JP2011184557A - Thermally conductive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting thermally conductive composition which has excellent heat resistance and durability and in which the contact fault by a cyclic siloxane or the like, that is considered as a problem in a conventional technique, is remedied and which cures when it is heated, and to provide a thermally conductive material obtained by curing the composition. <P>SOLUTION: The thermally conductive material having a thickness of <0.5 mm is obtained by applying the thermally curable composition to between a heating element and a heat dissipation body and curing the applied composition between the heating element and the heat dissipation body, wherein the thermally curable composition is composed of a vinyl polymer (I) having on average at least one crosslinkable (meth)acryloyl group and a thermally conductive filler (II), and has viscosity of ≤6,000 Pa s before being cured and flowability at room temperature. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a heat conductive material used for heat dissipation of various devices such as electronic devices such as personal computers, mobile phones, and PDI, and lighting and display devices such as LEDs and EL. More specifically, it contains a vinyl polymer (I) having an average of at least one crosslinkable (meth) acryloyl group, and a thermally conductive filler (II), and has a viscosity before curing of 6000 Pa · s or less. Then, after applying a composition that retains fluidity at room temperature and is curable by applying heat between the heating element and the radiator, the composition is cured between the heating element and the radiator. It is related with the heat conductive material whose thickness after hardening becomes less than 0.5 mm.

  In recent years, the performance of electronic devices such as personal computers, mobile phones, and PDI, and lighting and display devices such as LEDs and EL has been remarkably improved, which is due to the significant performance improvements of arithmetic elements and light emitting elements. As described above, the amount of heat generation is remarkably increased with the improvement of the performance of the arithmetic element and the light emitting element, and how to dissipate heat in electronic devices, lighting, and display devices is an important issue. As a countermeasure against heat, the method of radiating heat by spreading heat generated by arithmetic elements and light-emitting elements over a wide area as quickly as possible is intended to increase cooling efficiency, but does not actively cool. It is the most realistic cooling method for small electronic devices such as mobile phones and personal computers and lighting.

  As a heat conductive material used for the purpose of heat dissipation and heat transfer, for example, a soft heat dissipation sheet in which a heat conductive filler is highly filled and cured in a base rubber such as silicone rubber is known. A technique based on a combination of a thermally conductive filler and silicone rubber is disclosed (see Patent Documents 1 to 3).

  The heat-dissipating sheet for the purpose of such heat conduction requires not only the heat conduction of the material itself, but also the heat resistance with the heat-generating body and the heat-dissipating element, so the adhesion with the heat-generating body and the heat dissipating element Is considered important. For the adhesion to the heating element and the radiator, the adhesion to the heating element and the surface of the radiator and the followability to the shape and deformation of the heating element and the radiator are important. However, if the heat conductive filler is highly filled to increase the thermal conductivity of the heat radiating sheet, the hardness of the sheet becomes hard, and the adhesiveness to the heating element and the surface of the heat radiating body and the shape followability are reduced. There was a problem that.

  In order to solve these problems, for example, Patent Document 4 discloses a room temperature curing type heat conduction that can be cured at room temperature after applying a liquid material in which a silicone rubber before curing is highly filled with a heat conductive filler. An adhesive silicone rubber composition has been disclosed, and since it is a liquid material, the adhesiveness to a heat body and a heat radiating body is very good, which is preferable. However, since it is an uncured silicone rubber composition, there is a problem that volatilization of low molecular siloxane components and cyclic siloxane components increases during use. Problems have been pointed out that silicone resins often cause poor contact of electrical components and poor reading of precision devices such as hard disks due to volatilization of cyclic siloxane, which is a low molecular component.

  On the other hand, for example, Patent Document 5 discloses a heat conductive grease in which a poly α-olefin oligomer is highly filled with a heat conductive filler. If such a composition is used, since it is a liquid substance, the adhesiveness with a heat body and a heat radiator becomes very good, and there is little possibility that a low molecular weight siloxane component volatilizes at the time of use. However, since such a composition does not cure at room temperature, when the heating element reaches a high temperature, the liquid grease having a low viscosity flows out and may contaminate surrounding electronic devices. There is a problem of being.

  Patent Document 6 includes a hydrolyzable silyl group-containing oligomer having a hydrolyzable silyl group, such as polyalkylene glycol and polyisobutylene, which is blended with a heat conductive filler and has excellent strength and adhesion. It is disclosed that it is a resin composition possessed together. However, hydrolyzable silyl group-containing polyalkylene glycol-based oligomers may not have sufficient heat resistance, and hydrolyzable silyl group-containing polyisobutylene-based oligomers are relatively viscous and difficult to handle, and have a curing rate. Since it is slow, it is often difficult to use it as a one-component composition.

