JP2006278476A - Composition for heat dissipating sheet and heat dissipating sheet cured thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a heat dissipating sheet which has good thermal conductivity for outstanding ruggedness and for high productivity in which surface adhesiveness is controlled easily, and to provide a heat dissipation sheet obtained by hardening this composition. <P>SOLUTION: The composition for the heat dissipating sheet contains (A) a general formula (1): -OC(O)C(R<SP>a</SP>)=CH<SB>2</SB>(in the formula, R<SP>a</SP>is a hydrogen atom or carbon number organic group of 1-20) expressing a basis expressed by two or more per molecule having one or more vinyl polymer at a molecule end by the above general formula (1) among those, (B) an initiator, and (C) a thermally conductive loading material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a heat radiating sheet composition and a heat radiating sheet obtained by curing the composition. More specifically, the present invention relates to a heat radiation sheet composition comprising a vinyl polymer having a (meth) acryloyl group, an initiator and a heat conductive filler, and a heat radiation sheet obtained by curing the composition.

Conventionally, heat-conductive materials having rubber elasticity have been widely used as heat dissipation / heat transfer spacers for electronic components such as various heaters, temperature sensors, and the like, as well as semiconductors such as transistors, diodes, and ICs. As such a heat conductive material, for example, a material in which a heat conductive filler is blended with a base rubber such as silicone rubber or EPDM rubber is known (see Patent Document 1). Technologies and the like are disclosed. Moreover, what uses silicone rubber is the best known, and the technique by the combination of various heat conductive fillers and silicone rubber is disclosed (refer patent documents 2-4).
In such a material for heat conduction, not only the heat conductivity of the material itself but also the adhesion to the base material is important. For the adhesion to the substrate, the adhesion to the substrate surface and the followability to the substrate shape and deformation are important. A material having rubber elasticity is suitable in the latter aspect. In addition, with regard to the former, except in the case of an irregular adhesive, etc., in the case of a fixed form, such as a sheet or tape, the adhesive layer or the adhesive layer is separately provided, or the adhesiveness can be increased by expressing the surface adhesiveness. Secured.

However, in a heat conductive material, in order to increase the heat conductivity, a high amount of heat conductive filler is usually filled. However, the higher the filler is filled, the more the elasticity of the material itself is lost and the surface tackiness is also reduced. As a result, there is a problem that the adhesion to the substrate is impaired. On the other hand, the method of providing the adhesive layer and the pressure-sensitive adhesive layer is an effective method with little influence on the surface property of the material itself, but there is a problem that the process of newly forming those layers is required and the productivity is poor. is there.
On the other hand, based on a hydrolyzable silyl group-containing compound having a hydrolyzable silyl group such as polyalkylene glycol or polyisobutylene, a compound containing a heat conductive filler has a resin composition having both excellent strength and adhesion It is disclosed that it is a thing (refer patent document 5). However, the method for controlling the adhesion is not particularly shown, and since the curing type is a moisture curing type, curing curing requires several hours or more, so that the productivity is inferior.
JP 2001-139733 A Japanese Patent Publication No. 6-55891 Japanese Examined Patent Publication No. 6-38460 Japanese Patent Publication No. 7-91468 JP 2001-302936 A

An object of the present invention is to provide a highly heat-dissipating sheet composition having excellent durability and good thermal conductivity, and capable of easily controlling surface tackiness, and curing the composition. It is providing the thermal radiation sheet obtained by making it.

The present inventors have found that the above-mentioned problems can be solved by a composition for a heat-dissipating sheet in which a vinyl polymer having a (meth) acryloyl group and an initiator are further blended with a thermally conductive filler, and the present invention is It came to be completed.

That is, this invention relates to the following composition for thermal radiation sheets and a thermal radiation sheet.
(1) (A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl-based polymer (B) initiator (C) having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular terminals. A composition for a heat radiation sheet containing a filler.
(2) The composition for a heat dissipation sheet according to (1), wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer.
(3) The composition for a heat radiation sheet according to any one of (1) to (2), wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer.
(4) Any of (1) to (3), wherein the vinyl monomer constituting the main chain of component (A) contains at least one selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. The composition for heat dissipation sheets as described in any one of Claims 1-3.
(5) The composition for a heat radiation sheet according to any one of (1) to (4), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. .

(6) The composition for a heat radiation sheet according to (5), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group.
(7) The composition for heat radiating sheets as described in any one of (1) to (6), which is used for a portion requiring heat resistance.
(8) The composition for heat radiating sheets as described in any one of (1) to (7), which is used for a portion requiring oil resistance.
(9) The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The composition for heat dissipation sheets according to any one of (1) to (8), which is produced by reacting the compound represented by formula (1).
(10) A vinyl polymer having a halogen group at the terminal is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The composition for heat-radiation sheets as described in (9) which has group shown by these.

(11) The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The composition for heat dissipation sheets according to any one of (1) to (8), which is produced by reacting the compound represented by formula (1).
(12) The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The composition for heat dissipation sheets according to any one of (1) to (8), which is produced by reacting with a compound represented by formula (1).
(13) The composition for a heat radiation sheet according to any one of (1) to (12), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
(14) The composition for a heat radiation sheet according to (13), wherein the living radical polymerization is atom transfer radical polymerization.

(15) The composition for a heat radiation sheet according to (14), wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron.
(16) The composition for a heat radiation sheet according to (15), wherein the transition metal complex is a copper complex.
(17) The composition for a heat radiation sheet according to any one of (1) to (12), wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.
(18) The composition for a heat radiation sheet according to any one of (1) to (17), wherein the number average molecular weight of the component (A) is 3000 or more.
(19) Any of (1) to (18), wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. The composition for heat-radiation sheets of crab.

