JP2009179743A - Composition for heat-dissipation sheet and heat-dissipation sheet produced by curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a heat-dissipation sheet, capable of imparting excellent flame-retardancy, durability and heat-conductivity, having low volatile content, enabling easy control of surface tackiness and producible in high productivity, and to provide a heat-dissipation sheet produced by curing the composition. <P>SOLUTION: The composition for the heat-dissipation sheet contains the following components (A) to (D): (A) a vinyl polymer having two or more groups expressed by 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 a 1-20C organic group) in one molecule, provided that one or more groups expressed by general formula (1) is present on a molecular terminal; (B) an initiator; (C) a heat-conductive filler; and (D) a condensed aromatic phosphoric acid ester expressed by general formula (15) (in the formula, R<SP>19</SP>to R<SP>22</SP>are each a univalent aromatic group or aliphatic group; R<SP>23</SP>is a bivalent aromatic group; and n is 1-16; n R<SP>21</SP>and R<SP>23</SP>groups may be different from each other). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame retardant heat-dissipating sheet composition and a heat-dissipating sheet obtained by curing the composition. More specifically, a composition for a flame-retardant heat-dissipating sheet with a small amount of volatile components, comprising a vinyl polymer having a (meth) acryloyl group, an initiator, a thermally conductive filler, and a condensed aromatic phosphate. And, it relates to a flame retardant heat dissipation sheet obtained by curing it.

  Conventionally, a heat conductive material having rubber elasticity is widely used as a heat dissipation / heat transfer spacer for semiconductors such as transistors, diodes and ICs, as well as various heaters, temperature sensors and other electronic components. 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, a sheet using silicone as a base resin has a limited range of application because of problems such as generation of a low molecular weight siloxane component that causes contact failure during use.

  In addition, in heat conductive materials, high heat conductive filler is usually filled to increase heat conductivity. However, the higher the filler is filled, the more the elasticity of the material itself is lost and the surface stickiness tends to decrease. 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 inferior. 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.

In order to solve these problems, a heat dissipation sheet based on a non-silicone resin is prepared by adding a large amount of plasticizer to a mixture of an acrylic oligomer such as acrylic rubber and a thermally conductive filler and solidifying the mixture. Thus, a technique for obtaining a soft heat radiation sheet in which a resin other than silicone is used as a base resin is disclosed. However, since the sheet prepared by such a method contains a large amount of a plasticizer and a low molecular weight acrylic oligomer component, an organic volatile component is generated at the time of use at a high temperature. There is a problem that there is a possibility of contaminating the equipment. Even in Patent Documents 7 and 8, which are characterized by a small amount of volatile components, a large amount of weight even under relatively mild conditions, such as a weight loss of 3% or less at 10 minutes at 100 ° C. or 10% or less at 168 hours at 130 ° C. Since the reduction occurs, components such as plasticizers and oligomers volatilize and fly once processed at a high temperature, so there is a fatal problem that the sheet becomes hard after heat treatment, which is a practical problem. Yes. Patent Documents 9 and 10 succeeded in obtaining a flexible heat-dissipating sheet by polymerizing and using an acrylic oligomer with a controlled molecular weight using an innovative polymerization method called living radical polymerization. There is no practical problem with volatile components because the flame retardant used to impart flame retardancy is volatile, plasticizer is used to supplement flexibility, or silicone resin is used as a curing agent. It cannot be reduced to the range.
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 JP 2001-310974 A Japanese Patent Laid-Open No. 2003-249609 JP-A-2005-48124 JP 2006-278476 A JP 2006-312708 A

  An object of the present invention is to impart excellent flame retardancy, durability, and thermal conductivity, and have a low productivity of volatile components and high productivity, and a heat dissipation obtained by curing the composition. Is to provide a sheet.

  The inventors of the present invention can solve the above problems by using a composition for a heat-dissipating sheet containing a vinyl polymer having a (meth) acryloyl group, an initiator, a thermally conductive filler, and a condensed aromatic phosphate ester. The headline and the present invention were completed.

That is, the present invention relates to the following heat radiating sheet composition and heat radiating 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 polymer having an average of one or more groups represented by the formula (1) and 0.8 or more of the groups represented by the general formula (1) at the molecular terminals, (B) an initiator, A composition for a heat dissipation sheet, comprising (C) a thermally conductive filler and (D) a condensed aromatic phosphate represented by the following general formula (15).

