessel as in the above synthesis example, a oxoxane monomer (GPTS, PTMS, DMDMS) was charged by the composition shown in Table 2-1 and Table 2-2, followed by 107.7 parts of n-butyl acetate. The temperature was raised to 95 ° C while stirring under a nitrogen atmosphere. Next, at this temperature, under stirring at a temperature of nitrogen gas, polymerization was carried out in the reaction vessel over 4 hours in a manner other than the mixture of the oxoxane monomers mixed according to Table 2-1 and Table 2-2. a mixture of sexual monomers. Then, after stirring at this temperature for 2 hours, a mixture of 0.07 parts of "A-4" and 17.1 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and stirred at the temperature for 5 hours, followed by the temperature. The mixture was stirred for 10 hours to obtain a reaction product of a residual amount of TBPEH of 0.1% or less, that is, each of the ethylene-based polymers (a21-2 to a21-4, a21-6 to a21-12).

The blending amount (unit: parts by weight) of the polymerizable monomer in the synthesis of the above vinyl polymer (a21-1 to a21-12) is shown in Table 2-1 and Table 2-2.

(Preparation Example of Composite Resin (A-1))

In a reaction vessel similar to the above-mentioned synthesis example, 20.1 parts of PTMS, 24.4 parts of DMDMS, and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C while stirring under a nitrogen atmosphere. Next, 15 parts of MMA, 45 parts of BMA, and 2-ethylhexyl methacrylate (EHMA) 39 were added dropwise to the reaction vessel at this temperature under aeration of nitrogen gas under aeration for 4 hours. Share, AA 1.5 A mixture of 1.5 parts of BA, 4.5 parts of MPTS, 45 parts of HEMA, 15 parts of n-butyl acetate, and 6 parts of TBPEH. Then, after stirring at this temperature for 2 hours, a mixture of 0.07 parts of "A-4" and 12.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was stirred at the same temperature for 5 hours to carry out PTMS. , hydrolysis reaction of DMDMS, MPTS. The reaction product was analyzed by 1 H-NMR, and as a result, almost 100% of the trimethoxydecyl group of the decane monomer in the above reaction vessel was hydrolyzed. Then, by stirring at this temperature for 10 hours, a reaction product in which the residual amount of TBPEH was 0.1% or less was obtained. In addition, the residual amount of TBPEH was measured by iodine titration.

Next, the polyfluorene obtained in Synthesis Example 1 was added to the preliminary reaction product. After 82.4 parts of the alkane (a1-1), after stirring for 5 minutes, 7.2 parts of deionized water was added, and the mixture was stirred at 80 ° C for 4 hours to carry out a hydrolysis condensation reaction of the preliminary reaction product with the polyoxyalkylene. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of methyl ethyl ketone (MEK) 150 parts. 28.6 parts of n-butyl acetate, and 428 parts of a composite resin (A-1) solution containing a polyoxyalkylene fragment and an ethylene polymer fragment and having a polyoxyalkylene fragment (a1-1) content of 50% by weight was obtained. (solid content was 50.1%).

(Preparation example of composite resin (A-3))

In a reaction vessel similar to the above-mentioned synthesis example, 46.7 parts of PTMS, 18.9 parts of DMDMS, and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C while stirring under a nitrogen atmosphere. Then, at this temperature, under aeration of nitrogen, While stirring, 45 parts of glycidyl methacrylate (GMA), 0.8 parts of styrene (St), 60.8 parts of MMA, 1.5 parts of BA, 4.5 parts of MPTS, and HEMA 37.5 were added dropwise to the above reaction vessel over 4 hours. A mixture of 15 parts of n-butyl acetate and 7.5 parts of TBPEH. Then, after stirring at this temperature for 2 hours, a mixture of 0.07 parts of "A-4" and 13.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was stirred at this temperature for 5 hours to carry out PTMS. , hydrolysis reaction of DMDMS, MPTS. The reaction product was analyzed by 1 H-NMR, and as a result, the trimethoxydecyl group of the decane monomer in the above reaction vessel was almost 100% hydrolyzed. Then, by stirring at this temperature for 10 hours, a reaction product in which the residual amount of TBPEH was 0.1% or less was obtained. In addition, the residual amount of TBPEH was measured by iodine titration.

Next, in the pre-reaction product, polypyroxyline (a1-2) 143.9 was added. After stirring for 5 minutes, 71.5 parts of deionized water was added, and the mixture was stirred at 80 ° C for 4 hours to carry out a hydrolysis condensation reaction of the preliminary reaction product with polyoxyalkylene. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of methyl ethyl ketone (MEK) 150 parts. And 29.3 parts of n-butyl acetate, and 600 parts of a composite resin (A-3) solution containing a polyoxyalkylene fragment and an ethylene polymer fragment and having a polyoxyalkylene fragment (a1-2) content of 50% by weight was obtained. (solid content was 50.3%).