(20) The composition for a heat radiation sheet according to any one of (1) to (19), which contains a monomer and / or an oligomer having a radical polymerizable group.
(21) The composition for a heat dissipation sheet according to any one of (1) to (19), which contains a monomer and / or an oligomer having an anion polymerizable group.
(22) The composition for a heat radiation sheet according to any one of (21) to (22), which contains a monomer and / or an oligomer having a (meth) acryloyl group.
(23) The composition for a heat-dissipating sheet according to (22), comprising a monomer and / or an oligomer having a (meth) acryloyl group and having a number average molecular weight of 5000 or less.
(24) The composition for a heat radiation sheet according to any one of (1) to (23), wherein the initiator of the component (B) is a photopolymerization initiator and / or a thermal polymerization initiator.
(25) The composition for a heat radiation sheet according to any one of (1) to (23), wherein the initiator of the component (B) is a redox initiator.

(26) The component (C) is at least one selected from metal oxide, metal nitride, metal carbide, metal hydroxide, crystalline silica, organic polymer fired product, and nitrogen carbide (1) to (25) ). The composition for heat dissipation sheets in any one of 1).
(27) The composition for a heat radiation sheet according to (26), wherein the component (C) is at least one selected from aluminum oxide, boron nitride, aluminum nitride, and aluminum hydroxide.
(28) The composition for a heat radiating sheet according to any one of (1) to (27), wherein a filling ratio of the thermally conductive filler as the component (C) is 25% by volume or more in the entire composition.
(29) In addition to the components (A), (B), and (C), an organic carboxylic acid compound is further contained as the component (D), according to any one of (1) to (28) A composition for a heat dissipation sheet.
(30) The composition for a heat radiation sheet according to (29), wherein the component (D) is a stearic acid compound.

(31) The composition for a heat radiation sheet according to (30), wherein the component (D) is a metal stearate.
(32) The composition for a heat radiation sheet according to (31), wherein the component (D) is at least one selected from lead stearate, zinc stearate, and calcium stearate.
(33) A heat radiation sheet obtained by curing the composition for heat radiation sheet according to any one of (1) to (32).

Below, the composition for heat-radiation sheets of this invention is demonstrated in detail.
The composition for heat radiating sheets of the present invention is a composition comprising the following components (A), (B), and (C).
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer (B) initiator (C) having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular terminals. Filler.

<< (A) component >>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having 2 or more groups per molecule, and having 1 or more groups represented by the general formula (1) at the molecular terminals.

The number of groups ((meth) acryloyl group) represented by the general formula (1) in the component (A) is 2 or more per molecule, and 1 or more at the molecular end. Two per molecule are preferred.
Since the side reaction may actually occur when the component (A) is produced, the average number of the (meth) acryloyl group in the produced vinyl polymer mixture is less than 2. May be. In the present invention, when the average value of the number of (meth) acryloyl groups in the actually produced vinyl polymer mixture is 1.1 or more, this mixture is referred to as component (A). That is, the component (A) includes a mixture of vinyl polymers containing a vinyl polymer having two or more (meth) acryloyl groups per molecule and one or more at the molecular end.
From the viewpoint of crosslinking, the average value of the number of the (meth) acryloyl group is preferably 1.5 or more per molecule.
Furthermore, one or more of the (meth) acryloyl group is present at the molecular end, but the position of the other (meth) acryloyl group is not particularly limited. From the viewpoint that the distance between cross-linking points can be increased, a form close to the other molecular end is preferable, and a form close to the other molecular end is particularly preferable.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. And the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.
Preferred examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, —CN and the like can be mentioned, and preferably —H, —CH ₃ .

(A) There is no limitation in particular as a vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and their salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyl Silicon-containing vinyl monomers such as trimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as reimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of oil resistance and the like, it is particularly preferable that the vinyl monomer constituting the main chain includes at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate.

In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The molecular weight distribution of component (A) [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)] is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.
In the GPC measurement in the present invention, usually, chloroform or tetrahydrofuran is used as a mobile phase, a polystyrene gel column is used, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

<Production method of component (A)>
(A) There is no limitation in particular about the manufacturing method of a component.
The vinyl polymer is generally produced by anionic polymerization or radical polymerization, but radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

The radical polymerization method used for the production of the component (A) is a method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide or the like as a polymerization initiator. Can be classified into “radical polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced increases. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. Can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Therefore, in the “living radical polymerization method”, a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

Living polymerisation means, in a narrow sense, polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules, 1994, Vol. 27, page 7228, using radical scavengers such as nitroxide compounds, organic halides and the like as initiators and transition metal complexes as catalysts. Atom transfer radical polymerization (ATRP) etc. are mentioned.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of "", it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a great degree of freedom in designing initiators and catalysts. Therefore, production of vinyl polymers having specific functional groups The method is more preferable.

Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO 96/30421 pamphlet, WO 97/18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, The method described in page 1721 etc. is mentioned.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the viewpoint of ease of control, and particularly an atom transfer radical. A polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Next, the living radical polymerization method will be described.
First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.
In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

Specific examples of the nitroxy free radical compound include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl- 1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, Examples include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds.
Although the combined ratio of both is not particularly limited, 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable.
The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis Examples include peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate, and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.
Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as described above, a polymer having a functional group at the terminal can be obtained. When this is used in the present invention, a polymer having a functional group at the terminal can be obtained.