Wherein R ^{19 to} R ²² are monovalent aromatic groups or aliphatic groups, R ²³ is a divalent aromatic group, n is 1 to 16, and n R ²¹ and R ²³ are different from each other. May be)
2) The component (A) is
(A-1) a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule, and
(A-2) a vinyl polymer having a group represented by the general formula (1) at one end of the molecule;
1) The composition for heat-radiating sheets as described in 1) above.
3) The component (A) is
(A-1) 99 to 1% by weight of a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule;
(A-2) 1 to 99% by weight of a vinyl polymer having a group represented by the general formula (1) at one end of the molecule, and
(A-3) 0 to 20% by weight of a vinyl polymer having no group represented by the general formula (1) in the molecule,
(However, the total of (A-1), (A-2), and (A-3) is 100% by weight)
The composition for heat radiating sheets according to any one of 1) to 2), which comprises:
4) The component (A) is
(A-1) 50 to 10% by weight of a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule;
(A-2) 5 to 90% by weight of a vinyl polymer having a group represented by the general formula (1) at one end of the molecule, and
(A-3) 0 to 20% by weight of a vinyl polymer having no group represented by the general formula (1) in the molecule,
(However, the total of (A-1), (A-2), and (A-3) is 100% by weight)
The composition for heat radiating sheets according to any one of 1) to 3), comprising:
5) It relates to the composition for thermal radiation sheets in any one of 1) -4) whose vinyl monomer which comprises the principal chain of (A) component is a (meth) acrylic monomer.
6) The composition for a heat radiation sheet according to any one of 1) to 5), wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer.
7) 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 for heat dissipation sheet.
8) The composition for a heat radiation sheet according to any one of 1) to 7), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group.
9) The composition for a heat dissipation sheet according to any one of 1) to 8), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
10) The composition for a heat radiation sheet according to 9), wherein the living radical polymerization is atom transfer radical polymerization.
11) The composition for thermal radiation sheets in any one of 1) -10) whose number average molecular weights of the said (A) component are 3000 or more.
12) The vinyl polymer as the component (A) is any one of 1) to 11) in which the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. A composition for a heat dissipation sheet.
13) The component (C) is a carbon compound, metal oxide, metal nitride, metal carbide, metal hydroxide, metal carbonate, crystalline silica, organic polymer fired product, nitrogen carbide, composite ferrite with Zn ferrite, The composition for heat-radiating sheets according to any one of 1) to 12), which is at least one selected from Fe-Al-Si ternary alloys and metal powders.
14) The component (C) is at least one selected from graphite, diamond, aluminum oxide, boron nitride, aluminum nitride, aluminum hydroxide, and Fe—Al—Si ternary alloy 1) to 13) The composition for heat dissipation sheets in any one.
15) The composition for a heat radiation sheet according to any one of 1) to 14), wherein the volume ratio of the component (C) is 25% by volume or more in the entire composition.
16) The composition for a heat-dissipating sheet according to any one of 1) to 15), wherein the (D) condensed aromatic phosphate is liquid at 23 ° C.
17) A heat radiation sheet obtained by curing the composition for heat radiation sheet according to any one of 1) to 16).
18)
The heat dissipation sheet according to 17), wherein the durometer hardness type E is less than 55.
19)
The heat-dissipating sheet according to 18), which has V-0 flame retardancy in a UL94 combustion test and has a weight loss of 0.1% or less after treatment at 150 ° C for 1 hour.

  The composition for heat-dissipating sheets of the present invention has excellent thermal conductivity and flame retardancy by blending a (meth) acryloyl group-containing vinyl polymer and a thermally conductive filler. Moreover, since there are few volatile components and surface adhesiveness can be controlled easily, it is suitable for the heat radiating material in which adhesion is particularly important. In addition, the composition for a heat-dissipating sheet of the present invention can be molded in a short time by heating, is excellent in productivity, and has good flame retardancy, so it is suitable for use in electric and electronic devices. .

Below, the composition for heat-radiation sheets of this invention is demonstrated in detail.
The composition for heat-radiation sheets of this invention is a composition formed by containing the following (A), (B), (C), (D) component. (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 having 2 or more groups per molecule and one or more groups represented by the general formula (1) at the molecular end, (B) initiator, (C) heat Conductive filler, (D) a condensed aromatic phosphate represented by the following general formula (15).

Wherein R ^{19 to} R ²² are monovalent aromatic groups or aliphatic groups, R ²³ is a divalent aromatic group, n is 1 to 16, and n R ²¹ and R ²³ are different from each other. May be)
<< (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 two or more groups represented by general formula (1) and one 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 1 or more on average per molecule, and 0.8 on average at the molecular terminals. That's it. Further, the average number of (meth) acryloyl groups at the molecular terminals is preferably 1 or more per molecule. Since the side reaction may actually occur when the component (A) is produced, the average number of the (meth) acryloyl groups in the produced vinyl polymer mixture is 1 on average. May be less than one. In the present invention, when the average value of the number of (meth) acryloyl groups in the actually produced vinyl polymer mixture is 0.8 or more, this mixture is referred to as component (A). That is, as the component (A), a vinyl polymer containing a vinyl polymer having an average of 1 or more (meth) acryloyl groups per molecule and an average of 0.8 or more at the molecular terminals per molecule is used. It contains a mixture. Further, from the viewpoint of crosslinking, the average value of the number of the (meth) acryloyl group is preferably 1.0 or more, more preferably 1.1 or more per molecule. The upper limit is preferably 2.0 or less per molecule from the viewpoint of flexibility when formed into a sheet. Even if the number of (meth) acryloyl groups exceeds 2.0 on average, a flexible sheet can be obtained if a large amount of plasticizer is added, but bleed-out may occur during heating. Further, on average, 0.8 or more of the (meth) acryloyl groups are present at the molecular terminals, but the positions of other (meth) acryloyl groups are not particularly limited. From the viewpoint that the distance between cross-linking points can be increased, a form in which both are close to the molecular end is preferable, and a form in which both are close to the molecular end is particularly preferable.