(Preparation example of composite resin (A-9))

In 421.5 parts of the ethylene-based polymer (a2-3) obtained in the above Synthesis Example, 107.5 parts of polyoxyalkylene oxide (a1-9) was added, and after stirring for 5 minutes, deionized water was added thereto. 30.0 parts of the mixture was stirred at 80 ° C for 4 hours to carry out a hydrolysis condensation reaction of the above reaction product with polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of 122.5 parts of n-butyl acetate to obtain a non- 545.3 parts of a composite resin (A-9) having a volatile component of 55.0%.

(Preparation example of composite resin (A-10))

In 422.3 parts of the ethylene-based polymer (a2-3) obtained in the above Synthesis Example, 107.6 parts of polyoxyalkylene (a1-10) was added, and after stirring for 5 minutes, 28.9 parts of deionized water was added thereto, and the mixture was carried out at 80 ° C. The mixture was stirred for 4 hours to carry out a hydrolysis condensation reaction of the above reaction product with polyoxyalkylene. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of 141.5 parts of n-butyl acetate to obtain a non- The composite resin (A-10) having a volatile component of 55.0% was 548.2 parts.

(Preparation example of composite resin (A-21))

120 parts of polyoxyalkylene (a11-1) was added to 20 parts of the ethylene-based polymer (a21-1) obtained in the above synthesis example, and after stirring for 5 minutes, 62.3 parts of deionized water was added, and it was carried out at 80 °C. The mixture was stirred for 4 hours to carry out a hydrolysis condensation reaction of the above reaction product with polyoxyalkylene. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of 81.8 parts of methyl ethyl ketone. The nonvolatile component was 55% of a composite resin (A-21) comprising a polyoxyalkylene fragment and an ethylene polymer fragment (181.8 parts).

(Preparation of composite resin (A-22~A-24, A-26~A-30)) In the ethylene-based polymer (a21-2~a21-4, a21-6~a21-10) obtained in the above synthesis example, polypyroxane (a11-2~a11-4, according to the amount ratio of Table 3) was added. A11-6~a11-10), after stirring for 5 minutes, 62.3 parts of deionized water was added, and the mixture was stirred at 80 ° C for 4 hours to carry out a hydrolysis condensation reaction of the above reaction product with polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 kPa to 300 kPa at 40 ° C to 60 ° C for 2 hours to remove the produced methanol and water, followed by addition of 81.8 parts of methyl ethyl ketone. The non-volatile component was 55% of each of 181.8 parts of a composite resin (A-22~A-24, A-26~A-30) containing a polyoxyalkylene fragment and an ethylene polymer fragment.

Table 3 shows the blending amount (unit: parts by weight) of the polymerizable monomer when the above composite resin (A-22 to A-24, A-26 to A-30) was synthesized.

<Example 1> Heat resistant material 1

50 parts of a composite resin (A-1) solution having a solid content of 50%, 25 parts of cerium oxide microparticles (Aerosil 50 manufactured by Aerotech Co., Ltd.), and 250 parts of methyl isobutyl ketone (MIBK) were blended.

This adjustment was made using Ultra Apex Mill UAM015 manufactured by Shou Industrial Co., Ltd. Dispersion of cerium oxide microparticles in the formulation. In the preparation of the composition, 50% of 30 μm-type zirconia beads as a medium was filled in the grinder with respect to the volume of the grinder, and the formulation was subjected to cyclic pulverization at a flow rate of 1.5 liter per minute. The cycle pulverization was carried out for 30 minutes to obtain a composition in which cerium oxide fine particles were dispersed in a mixture of the composite resin (A-1) and a dispersion medium. The obtained composition was taken out from the outlet of Ultra Apex Mill UAM015, and the concentration of the dispersion medium was adjusted using an evaporator to obtain a composition containing cerium oxide microparticles having a solid concentration of 50%.

To the obtained composition, 0.5 parts of a photopolymerization initiator (Irgacure 184 (Ir 184): manufactured by BASF Corporation) was prepared and used as a heat resistant material 1.

<Example 2 to Example 14>

In the same manner as in Example 1, the respective heat resistant materials were obtained by blending the amounts described in the following Tables 4-1 and 4-2. When the cerium oxide microparticles are dispersed, dispersion is carried out in the same manner as in the previous stage to obtain a heat resistant material.

<Comparative Example 1 and Comparative Example 2>

MIBK and 2-methyl-4-imidazole were prepared for each of the ethylene-based polymers a21-11 and a21-12 by the blending amounts described in the following Table 4-3 to obtain a heat-resistant material for comparison.

[Evaluation]

The obtained heat resistant material was molded, and evaluation of light resistance and heat resistance was performed.