There are no particular limitations on the polymerization conditions such as the monomer, solvent, and polymerization temperature used in the polymerization using a radical scavenger such as the nitroxide compound, but it may be the same as that used for the atom transfer radical polymerization described below.

Next, an atom transfer radical polymerization method that is more preferable as the living radical polymerization method used in the present invention will be described.
In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen A sulfonyl chloride compound or the like is used as an initiator.

For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom),
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4
(Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom) ),
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.
Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having the alkenyl group is not particularly limited. For example, the general formula (6):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or others. R ⁸ is —C (O) O— (ester group), —C (O) — (keto group) or o-, m-, p-phenylene group, R ⁹ is a direct bond Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by this is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.
Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. An alkylene group etc. are mentioned.

Specific examples of the organic halide having an alkenyl group represented by the general formula (6) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
(H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2
(In the above formulas, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20)
Etc.

The organic halide having an alkenyl group is further represented by the general formula (7):
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group ) Or o-, m-, p-phenylene group)
The compound shown by these is mentioned.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to the carbon, and is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound represented by the general formula (7) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (8):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (8)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as described above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). An organosiloxy group, when two or more R ¹¹ or R ¹² are present, they may be the same or different; Y represents a hydroxyl group or a hydrolyzable group; and Y is two or more When present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfy)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formula, X is a chlorine atom, bromine atom, iodine atom, n is an integer of 0-20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(Wherein X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3
(In the above formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (9):
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X, Y are the same as above, m is an integer of 0-19)
What is shown by this is illustrated.

If the compound represented by the general formula (9) is specifically exemplified,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said hydroxyl group, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.
There is no restriction | limiting in particular in the vinyl-type monomer used in this superposition | polymerization, and all already illustrated can be used suitably.

Further, the transition metal complex used as a polymerization catalyst is not particularly limited, but preferably a metal complex having a central metal of Group 7, Group 8, Group 9, Group 11 or Group 11 of the periodic table, for example, copper, It is a metal complex of nickel, ruthenium and iron. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Is mentioned.
When a copper compound is used, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.
When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.
Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
The method for producing the component (A) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the method described above, and the reactive functional group is changed to a substituent having a (meth) acryloyl group. It can be manufactured by converting.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction method 1) A vinyl polymer having a halogen group (halogen atom) at the terminal, and the general formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.
As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl-based polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
The vinyl polymer having a halogen group at the terminal is not particularly limited, but a vinyl polymer having a terminal group represented by the general formula (3) is preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ¹ and R ² in the general formula (3) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-mentioned organic halide or halogenated sulfonyl compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer, or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

There is no limitation in particular in the compound represented by General formula (2).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (2) are the same as those described above, and specific examples thereof are the same as those described above.
M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples of the type include alkali metal ions and quaternary ammonium ions.

Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion.
Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.
Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (4) are the same as those described above, and specific examples thereof are the same as those described above.

The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Is produced by a method of polymerizing a vinyl monomer, but the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following method is illustrated.
(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
(In the formula, R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁴ is a phenylene group, it is a styrene compound. A specific example of R ¹⁵ is the same as the specific example of R ⁹ .
There is no limitation on the timing of reacting a compound having a polymerizable alkenyl group and hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, it has a low polymerizable alkenyl group and hydroxyl group in the molecule as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Although there is no limitation in particular in the said compound, For example, General formula (11):
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as described above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like.
A specific example of R ¹⁶ is the same as the specific example of R ⁹ .

Although there is no limitation in particular in the compound shown by General formula (11), The alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable from the point that acquisition is easy.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as described above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group)
A method in which a halogen atom is substituted by reacting a stabilized carbanion having a hydroxyl group represented by formula (1).

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, —CO ₂ R, —C (O) R, —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a halogen atom at the terminal of the polymer, is represented by the general formula (13):
HO-R ^{< 16 >} -O ^- M ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although reaction temperature does not have limitation in particular, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (5) are the same as those described above, and specific examples thereof are the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And an arylene group having 7 to 20 carbon atoms.
Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mentioned.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Xylylene diisocyanate, isophorone diisocyanate and the like. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.
The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
The reaction solvent is not particularly limited, but an aprotic solvent is preferable.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

<< (B) component >>
(B) Although there is no limitation in particular as an initiator of a component, a photoinitiator, a thermal-polymerization initiator, a redox-type initiator, etc. are mentioned.
The photopolymerization initiator, the thermal polymerization initiator, and the redox initiator may be used alone or as a mixture of two or more. When used as a mixture, various initiators are used. It is preferable that the usage-amount of an agent exists in each below-mentioned range.

As a photoinitiator, a photoradical initiator, a photoanion initiator, a near-infrared photoinitiator, etc. are mentioned, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is especially preferable.
Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin Tyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- Examples include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl and the like.
Of these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred.

Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. .

As the near infrared photopolymerization initiator, a near infrared light absorbing cationic dye or the like may be used.
Near-infrared light absorbing cationic dyes are excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

These photopolymerization initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.
Specific examples of combinations with other compounds include combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, and combinations with iodonium salts such as diphenyliodonium chloride, methylene blue, and the like. Examples include those combined with a dye and an amine.

In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

(B) When using a photoinitiator as a component, the addition amount does not have a restriction | limiting in particular, However, 0.001-10 with respect to 100 weight part of (A) component from the point of sclerosis | hardenability and storage stability. Part by weight is preferred.