  Furthermore, from the point that the distance between the crosslinking points can be increased and a flexible sheet can be easily obtained, the component (A) is a group represented by the general formula (1) at both ends of the molecule (A-1). It is preferable to contain the vinyl polymer which has and (A-2) the vinyl polymer which has the group represented by the said General formula (1) in the one terminal of a molecule | numerator. The weight ratio of (A-1) to (A-2) is preferably 99/1 to 1/99, more preferably 95/5 to 5/95, and still more preferably 90/10 to 10/90. .

  In fact, since side reactions may occur when the component (A) is produced, the produced vinyl polymer mixture may contain a small amount of resin having no (meth) acryloyl group. is there. The component (A) is (A-1) 99 to 1% by weight of a vinyl polymer having groups represented by the general formula (1) at both ends of the molecule, and (A-2) the molecule at one end of the molecule. 1 to 99% by weight of a vinyl polymer having a group represented by the general formula (1), and (A-3) a vinyl polymer 0 to 0 having no group represented by the general formula (1) in the molecule. It may be 20% by weight (provided that the total of (A-1), (A-2), and (A-3) is 100% by weight).

  Further, the component (A) is a vinyl polymer having groups represented by the general formula (1) at both ends of the molecule (A-1) (50) by weight, and (A-2) one end of the molecule. 5 to 90% by weight of a vinyl polymer having a group represented by the general formula (1), and (A-3) a vinyl polymer having no group represented by the general formula (1) in the molecule. A content of 0 to 20% by weight (provided that the total of (A-1), (A-2), and (A-3) is 100% by weight) is preferable because a more flexible heat dissipation sheet can be obtained.

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 the component (A) [the ratio of the weight average molecular weight (Mw) and the 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)> The production method of the component (A) is not particularly limited. 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 production method of 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 "(Atom Transfer Radical Polymerization: ATRP) and the like.

  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 features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the 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 the polymerization temperature condition 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-butylperoxyoctate, 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, and 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 what is shown by the C1-C20 bivalent organic group which may contain the 1 or more ether bond, X is a chlorine atom, a bromine atom, or an iodine atom) 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) nCH = 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) mCH = 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 , 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. If R9 is not a direct bond, - for activating the carbon-halogen ^bond as ^{R 10} is C (O) O group, C (O) group, a phenylene group is preferred.

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)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X are the same as above, R ¹¹ , 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).
And 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, Y When two or more are present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, and m is an integer of 0 to 19, provided that A + mb ≧ 1)
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 (OCH3) 3,
o, m, p-CH3CH2C ( H) (X) -C6H4- (CH2) 3 Si (OCH 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 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 production method of the component (A) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the above-described method, and the reactive functional group is a (meth) acryloyl type. It can manufacture by converting into the substituent which has group. 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 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] Introduction method 1 is a method of reacting a vinyl polymer having a halogen group at a terminal with 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 (4), 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 ions include lithium ions, sodium ions, and potassium ions. 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] Introduction method 2 is a method in which a vinyl polymer having a hydroxyl group at the terminal is reacted with a compound represented by 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 methods are 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 both a polymerizable alkenyl group and a 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 C 1-20 divalent organic group optionally having 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). ), - NO2 (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 >} -OM ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as described above) and the like, and the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
A method of reacting a hydroxyl group-containing compound represented by the formula (wherein R ¹⁶ and M ⁺ are the same as above) to substitute the halogen atom with a hydroxyl group-containing substituent.

  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 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 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 preferred. 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 >> The initiator of the (B) component is not particularly limited, and examples thereof include a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator. 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, benzoy Methyl 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. Among 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. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, 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) (VAZO33), 2,2′-azobis (2-amidino). Propane) dihydrochloride (VAZO50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO52), 2,2'-azobis (isobutyronitrile) (VAZO64), 2,2'-azobis 2-methylbutyronitrile (VAZO67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO88) (all available from DuPont Chemical), 2,2'-azobis (2-cyclopropylpropionitrile), And 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries). That.