(Production of cured product for evaluation by ultraviolet light curing)

On the mirror layer of a single-sided mirror aluminum plate (100 mm × 250 mm × 0.3 mm), the heat-resistant material 1, the heat-resistant material 10, the heat-resistant material 14, and the heat-resistant material 18 were bar-coated to a thickness of 10 μm, and the shares in Yamato Scientific were limited. In the precision thermostat DH610S manufactured by the company, after prebaking at 80 degrees for 4 minutes, ultraviolet irradiation was performed under an 80 W/cm ² high-pressure mercury lamp at an irradiation dose of about 1000 mJ to obtain a cured product for evaluation.

(Production of cured product for evaluation by thermal hardening)

On the mirror layer of a single-sided mirror aluminum plate (100 mm × 250 mm × 0.3 mm), a heat-resistant material other than the heat-resistant material 1, the heat-resistant material 10, the heat-resistant material 14, and the heat-resistant material 18 is coated to a thickness of 100 μm, and is limited in Daiwa Scientific Co., Ltd. In the precision thermostat DH610S manufactured by the company, heat treatment was performed at 150 degrees for 3 hours, and the obtained cured coating film was peeled off from the aluminum plate, thereby obtaining a cured product for evaluation having a film thickness of 100 μm.

The obtained cured product for evaluation was evaluated as follows, and the results are shown in the first table.

[Light resistance measurement]

Light resistance test (UV resistance test) by SUV test (100 mW/cm ² , 60 degrees, 50%) was carried out using a super ultraviolet tester (EYE SUPER UV TESTER) manufactured by Iwasaki Electric Co., Ltd., by visual inspection Observations were made to compare and evaluate the unexposed test body with the test body after 360 hours. The person who has no change in the surface state or the like is evaluated as (○). In addition, it was confirmed by visual observation that the yellowish tone was evaluated as Δ, and it was confirmed that the crack occurrence was evaluated as ×.

[Heat resistance test line expansion coefficient]

The linear expansion coefficient (CTE) of the cured product for evaluation at 50 degrees was measured using TMA-50 manufactured by Shimadzu Corporation.

About abbreviations

Ir184: Photopolymerization initiator (manufactured by BASF Corporation)

2E4MZ: 2-methyl-4-imidazole (thermal polymerization catalyst)

SP-170: Photoacid generator (made by ADEKA)

[Industrial availability]

Since the heat resistant material of the present invention is excellent in light resistance and heat resistance and has a small coefficient of linear expansion, it can be preferably used for a heat resistant adhesive, a sealing material for power semiconductors, a sealing material for high-brightness LEDs, a heat-resistant coating material, Copper foil laminates, etc. In addition, the heat-resistant member obtained by curing the heat-resistant material does not cause deterioration due to light such as sunlight, fluorescent lamps, LED light, or UV lamps, and also has excellent dimensional change due to heat. Heat resistance, so it can be used stably for a long time.

Claims (7)

A heat resistant material comprising a composite resin (A), wherein the composite resin (A) is a polysiloxane derivative (a1) and a vinyl polymer fragment (a2) by a bond represented by the general formula (3) Bonded, the polyoxyalkylene fragment (a1) has a structural unit represented by the formula (1) and/or the formula (2), and a stanol group and/or a hydrolyzable decyl group: (In the general formulae (1) and (2), R ¹ , R ² and R ³ each independently represent: having a selected from -R ⁴ -CH=CH ₂ , -R ⁴ -C(CH ₃ )=CH ^{_{2, -R 4 -O-CO-}} C (CH 3) = CH 2, and ^{-R 4 -O-CO-CH =} CH group of one kind of polymerizable double bond group consisting of ₂ (wherein, R ⁴ represents a single bond or an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon atom; 7~12 aralkyl) (In the formula (3), a carbon atom constitutes a part of the above-mentioned ethylene-based polymer fragment (a2), and only a ruthenium atom bonded to an oxygen atom constitutes a part of the above-mentioned polyoxyalkylene fragment (a1). The heat resistant material according to claim 1, wherein in the above composite resin (A), the polyoxyalkylene fragment (a1) is a condensed decane compound having a stanol group and/or a hydrolyzable decyl group. In the obtained fragment, the decane compound having a decyl alcohol group and/or a hydrolyzable decyl group has an epoxy group-containing decane compound in an amount of 25% by weight or more and 90% by weight or less. The heat resistant material according to claim 1 or 2, further comprising inorganic fine particles. The heat resistant material according to any one of the items 1 to 3, wherein, in the composite resin (A), the polysiloxane derivative is the total solid content of the composite resin (A) The content of (a1) is from 45% by weight to 95% by weight. The heat resistant material according to any one of claims 1 to 4, wherein in the above composite resin (A), the polyoxyalkylene fragment (a1) has a stanol group and/or a hydrolyzable property. A fragment obtained by condensing a decyl group of a decyl group, and the decane compound having a decyl alcohol group and/or a hydrolyzable decyl group has a trialkoxy decane of 40 mol% or more. The heat resistant material according to any one of claims 1 to 5, wherein the trialkoxydecane as described in claim 5 is a monoalkyltrialkoxydecane. A heat-resistant member characterized by molding a heat-resistant material according to any one of claims 1 to 6.