Further, the thermal polymerization initiator is not particularly limited, and examples thereof include azo initiators, peroxide initiators, persulfate initiators and the like.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2, 2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2- Cyclopropylpropionitrile), and 2,2′-azobis (methylisobutylate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) And the like.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

A preferable thermal polymerization initiator is selected from the group consisting of an azo initiator and a peroxide initiator. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

A thermal polymerization initiator may be used independently or may use 2 or more types together.
When a thermal polymerization initiator is used as the component (B), the thermal polymerization initiator is present in a catalytically effective amount, and its addition amount is not particularly limited, but can be added to the component (A) of the present invention and others. When the total amount of the monomer and / or oligomer mixture described below is 100 parts by weight, it is preferably about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight.

Furthermore, the redox (oxidation-reduction) type initiator that can be used as the component (B) can be used in a wide temperature range. In particular, the following initiator species can be advantageously used at room temperature.
Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators and reducing agents (sodium metabisulfite, sodium bisulfite, etc.); organic peroxides and tertiary amines. Combinations such as a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines; a combination of organic peroxide and transition metal, such as a combination of cumene hydroperoxide and cobalt naphthate, and the like.
Preferred redox initiators are a combination of organic peroxide and tertiary amine, a combination of organic peroxide and transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide. And cobalt naphthate.

A redox initiator may be used independently or may use 2 or more types together.
When a redox initiator is used as the component (B), the redox initiator is present in a catalytically effective amount, and the amount added is not particularly limited, but can be added to the component (A) of the present invention and others. When the total amount of the monomer and / or oligomer mixture described below is 100 parts by weight, it is preferably about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight.

<< (C) component >>
As the heat conductive filler of component (C), a commercially available general heat conductive filler can be used. Among these, metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, and zinc oxide from the viewpoint of thermal conductivity, availability, electrical insulation, etc .; boron nitride, aluminum nitride, silicon nitride, etc. Metal nitrides such as boron carbide, aluminum carbide, silicon carbide, etc .; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; crystalline silica; acrylonitrile-based polymer fired product, furan resin fired product, cresol resin fired Preferably, organic polymer baked products such as products, polyvinyl chloride baked products, sugar baked products, charcoal baked products; nitrogen carbide and the like.
Further, from the viewpoints of availability and thermal conductivity, aluminum oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, and crystalline silica are more preferable, and aluminum oxide, boron nitride, aluminum nitride, and aluminum hydroxide are particularly preferable. .

In addition, these thermally conductive fillers have a silane coupling agent (vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, chlorosilane, aminosilane, etc.) Titanate coupling agents (alkoxy titanate, amino titanate, etc.) or fatty acids (caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and other saturated fatty acids, sorbic acid, elaidic acid , Oleic acid, linoleic acid, linolenic acid, erucic acid and other unsaturated fatty acids) and resin acids (abietic acid, pimaric acid, levopimaric acid, neoabietic acid, parastrinic acid, dehydroapietic acid, isopimaric acid, sandaracopimar Acid, komuric acid, secodehydroabie Phosphate, the dihydroabietic acid, etc.) or the like, it is preferable that the surface has been treated.

The amount of the heat conductive filler used is such that the heat conductivity of the heat conductive material obtained from the heat radiating sheet composition of the present invention can be increased. (%) Is preferably 25% by volume or more of the total composition. If it is less than 25% by volume, the thermal conductivity tends to be insufficient. When a higher thermal conductivity is desired, the amount of the thermally conductive filler used is more preferably 40% by volume or more in the total composition.

Here, the volume fraction (%) of the thermally conductive filler is calculated from the weight fraction and specific gravity of the resin component and the thermally conductive filler, and is obtained by the following equation. In the following formula, the heat conductive filler is simply referred to as “filler”.
Filler volume ratio (volume%) = (filler weight ratio / filler specific gravity) ÷ [(resin weight ratio / resin weight specific gravity) + (filler weight ratio / filler specific gravity)] × 100
Here, the resin component refers to all components excluding the thermally conductive filler, and specifically refers to the components (A) to (B), the component (D), and other various additives.

Moreover, it is suitable to use together 2 or more types of thermally conductive fillers from which a particle diameter differs as one technique which raises the filling rate of the thermally conductive filler with respect to (A) component. In this case, it is preferable that the heat conductive filler having a large particle diameter exceeds 10 μm, and the heat conductive filler having a small particle diameter is 10 μm or less.
Moreover, these heat conductive fillers can use not only the same kind of heat conductive filler but also two or more kinds of different kinds in combination.

<< (D) component >>
The composition for heat-radiation sheets of this invention may contain the organic carboxylic acid compound of (D) component as needed.
Examples of the organic carboxylic acid compound include a stearic acid compound, and other than the stearic acid compound, a saturated fatty acid compound having 1 to 18 carbon atoms, an unsaturated fatty acid compound having 3 to 18 carbon atoms, and an aliphatic group having 2 to 36 carbon atoms. And dicarboxylic acid compounds.
As stearic acid compounds, lead stearate, lithium stearate, lithium 12-hydroxystearate, sodium stearate, sodium 12-hydroxystearate, potassium stearate, potassium 12-hydroxystearate, magnesium stearate, 12-hydroxy Stearic acid metal salts such as magnesium stearate, calcium stearate, calcium 12-hydroxystearate, barium stearate, barium 12-hydroxystearate, zinc stearate, zinc 12-hydroxystearate; stearic acid, monoglyceride stearate, stearic acid And methyl.
Of these, calcium stearate, lead stearate, and zinc stearate are preferred.
In addition, the said organic carboxylic acid compound may be used independently and may be used together 2 or more types.