  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 AkzoNobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from ElfAtochem), t-butyl peroxy-2- Examples include ethyl hexanoate (Trigonox 21-C50) (available from AkzoNobel), 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 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.

  << (C) Component >> As the heat conductive filler of the component (C), a commercially available general heat conductive filler can be used. Among them, from the viewpoint of thermal conductivity, availability, etc., carbon compounds such as graphite and diamond; acrylonitrile-based polymer fired products, furan resin fired products, cresol resin fired products, polyvinyl chloride fired products, sugar fired products Fired organic polymer such as fired charcoal; Metal oxide such as aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, zinc oxide; Metal nitride such as boron nitride, aluminum nitride, silicon nitride; Metal carbides such as boron, aluminum carbide and silicon carbide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as magnesium carbonate; crystalline silica; nitrogen carbide; composite ferrite with Zn ferrite; Preferable examples include Al-Si ternary alloys; metal powders, and the like. Furthermore, from the viewpoints of availability and thermal conductivity, graphite, aluminum oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, crystalline silica, Mn—Zn soft ferrite, Ni—Zn soft ferrite, Fe— Al-Si ternary alloy (Sendust), pure iron (purity of 95% or more), and iron-nickel alloy (Permalloy) are more preferable. Aluminum oxide, boron nitride, aluminum nitride, aluminum hydroxide, Mn-Zn soft Ferrite, Fe—Al—Si ternary alloy (Sendust), and pure iron (having a purity of 95% or more) are particularly preferable.

  (C) The shape of a heat conductive filler is not specifically limited, The thing of desired shapes, such as spherical shape, plate shape, fiber shape, and an indefinite shape, can be used. However, when it is desired to impart flexibility such as low hardness to the heat-dissipating sheet obtained from the composition for heat-dissipating sheet of the present invention, it is preferable to use a filler having a shape close to a sphere. The particle size of the (C) heat conductive filler is not particularly limited, but is preferably about 0.1 to 500 μm from the viewpoint of compatibility with the component (A), reinforcing properties, heat conduction performance, and the like.

  In addition, (C) a thermally conductive filler is a silane coupling agent (vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, chlorosilane, amino silane, etc.) because of its improved dispersibility with respect to component (A). Or 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, elaidin 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, parastolic acid, dehydroapietic acid, isopimaric acid, sandaracopi Maric acid, komuric acid, secodehydroabietic Acid, the dihydroabietic acid, etc.) or the like, it is preferable that the surface has been treated.

  (C) As a usage-amount of a heat conductive filler, since the heat conductivity of the heat radiation sheet material obtained from the composition for heat radiation sheets of this invention can be made high, the volume ratio (%) of the whole filler. 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 filler used is more preferably 30% by volume or more in the entire composition, and most preferably 35% by volume or more in the entire composition.

Here, the volume fraction (%) of the filler is calculated from the weight fraction and specific gravity of the resin component and the filler, and is obtained by the following equation. In the following formula, the thermally 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 filler. Specifically, among the components (A) to (B) and other components, organic components excluding inorganic compounds and other various organic additives Refers to an agent.

  Further, as one method for increasing the filling rate of the filler with respect to the component (A), it is preferable to use two or more kinds of fillers having different particle diameters in combination. In this case, it is preferable that the filler having a large particle diameter exceeds 10 μm, and the filler having a small particle diameter is 10 μm or less. Moreover, these fillers can use not only the same kind of filler but also two or more kinds of different kinds in combination.

  << (D) Component >> As the condensed aromatic phosphate ester of the (D) component, the following general formula (15):

Wherein R ^{19 to} R ²² are monovalent aromatic groups or aliphatic groups, R ²³ is a divalent aromatic group, n is 1 to 16, and n R ²¹ and R ²³ are different from each other. May be)
The condensed phosphoric acid ester represented by these is used. Among these condensed phosphates, a compound that is liquid at 23 ° C. is preferable because it is excellent in flexibility when processed into a sheet at room temperature.

  (D) As a specific example of the condensed aromatic phosphate ester,

(In the formula, n represents 1 to 16)
Etc. These organophosphorous flame retardants are used alone or in combination of two or more. More preferable compounds include resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, hydroquinone bis (di-2,6-xylyl) phosphate, and condensates thereof. It is done.

  (D) In order to increase the flame retardancy, the higher the phosphorus content, the more preferable the condensed aromatic phosphate ester. Specifically, flame retardancy can be enhanced by using a compound having a phosphorus content exceeding 8 wt%.

  (D) As for the addition amount of condensation type aromatic phosphate ester, it is preferable that the volume ratio (%) of (D) condensation type aromatic phosphate ester will be 0.1 volume%-80 volume% in a whole composition. If the amount is less than 0.1% by volume, the flame retardancy tends to be insufficient, and if it exceeds 80% by volume, a heat dissipation sheet may not be obtained. A more preferable volume ratio is 1 volume% to 60 volume%, a further preferable volume ratio is 2 volume% to 50 volume%, and a most preferable volume ratio is 5 volume% to 40 volume%.