Component (D) is preferably used in an amount of 0.025 to 5 parts by weight, more preferably 0.05 to 4 parts per 100 parts by weight of component (A) from the viewpoint of releasability and sheet physical property balance. Parts by weight.

<< Composition for heat dissipation sheet >>
It is preferable to use the composition for heat-radiation sheets of this invention in the site | part which requires oil resistance and heat resistance.
The composition for heat-radiation sheets of this invention is a composition formed by containing (A), (B), (C) component as mentioned above. Moreover, (D) component can be contained as needed.
Furthermore, polymerizable monomers and / or oligomers can be used in combination for the purpose of improving surface curability, imparting toughness, and improving workability by reducing viscosity.
Furthermore, you may mix | blend various additives etc. in order to adjust a physical property with the composition for thermal radiation sheets of this invention as needed.

<Polymerizable monomer and / or oligomer>
As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable from the viewpoint of curability.

Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Examples of the anionic polymerizable group include a (meth) acryloyl group such as a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides. -A vinylidene halide monomer, a polyfunctional monomer, etc. are mentioned.

(Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) acrylic Benzyl, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meta ) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate , Perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl. Moreover, the compound etc. which are shown by the following Formula can also be mention | raise | lifted. In the following formula, n represents an integer of 0-20.

Examples of the styrenic monomer include styrene and α-methylstyrene.
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Examples of acrylamide monomers include acrylamide and N, N-dimethylacrylamide.
Examples of the conjugated diene monomer include butadiene and isoprene.
Examples of the vinyl ketone monomer include methyl vinyl ketone.
Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexa Chlorate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1 , 3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetra Chi glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate A urethane resin obtained from a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.)} Urethane acrylate resin obtained by reaction; resin in which a (meth) acryl group is introduced into the polyol via an ester bond; polyester acrylate resin, poly (meth) acryl acrylate resin (having a polymerizable reactive group) Poly (meth) acrylic ester resin) and the like.

Among the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Furthermore, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

The amount of the polymerizable monomer and / or oligomer used is from 100 parts by weight of the component (A) (hereinafter also simply referred to as “parts”) from the viewpoint of improving surface curability, imparting toughness, and workability by reducing viscosity. 1 to 200 parts is preferable, and 5 to 100 parts is more preferable.

<Reinforcing silica>
Reinforcing silica may be added to the heat radiating sheet composition of the present invention from the viewpoint of improving the strength of the heat radiating sheet.
Examples of the reinforcing silica include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect. In addition, the measuring method of a specific surface area is as the below-mentioned.

Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it easily exhibits fluidity suitable for molding.
As a more specific example of the reinforcing silica, there is no particular limitation. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil and the like.

The reinforcing silica may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the addition amount of reinforcing silica, Preferably it is 0.1-100 parts with respect to 100 parts of (A) component, More preferably, it is 0.5-80 parts, More preferably, it is 1-50 parts. It is. When the blending amount is less than 0.1 part, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts, the workability of the heat radiating sheet composition may be lowered.

<Filler>
In addition to the reinforcing silica, various fillers may be used as necessary in the heat radiating sheet composition of the present invention.
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, dolomite, silicic anhydride, Reinforcing fillers such as hydrous silicic acid and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara, Fillers such as fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; fibrous fillers such as asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc. Is mentioned. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, when it is desired to obtain a heat dissipation sheet having low strength and large elongation, a filler selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. may be added. it can.

In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the heat-dissipating sheet may not be sufficient. As the value of the specific surface area is larger, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the heat-dissipating sheet becomes greater. Moreover, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case of using non-surface-treated calcium carbonate, and the heat dissipation sheet composition has adhesion and weather resistance. It is thought that the improvement effect of is improved.

Examples of the surface treatment agent include organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Sodium salts and potassium salts of these fatty acids, and alkyl esters of these fatty acids.
Specific examples of surfactants include sodium anion surfactants such as polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, sulfate-type anionic surfactants such as potassium salts, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, paraffins Examples thereof include sulfonic acid type anionic surfactants such as sodium salts and potassium salts such as sulfonic acid, α-olefin sulfonic acid and alkylsulfosuccinic acid.

The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight (hereinafter referred to as “%”) with respect to calcium carbonate, and more preferably in the range of 1 to 5%. When the treatment amount is less than 0.1%, the workability, adhesiveness and weatherability may not be sufficiently improved. When the treatment amount exceeds 20%, the storage stability of the heat-dissipating sheet composition decreases. There are things to do.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as the thixotropy of the composition, the breaking strength of the heat dissipation sheet, the breaking elongation, the adhesiveness and the weather resistance adhesiveness are used. Is preferred.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, the following may be added as necessary. Can be used.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry methods and wet methods for pulverization methods, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the heat-dissipating sheet composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters by classification. Although there is no particular limitation, when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance adhesion of the heat dissipation sheet is expected, the value of the specific surface area is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or only for the purpose of increasing the viscosity.

In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although not particularly limited, for example, when heavy calcium carbonate with a specific surface area value of 1.5 m ² / g or more and collagen calcium carbonate are combined, the increase in viscosity of the compound is moderately suppressed. The effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the heat radiation sheet can be greatly expected.

When the filler is used, the addition amount is preferably 5 to 1000 parts, more preferably 20 to 500 parts, with respect to 100 parts of component (A), It is particularly preferable to use in the range of 40 to 300 parts. When the blending amount is less than 5 parts, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the heat dissipation sheet may not be sufficient. May decrease. A filler may be used independently and may be used together 2 or more types.