  << Composition for heat-dissipating sheet >> The composition for heat-dissipating sheet of the present invention is preferably used in a site requiring oil resistance and heat resistance. The composition for heat dissipation sheets of the present invention is a composition comprising the components (A), (B), (C), and (D) as described above. Moreover, other components can be contained as needed. Furthermore, a polymerizable monomer and / or oligomer 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 heat dissipation sheets of this invention as needed.

  <Polymerizable monomer and / or oligomer> As the polymerizable monomer and / or oligomer, the monomer and / or oligomer having a radical polymerizable group, or the monomer having an anion polymerizable group and / or Oligomers are preferred 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, and vinyl butyrate. Examples of the acrylamide monomer 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 trimethylol propane triacrylate, neopentyl glycol polypropoxy diacrylate, trimethylol propane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, bisphenol A polyethoxy diacrylate, 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.

  Examples of oligomers include bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolak type epoxy acrylate resins, and COOH group-modified epoxy acrylate type resins; polyols (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.

  Of 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.

  <Other fillers> In addition to the component (C), various fillers may be used as necessary in the composition for a heat radiation sheet of the present invention. The filler is not particularly limited, but fumed silica, precipitated silica, wood powder, pulp, cotton chips, asbestos, glass fiber, mica, walnut shell powder, rice husk powder, diatomaceous earth, white clay, dolomite, anhydrous Reinforcing fillers such as silicic acid, hydrous silicic acid, carbon black; heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara, Examples thereof include fillers such as fine aluminum powder, flint powder, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; and fibrous fillers such as asbestos, glass fibers and glass filaments, Kevlar fibers and polyethylene fibers. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. Moreover, when it is desired to obtain a heat dissipation sheet having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, shirasu balloon, and the like can be added. These fillers are more preferably surface-treated using a surface treatment agent. As the surface treatment agent, 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 are used. A filler may be used independently and may be used together 2 or more types.

  <Releasability-imparting agent> The heat-dissipating sheet composition of the present invention may contain an organic carboxylic acid compound as necessary for the purpose of imparting releasability. 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.

  The use amount of the other components is preferably 0.025 to 5 parts by weight, more preferably 0.05 to 4 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of releasability and sheet physical property balance. It is.

  <Adhesion-imparting resin> The composition for a heat-dissipating sheet of the present invention is preferably composed mainly of a (meth) acrylic polymer, so that it is not always necessary to add an adhesion-imparting resin. Depending on the type, various types 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 a heat radiation sheet of the present invention in order to adjust physical properties. The acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not always necessary, but a conventionally known antioxidant and light stabilizer may be appropriately used. it can. Further, 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) published 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 ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by ADEKA CORPORATION); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals) And phosphorous antioxidants such as hindered phenolic compounds. 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-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-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 product 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 Manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO- 80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, ADK STAB AO-37 (all manufactured by ADK), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, RGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumilizer GA-80 (The above are all manufactured by Sumitomo Chemical Co., Ltd.), but are not limited thereto.

  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, in order to improve the heat resistance and weather resistance of the obtained heat radiating sheet, an anti-aging agent may be added, 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 dissipation 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> A plasticizer may be blended in the composition for heat dissipation sheet of the present 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; partial water Examples thereof include 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 component (A) from the viewpoint of imparting elongation and workability. Particularly in the composition of the present invention, since (D) the condensed aromatic phosphate ester also has a role as a plasticizer, the amount of other plasticizers added is small from the viewpoint of preventing bleeding from the heat-radiating sheet. The more preferable. Further, the preferred amount of plasticizer is 100 parts or less, and the most preferred amount of plasticizer is 20 parts or less.

  <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 finish of the heat radiation sheet, workability, and the balance of drying. Furthermore, the usage-amount of a preferable solvent is 1-100 parts, and the usage-amount of the most preferable solvent is 1-20 parts.

  <Adhesion improver> In order to improve the adhesiveness to various supports (plastic film, etc.), various adhesive improvers may be added to the composition for heat dissipation sheet of the present invention. Examples of the adhesion improver include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy 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-dissipating sheet> The composition for heat-dissipating sheet of the present invention can be prepared as a one-pack type in which all the ingredients are pre-blended and sealed. It can also be prepared as a two-component type in which the B liquid mixed with a filler, a plasticizer, a solvent and the like is mixed immediately before molding.

  << Heat Dissipation Sheet >> The heat dissipation sheet of the present invention is obtained by curing the composition for heat dissipation sheet. The method for curing the heat radiating sheet composition is not particularly limited. (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 is 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.

  The hardness of the heat-dissipating sheet is preferably less than 55 in durometer hardness type E measured according to JIS K-6253, because the sheet has high flexibility and excellent adhesion to the heating element. The value of durometer hardness type E is preferably less than 52, more preferably less than 50.