<Adhesive resin>
Since the composition for a heat dissipation sheet of the present invention is preferably composed mainly of a (meth) acrylic polymer, it is not always necessary to add an adhesion-imparting resin. Can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.
The amount of the adhesion-imparting resin used is preferably 0.1 to 100 parts with respect to 100 parts of the component (A) from the viewpoint of the balance between mechanical properties, heat resistance, oil resistance and adhesiveness of the heat dissipation sheet.

<Anti-aging agent>
An anti-aging agent may be blended in the composition for heat dissipation sheet of the present invention in order to adjust the physical properties.
An acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not necessarily required, but a conventionally known antioxidant and light stabilizer may be appropriately used. it can. In addition, the anti-aging agent can be used for polymerization control during polymerization, and physical properties can be controlled.

Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
Examples of the antioxidant include thioethers such as MARK PEP-36 and MARK AO-23 (all are manufactured by Asahi Denka Co., Ltd.); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all are Ciba Specialty And phosphorous antioxidants such as Chemicals Co., Ltd .; hindered phenolic compounds, and the like. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-tert-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyl Enyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Ntamechiru 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024 , IRG NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumitizer GA-80 (and above, any Can also be exemplified by, but not limited to, Sumitomo Chemical Co., Ltd.).

Furthermore, a monoacrylate phenolic antioxidant having both an acrylate group and a phenol group, a nitroxide compound, and the like can be given.
Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilyzer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name Sumitizer GS) and the like.

Nitroxide compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals, cyclic hydroxyamines, etc. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.
Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

Antioxidants may be used in combination with light stabilizers, and when used together, the effects are further exerted, and the heat resistance may be particularly improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

When using a vinyl polymer having a (meth) acryloyl group in the molecule to produce a heat-dissipating sheet by photo radical curing, since the polymerization proceeds fast, it is difficult to control, and the polymerization is excessive. There are many cases where the mechanical strength is insufficient, such as being in an overcrosslinked state and the obtained heat-dissipating sheet does not exhibit sufficient elongation. As a method for controlling the polymerization, by making the functional group involved in the polymerization a methacryloyl group, the polymerizability can be lowered as compared with the case of the acryloyl group, but in this case, the polymerizability may be extremely lowered. Many are not practical. In general, a polymerization inhibitor may be used, but this is for the purpose of suppressing the polymerization itself and is not suitable for controlling the polymerization. On the other hand, an anti-aging agent may be added in order to improve the heat resistance and weather resistance of the obtained heat radiating sheet, but this is not used for the purpose of improving the initial physical properties of the heat radiating sheet.
The monoacrylate phenol-based antioxidant can not only be used as an antioxidant but also can control polymerization, and can improve the elongation of the heat-dissipating sheet. Since the physical property control of the heat dissipation sheet can be easily performed, the same ones as described above are exemplified. The said monoacrylate phenolic antioxidant may be used independently and may be used in combination of 2 or more type.

Although the usage-amount of the said various antioxidants including a monoacrylate phenolic antioxidant is not specifically limited, For the purpose of giving the effect with a favorable mechanical physical property of the obtained heat-radiation sheet, it is 100 parts of (A) component. On the other hand, 0.01 part or more is preferable and 0.05 part or more is more preferable. Moreover, 5.0 parts or less are preferable, 3.0 parts or less are more preferable, and 2.0 parts or less are more preferable.

<Plasticizer>
You may mix | blend a plasticizer with the composition for thermal radiation sheets of this invention.
As a plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. Non-aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl and partial water And hydrocarbon oils such as terphenyl. These can be used alone or in admixture of two or more, but are not necessarily required. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.
The amount of the plasticizer used is preferably 5 to 800 parts with respect to 100 parts of the component (A) from the viewpoint of imparting elongation, workability, and preventing bleeding from the heat-radiating sheet.

<Solvent>
An organic solvent may be added to the heat radiating sheet composition of the present invention from the viewpoints of workability during coating, drying before and after curing, and the like.
As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 900 parts with respect to 100 parts of component (A) from the viewpoint of the balance of the finish of the heat dissipation sheet, workability, and drying.

<Adhesion improver>
In order to improve the adhesiveness to various supports (plastic film etc.), you may add various adhesive improvement agents to the composition for thermal radiation sheets of this invention.
Examples of adhesion improvers include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropyl methyl diisopropenoxy silane, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl methoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopro Le trimethoxysilane, .gamma.-mercaptopropyl alkoxysilanes having a functional group such as a methyl dimethoxy silane; silicone varnishes; polysiloxanes and the like.
From the viewpoint of the balance between the mechanical properties (elongation and strength) and the adhesiveness of the heat-dissipating sheet, the amount of the adhesive improver used is preferably 0.1 to 20 parts with respect to 100 parts of component (A).

<Preparation of composition for heat dissipation sheet>
The composition for a heat dissipation sheet of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed, and the initiator as a filler, a plasticizer, a solvent, and the like. It can also be prepared as a two-component type in which the mixed B liquid is mixed immediately before molding.

<< Heat dissipation sheet >>
The heat radiating sheet of the present invention is obtained by curing the composition for heat radiating sheet.
It does not specifically limit as a method of hardening the said composition for thermal radiation sheets.
(B) When using a photoinitiator as a component, it can be hardened by irradiating light or an electron beam with an active energy ray source.
Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example.
When a photopolymerization initiator is used as the component (B), the curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.

When a thermal polymerization initiator is used as the component (B), the curing temperature varies depending on the type of the thermal polymerization initiator used, the component (A), the other compound added, etc., but usually 50 ° C to 250 ° C. Preferably, 70 ° C to 200 ° C is more preferable.
When a redox initiator is used as the component (B), the curing temperature is preferably −50 ° C. to 250 ° C., more preferably 0 ° C. to 180 ° C.