  << Use >> There is no particular limitation on the method of using the composition for a heat dissipation sheet of the present invention. When molding and forming 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 composition for a heat-dissipating sheet of the present invention can form a heat conductive material that dissipates heat from electronic components such as a heater, temperature sensor, CPU, transistor, and the like to a cooling member. In addition, when a (meth) acryloyl group-containing vinyl polymer is used as the base resin as the component (A), it has excellent heat resistance, weather resistance, chemical resistance, water resistance, and electrical insulation. It can endure.

  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 filled with polystyrene cross-linked gel (shodexGPCK-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”, and 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)
Polymerization of n-butyl acrylate using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and diethyl-2,5-dibromoadipate as an initiator, and a terminal having 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, ethyl 2-bromobutyrate as an initiator, and a one-terminal bromine group having a number average molecular weight of 11800 and a molecular weight distribution of 1.08 Poly (n-butyl acrylate) was obtained. 1050 g of this polymer was dissolved in N, N-dimethylacetamide (1050 g), 19.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere, and acryloyl group single-ended poly (acrylic acid n— 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 terminal polymer [2] was 11900, the molecular weight distribution was 1.09, and the average terminal acryloyl group number was 0.90.

Production Example 3 (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, and a one-terminal bromine group having a number average molecular weight of 3700 and a molecular weight distribution of 1.14 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 [3]) 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 [3]. The number average molecular weight of the purified acryloyl group single terminal polymer [3] is 3800, the molecular weight distribution is 1.15, and the average terminal acryloyl group number is 1.0 (that is, the introduction rate of acryloyl group at the terminal is almost 100%). Met.

Example 1
100 parts of the polymer [1] obtained in Production Example 1, 1700 parts of AS-40 (spherical alumina, manufactured by Showa Denko), 1 part of Nyper BW (benzoyl peroxide, manufactured by Nippon Oil & Fats), CR-733S (resorcinol bisdiphenyl) 250 parts of phosphate (manufactured by Daihachi Chemical), 1 part of Adekastab AO-60 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], made by Adeka), and enough And kneaded by passing three times through three rolls to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Example 2
50 parts of the polymer [1] obtained in Production Example 1, 50 parts of the polymer [2] obtained in Production Example 2, 1400 parts of AS-40 (spherical alumina, manufactured by Showa Denko), Nyper BW (benzoyl peroxide) , Manufactured by NOF Corporation), 1 part, CR-733S (resorcinol bisdiphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd.), 200 parts, Adekastab AO-60 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionate] and 1 part of Adeka) were added, mixed thoroughly, and further kneaded by passing three times through three rolls to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Example 3
40 parts of the polymer [1] obtained in Production Example 1, 60 parts of the polymer [3] obtained in Production Example 3, 1150 parts of AS-40 (spherical alumina, manufactured by Showa Denko), Nyper BW (benzoyl peroxide) , Manufactured by Nippon Oil & Fats Co., Ltd. 1 part, CR-733S (resorcinol bisdiphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd.) 130 parts, Adekastab AO-60 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionate] and 1 part of Adeka) were added, mixed thoroughly, and further kneaded by passing three times through three rolls to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Example 4
50 parts of the polymer [1] obtained in Production Example 1, 50 parts of the polymer [2] obtained in Production Example 2, 350 parts of PTX-60 (spheroidized boron nitride, manufactured by Momentive Performance Materials), Perbutyl I (T-butylperoxyisopropyl monocarbonate, manufactured by NOF Corporation) 1 part, CR-733S (resorcinol bisdiphenyl phosphate, manufactured by Daihachi Chemical) 200 parts, ADK STAB AO-60 (pentaerythritol tetrakis [3- (3,5- 1 part of di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Adeka) was added, mixed well, and further kneaded by passing three times through three rolls to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Example 5
50 parts of the polymer [1] obtained in Production Example 1, 50 parts of the polymer [2] obtained in Production Example 2, 70 parts of CGC-100 (spheroidized graphite, manufactured by Nippon Graphite Industries), BSF-547 ( 650 parts of Mn-Zn soft ferrite (manufactured by Toda Kogyo), 85 parts of CR-733S (resorcinol bisdiphenyl phosphate, manufactured by Daihachi Chemical), 1 part of perbutyl I (t-butyl peroxyisopropyl monocarbonate, manufactured by NOF Corporation), 1 part of Adeka Stub AO-60 (manufactured by Adeka) was added, mixed well, and further passed through 3 rolls 3 times and kneaded to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 180 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Example 6
25 parts of the polymer [1] obtained in Production Example 1, 75 parts of the polymer [2] obtained in Production Example 2, 500 parts of AS-50 (spherical alumina, Showa Denko), BF013 (aluminum hydroxide, Nippon Light Metal) 150 parts, Niper BW (benzoyl peroxide, manufactured by Nippon Oil & Fats) 1 part, CR-741 (bisphenol A bisdiphenyl phosphate, manufactured by Daihachi Chemical) 40 parts, Adeka Stub AO-60 (manufactured by Adeka) 1 part In addition, the mixture was sufficiently mixed and further passed through three rolls three times to knead to obtain a heat radiating sheet composition. The heat radiating sheet composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick heat radiating sheet.