<< Usage >>
There is no restriction | limiting in particular as a usage method of the composition for thermal radiation sheets of this invention. When used by molding into a fixed shape such as a sheet, film, molded product, gasket, etc. by various commonly used molding methods such as injection molding, extrusion molding, compression molding, liquid injection molding, coater, calendar, etc. It can be cured by applying and filling in an irregular shape like an adhesive, and then heating.
The heat-dissipating sheet composition of the present invention can form a heat conductive material that dissipates heat from electronic components such as a heater, a temperature sensor, a CPU, and a transistor, etc., to a cooling member. In addition, (A) component (meth) acryloyl group-containing vinyl polymer is used as the base resin, and it has excellent heat resistance, weather resistance, chemical resistance, water resistance, and electrical insulation, so it is used in harsh environments It can endure.

The composition for heat-dissipating sheets of the present invention, by blending a (meth) acryloyl group-containing vinyl polymer and a heat conductive filler, imparts excellent heat conductivity and durability and facilitates surface tackiness. Therefore, it is suitable for a heat conductive material used for a purpose such as a heat dissipation material in which adhesion is particularly important. Moreover, the composition for heat-radiation sheets of this invention can be shape | molded in a short time by heating, and is excellent also in productivity. Furthermore, by adding an organic carboxylic acid compound, it becomes excellent in releasability.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.
In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, from the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
In the following examples, “part” represents “part by weight”.

Production Example 1 (Synthesis of polyacrylic acid n-butyl acrylate at both ends)
Using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, diethyl-2,5-dibromoadipate as an initiator, and polymerizing n-butyl acrylate, a number average molecular weight of 22500 and a molecular weight distribution of 1.15 Bromine group poly (n-butyl acrylate) was obtained.
300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL), 8.3 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. Butyl) (hereinafter referred to as polymer [1]) was obtained. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, toluene was added to the residue, and insolubles were removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].
The purified polymer [1] had a number average molecular weight of 22,800, a molecular weight distribution of 1.15, and an average terminal acryloyl group number of 2.0.

Production Example 2 (Synthesis of n-butyl polyacrylate with one end of acryloyl group)
Polymerization of n-butyl acrylate using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and ethyl 2-bromobutyrate as an initiator. Poly (n-butyl acrylate) was obtained.
1050 g of this polymer was dissolved in N, N-dimethylacetamide (1050 g), 56.2 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. Butyl) (hereinafter referred to as polymer [2]) was obtained. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, toluene was added to the residue, and insolubles were removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [2].
The number average molecular weight of the purified acryloyl group single-ended polymer [2] is 3800, the molecular weight distribution is 1.15, and the average number of terminal acryloyl groups is 1.0 (that is, the introduction rate of acryloyl groups at the ends is almost 100%). Met.

Example 1
To 100 parts of the polymer [1] obtained in Production Example 1, 100 parts of TCP (tricresyl phosphate, manufactured by Daihachi Chemical Co., Ltd.), 400 parts of aluminum hydroxide (manufactured by Wako Pure Chemical Industries), Nyper BW (benzoyl peroxide, 1 part of Nippon Oil & Fats, 1 part of Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals), mixed well, further 3 The resulting roll was kneaded three times to obtain a heat radiating sheet composition.
The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 2 mm thick heat radiating sheet.

Example 2
To 100 parts of the polymer [1] obtained in Production Example 1, 100 parts of TCP (tricresyl phosphate, manufactured by Daihachi Chemical), 400 parts of boron nitride (manufactured by Wako Pure Chemical Industries), Nyper BW (benzoyl peroxide, Japan) 1 part of oil and fat) and 1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added, mixed thoroughly, and further kneaded by passing 3 times through 3 rolls to obtain a heat radiating sheet composition.
The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 2 mm thick heat radiating sheet.

Example 3
To 100 parts of the polymer [1] obtained in Production Example 1, 100 parts of the polymer [2] obtained in Production Example 2, 400 parts of aluminum hydroxide (manufactured by Wako Pure Chemical Industries), Nyper BW (benzoyl peroxide, Nippon Oil & Fats) 1 part, Irganox 1010 (Ciba Specialty Chemicals) 1 part, calcium stearate 0.5 part was added, mixed thoroughly, and further kneaded through 3 rolls 3 times to obtain a heat radiating sheet composition. .
The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 2 mm thick heat radiating sheet.

Comparative Example 1
100 parts of the polymer [1] obtained in Production Example 1 is 100 parts of TCP (tricresyl phosphate, manufactured by Daihachi Chemical), 1 part of Nyper BW (benzoyl peroxide, manufactured by Nippon Oil & Fats), Irganox 1010 (Ciba Specialty Chemicals) 1 part) was added and mixed well to obtain a heat radiating sheet composition.
The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 2 mm thick heat radiating sheet.

Using the heat-dissipating sheet composition and heat-dissipating sheet obtained in Examples 1 to 3 and Comparative Example 1, the thermal conductivity (heat dissipating characteristics), volume resistivity, hardness (DuroA), and releasability are as follows: And evaluated.
Further, Table 1 shows the blending amount (part) of each component in the composition and the measurement results.

<Thermal conductivity>
A 30 mL glass bottle was used, and all parts other than the mouth of the bottle were covered with a heat-dissipating sheet.
<Volume specific resistivity>
The volume specific resistivity of the heat radiating sheets obtained in Examples 1 to 3 and Comparative Example 1 was measured using ULTRA HIGH RESISTANCE NETTER R8340 + RESIST CHANBER R12702A (manufactured by Advantest) at an applied voltage of 500 V and 23 ° C. × 55% RH. did.