Comparative Example 1
50 parts of the polymer [1] obtained in Production Example 1, 50 parts of the polymer [2] obtained in Production Example 2, 1 part of Nyper BW (benzoyl peroxide, manufactured by NOF Corporation), CR-733S (resorcinol bis 125 parts of diphenyl phosphate (manufactured by Daihachi Chemical Co., Ltd.) and 1 part of Adeka Stub AO-60 (manufactured by Adeka) were added, mixed well and kneaded to obtain a comparative composition. The composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick sheet.

Comparative Example 2
100 parts of the polymer [1] obtained in Production Example 1, 580 parts of AS-40 (spherical alumina, manufactured by Showa Denko), 1 part of Niper BW (benzoyl peroxide, manufactured by Nippon Oil & Fats), Adeka Stub AO-60 (manufactured by Adeka) ) 1 part was added, mixed thoroughly, and further kneaded by passing 3 times through 3 rolls to obtain a comparative composition. The composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick sheet.

Comparative Example 3
25 parts of the polymer [1] obtained in Production Example 1, 75 parts of the polymer [2] obtained in Production Example 2, 600 parts of AS-40 (spherical alumina, manufactured by Showa Denko), Nyper BW (benzoyl peroxide) And 1 part of Adeka Stub AO-60 (manufactured by Adeka) were added, mixed well, and further kneaded by passing 3 rolls 3 times to obtain a comparative composition. The composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick sheet.

Comparative Example 4
50 parts of the polymer [1] obtained in Production Example 1, 50 parts of the polymer [2] obtained in Production Example 2, 1400 parts of AS-40 (spherical alumina, manufactured by Showa Denko), Nyper BW (benzoyl peroxide) , Nippon Oil & Fats) 1 part, TCP (tricresyl phosphate, manufactured by Daihachi Chemical) 200 parts, Adeka Stub AO-60 (manufactured by Adeka) 1 part, mixed thoroughly, and further kneaded 3 times through 3 rolls A comparative composition was obtained. The composition was pressed at 150 ° C. for 15 minutes to obtain a 1 mm thick sheet.

Comparative Example 5
Toacron AR860 (manufactured by Toupe), which is an acrylic rubber, 100 parts, AS-40 (spherical alumina, manufactured by Showa Denko) 1400 parts, CR-733S (resorcinol bisdiphenyl phosphate, manufactured by Daihachi Chemical) 200 parts, ADK STAB AO-60 (ADEKA) 1 part), 1 part of Disnet F (vulcanized, Sankyo Kasei Co., Ltd.), 1 part of Noxeller BZ (vulcanization accelerator, manufactured by Ouchi Shinsei Chemical), mixed well, and further into 3 rolls A comparative composition was obtained by kneading three times. The composition was pressed at 180 ° C. for 15 minutes to obtain a 1 mm thick sheet.

Comparative Example 6
Actflow CB-3098 (COOH group-containing acrylic copolymer, manufactured by Soken Chemical), which is an acrylic copolymer, 100 parts, AS-40 (spherical alumina, manufactured by Showa Denko), 1400 parts, CR-733S (resorcinol) Bisdiphenyl phosphate (manufactured by Daihachi Chemical) 200 parts, Adeka Stub AO-60 (manufactured by Adeka) 1 part, SR-MK3 (glycidyl curing agent, Sakamoto Pharmaceutical Co., Ltd.) 23 parts, Curesol 2E4MEZ (2-ethyl-4-methylimidazole) 1 part of a system catalyst, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added, mixed thoroughly, and further kneaded by passing three times through three rolls to obtain a comparative composition. The composition was pressed at 180 ° C. for 15 minutes to obtain a 1 mm thick sheet.

  Using the heat-dissipating sheet compositions and heat-dissipating sheets obtained in Examples and Comparative Examples, the thermal conductivity, heat loss, surface resistance, hardness (DuroE), heat-treated hardness, and flame retardancy 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>
Using a hot disk method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Co., Ltd.), thermal conductivity was measured by sandwiching a 4φ size sensor between two disk-shaped samples having a thickness of 3 mm and a diameter of 20 mm. .

<Heating loss>
Using a thermogravimetric measuring device TGA-50 (manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 150 ° C. at 5 ° C./min in a nitrogen atmosphere, then held at 150 ° C. for 1 hour, and weight loss at 150 ° C. The rate was measured.

<Surface resistance value>
According to JIS K7194, the surface resistance value was measured by an applied voltage = 250 V and 23 ° C. × 50% RH by a four-terminal method.

<Hardness>
According to JIS K-6253, durometer hardness type E was measured at 23 ° C. × 50% RH using an Asker rubber hardness meter E type.

<Hardness after heat treatment>
After the obtained sheet was treated at 120 ° C. for 60 hours, in accordance with JIS K-6253, durometer hardness type E was measured at 23 ° C. × 50% RH using an Asker rubber hardness meter E type.

<Flame retardance>
The flame retardancy of a sheet having a thickness of 1 mm was evaluated according to UL94 V standard.

  In the examples, compositions and sheets having excellent thermal conductivity and flame retardancy and low heat loss are obtained.

  The composition for a heat dissipation sheet of the present invention is excellent in flame retardancy, durability, by blending a (meth) acryloyl group-containing vinyl polymer, a thermally conductive filler, and a condensed aromatic phosphate. Thermal conductivity can be imparted. Moreover, since there are few volatile components and surface adhesiveness can be controlled easily, it is suitable for the heat dissipation material etc. from which adhesiveness is especially 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.

Claims (19)

(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 having an average of one or more groups represented by the formula (1) and 0.8 or more of the groups represented by the general formula (1) at the molecular terminals, (B) an initiator, A composition for a heat dissipation sheet, comprising (C) a thermally conductive filler and (D) a condensed aromatic phosphate represented by the following general formula (15).

Wherein R ^{19 to} R ²² are monovalent aromatic groups or aliphatic groups, R ²³ is a divalent aromatic group, n is 1 to 16, and n R ²¹ and R ²³ are different from each other. May be) The component (A) is
(A-1) a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule, and
(A-2) a vinyl polymer having a group represented by the general formula (1) at one end of the molecule;
The composition for heat-radiating sheets according to claim 1, comprising: The component (A) is
(A-1) 99 to 1% by weight of a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule;
(A-2) 1 to 99% by weight of a vinyl polymer having a group represented by the general formula (1) at one end of the molecule, and
(A-3) 0 to 20% by weight of a vinyl polymer having no group represented by the general formula (1) in the molecule,
(However, the total of (A-1), (A-2), and (A-3) is 100% by weight)
The composition for heat dissipation sheets according to claim 1, wherein the composition is for heat dissipation. The component (A) is
(A-1) 50 to 10% by weight of a vinyl polymer having a group represented by the general formula (1) at both ends of the molecule;
(A-2) 5 to 90% by weight of a vinyl polymer having a group represented by the general formula (1) at one end of the molecule, and
(A-3) 0 to 20% by weight of a vinyl polymer having no group represented by the general formula (1) in the molecule,
(However, the total of (A-1), (A-2), and (A-3) is 100% by weight)
The composition for heat radiating sheets according to any one of claims 1 to 3, wherein: (A) The vinyl-type monomer which comprises the principal chain of a component is a (meth) acrylic-type monomer, The composition for heat dissipation sheets in any one of Claims 1-4. The composition for a heat radiation sheet according to any one of claims 1 to 5, wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer. The heat dissipation sheet according to any one of claims 1 to 6, 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. Composition. (A) ^Ra in general formula (1) of ^a component is a hydrogen atom or a methyl group, The composition for heat dissipation sheets in any one of Claims 1-7. The composition for a heat dissipation sheet according to any one of claims 1 to 8, 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 9, wherein the living radical polymerization is atom transfer radical polymerization. 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 1-10. The heat dissipation according to any one of claims 1 to 11, 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. Component (C) is carbon compound, metal oxide, metal nitride, metal carbide, metal hydroxide, metal carbonate, crystalline silica, organic polymer fired product, nitrogen carbide, composite ferrite with Zn ferrite, Fe- It is at least 1 sort (s) chosen from an Al-Si type | system | group ternary alloy and a metal powder, The composition for heat dissipation sheets in any one of Claims 1-12. The component (C) is at least one selected from graphite, diamond, aluminum oxide, boron nitride, aluminum nitride, aluminum hydroxide, and Fe-Al-Si ternary alloy. The composition for heat-radiation sheets as described in any one of Claims 1-3. (C) The composition for heat-radiation sheets in any one of Claims 1-14 whose volume ratio of a component is 25 volume% or more in all the compositions. The composition for heat-radiating sheet according to any one of claims 1 to 15, wherein the (D) condensed aromatic phosphate ester is liquid at 23 ° C. A heat dissipating sheet obtained by curing the heat dissipating sheet composition according to claim 1. The heat dissipation sheet according to claim 17, wherein the durometer hardness type E is less than 55. The heat dissipation sheet according to claim 18, which has flame retardancy of V-0 in the UL94 combustion test and has a weight loss of 0.1% or less after treatment at 150 ° C for 1 hour.