<Hardness>
The hardness (DuroA) of the heat dissipation sheet obtained in Examples 1 to 3 and Comparative Example 1 was measured using a DuroA hardness meter at 23 ° C. × 55% R.D. H. Measured with
<Releasability>
As releasability of the heat dissipation sheet obtained in Examples 1 to 3 and Comparative Example 1, the ease of sheet peeling from the mold for sheet production can be removed by hand, or a tool such as a scraper is required. Judgment was made and evaluated according to the following criteria.
A: Excellent (peeled off by hand), △ acceptable (can be removed using a scraper)

In Examples 1 to 3 to which thermally conductive fillers such as aluminum hydroxide and boron nitride were added, the volume resistivity was lower and the thermal conductivity was superior to that of Comparative Examples in which these were not added. Moreover, in Example 3 to which calcium stearate was added, the release properties of the heat-dissipating sheet were further better than those of other examples and comparative examples.

The composition for heat-dissipating sheets of the present invention provides excellent thermal conductivity and durability and easy surface tackiness by blending a (meth) acryloyl group-containing vinyl polymer and a thermally conductive filler. Therefore, it is suitable for a heat conductive material used for a purpose such as a heat dissipation material in which adhesion is particularly important. Moreover, the composition for heat-radiation sheets of this invention can be shape | molded in a short time by heating, and is excellent also in productivity. Furthermore, by adding an organic carboxylic acid compound, it becomes excellent in releasability.

Claims (33)

(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl-based polymer (B) initiator (C) having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular terminals. A composition for a heat radiation sheet containing a filler. The composition for a heat radiation sheet according to claim 1, wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer. (A) The vinyl-type monomer which comprises the principal chain of a component is an acrylate-type monomer, The composition for heat-radiation sheets in any one of Claims 1-2. The heat dissipation sheet according to any one of claims 1 to 3, wherein the vinyl monomer constituting the main chain of the component (A) contains at least one selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Composition. (A) ^Ra in General formula (1) of ^a component is a hydrogen atom or a C1-C20 hydrocarbon group, The composition for heat-radiation sheets in any one of Claims 1-4. The composition for a heat radiation sheet according to claim 5, wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group. The composition for heat radiating sheets according to any one of claims 1 to 6, which is used for a portion requiring heat resistance. The composition for heat radiating sheets according to any one of claims 1 to 7, which is used for a portion requiring oil resistance. The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The composition for thermal radiation sheets in any one of Claims 1-8 manufactured by making the compound shown by these react. A vinyl polymer having a halogen group at the end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The composition for heat dissipation sheets of Claim 9 which has group shown by these. The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The composition for thermal radiation sheets in any one of Claims 1-8 manufactured by making the compound shown by these react. The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The composition for thermal radiation sheets in any one of Claims 1-8 manufactured by making it react with the compound shown by these. The composition for heat-radiating sheets according to any one of claims 1 to 12, wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer. The composition for heat dissipation sheets according to claim 13, wherein the living radical polymerization is atom transfer radical polymerization. The composition for a heat dissipation sheet according to claim 14, wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron. The composition for heat dissipation sheets according to claim 15, wherein the transition metal complex is a copper complex. The composition for heat-radiating sheets according to any one of claims 1 to 12, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The number average molecular weight of the said (A) component is 3000 or more, The composition for heat dissipation sheets in any one of Claims 1-17. The heat dissipation according to any one of claims 1 to 18, wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. Sheet composition. The composition for heat dissipation sheets according to any one of claims 1 to 19, comprising a monomer and / or an oligomer having a radical polymerizable group. The composition for heat dissipation sheets according to any one of claims 1 to 20, comprising a monomer and / or an oligomer having an anionically polymerizable group. The composition for heat dissipation sheets according to any one of claims 20 to 21, comprising a monomer and / or an oligomer having a (meth) acryloyl group. The composition for heat-radiating sheets according to claim 22, further comprising a monomer and / or an oligomer having a (meth) acryloyl group and further having a number average molecular weight of 5000 or less. (B) The initiator of a component is a photoinitiator and / or a thermal-polymerization initiator, The composition for heat-radiation sheets in any one of Claims 1-23. (B) The initiator of a component is a redox type initiator, The composition for heat-radiation sheets in any one of Claims 1-23. The component (C) is at least one selected from metal oxides, metal nitrides, metal carbides, metal hydroxides, crystalline silica, organic polymer fired products, and nitrogen carbides. The composition for heat dissipation sheets of description. 27. The heat radiating sheet composition according to claim 26, wherein the component (C) is at least one selected from aluminum oxide, boron nitride, aluminum nitride, and aluminum hydroxide. The volume ratio of the heat conductive filler which is (C) component is 25 volume% or more in all the compositions, The composition for heat-radiation sheets in any one of Claims 1-27. The composition for heat dissipation sheets according to any one of claims 1 to 28, further comprising (D) an organic carboxylic acid compound in addition to the components (A), (B), and (C). 30. The composition for a heat dissipation sheet according to claim 29, wherein the component (D) is a stearic acid compound. The composition for a heat radiation sheet according to claim 30, wherein the component (D) is a metal stearate. 32. The composition for a heat radiation sheet according to claim 31, wherein the component (D) is at least one selected from lead stearate, zinc stearate, and calcium stearate. A heat radiating sheet obtained by curing the composition for a heat radiating sheet according to claim 1.