  Patent Document 7 discloses a composition for a heat dissipation sheet in which a vinyl polymer produced by a living radical polymerization method having a molecular weight distribution of 1.8 or less is filled with a heat conductive filler. There is no description about the method of using as a room temperature curable heat conductive composition as it is. In addition, since the curing type is a moisture curing type, curing curing requires several hours or more, and there is a concern that productivity is inferior.

  Further, in Patent Document 8, as in Patent Document 7, there is no description regarding a specific method used as a composition for a heat radiation sheet.

Japanese Patent Publication No. 6-55891 Japanese Examined Patent Publication No. 6-38460 Japanese Patent Publication No. 7-91468 JP 2004-352947 A JP 2008-19319 A JP 2001-302936 A JP 2006-274094 A JP 2006-278476 A

  As described above, there have been various problems in the prior art in which the curable resin composition or the heat conductive grease is applied to the surface of the heat generator or the heat radiator. In the case of using a pre-cured heat dissipation sheet, there is a problem that the thermal resistance is increased. Although it is possible to reduce the thermal resistance of the heat radiating sheet itself by making the heat radiating sheet as thin as possible, the heat radiating sheet is softened in order to improve the adhesion to the heat generating body and the surface of the heat radiating body and the shape followability. On the other hand, when trying to make a thin sheet having a thickness of less than 0.5 mm, the heat-dissipating sheet is easily broken due to tearing or the like at the time of affixing to the heating element, resulting in a problem that handling becomes very complicated. Therefore, commercially available soft heat dissipation sheets generally have a thickness of 0.5 mm or more, and when the thickness is less than 0.5 mm, the heat dissipation sheet needs to be hardened to some extent. In addition, it is possible to use the heat conductive material before curing in the conventional heat conductive material, but in the conventional product, since the viscosity before curing is high, the productivity deteriorates due to poor handling property, and the high viscosity. Therefore, once air is involved, the possibility that the air is difficult to escape increases. As a result, there were concerns about problems such as a decrease in thermal conductivity.

  The present invention has excellent heat resistance and durability, has a low possibility of contact failure due to cyclic siloxane, which has been regarded as a problem in the prior art, and is low in viscosity so that operations such as coating are easy and productive. A thermosetting heat conductive composition that is high and can be cured by applying heat, and a heat conductive material obtained by curing the composition.

  As a result of intensive studies in view of the above-mentioned present situation, the present inventors contain a vinyl polymer (I) having an average of at least one crosslinkable (meth) acryloyl group, and a thermally conductive filler (II). In addition, by suppressing the viscosity before curing as low as 6000 Pa · s or less, it is possible to obtain a composition that has fluidity at room temperature with excellent coating properties and can be cured by applying heat. After thinly applying the object between the heating element and the radiator, it is cured between the heating element and the radiator, and the thickness after curing is less than 0.5 mm. The present inventors have found that it is possible to remarkably reduce the thermal resistance in the meantime, and have reached the present invention.

  That is, the first of the present invention includes 1) a vinyl polymer (I) having an average of at least one crosslinkable (meth) acryloyl group, and a thermally conductive filler (II), and has a viscosity before curing. A composition having fluidity at room temperature of 6000 Pa · s or less and curable by applying heat is applied between the heating element and the radiator, and then between the heating element and the radiator. The present invention relates to a thermally conductive material having a thickness of less than 0.5 mm after curing.

The second of the present invention relates to 2) the heat conducting material according to 1), which further contains an initiator (III) of the vinyl polymer (I).
The third of the present invention relates to 3) the heat conducting material according to 1), wherein the heat conducting material contains a plasticizer (IV).

  A fourth aspect of the present invention relates to 4) a heat conductive material according to 1), which contains a vinyl polymer (I) having a molecular weight distribution of less than 1.8.

5th of this invention is related with the heat conductive material in any one of 5) crosslinkable (meth) acryloyl group represented by General formula (1).
—OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)

  6th of this invention 6) The main chain is mainly polymerizing a monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. The heat conductive material according to any one of 1) to 5), which comprises a vinyl polymer (I) that is produced by the following method.

  A seventh aspect of the present invention relates to the heat conductive material according to 6), wherein the main chain contains a vinyl polymer (I) which is a (meth) acrylic acid ester polymer.

  8th of this invention is 8) The heat conductive material in any one of 1) -7) whose principal chain of vinyl polymer (I) is manufactured by the living radical polymerization method About.

  The ninth of the present invention relates to 9) the heat conducting material according to 8), wherein the main chain of the vinyl polymer (I) is produced by an atom transfer radical polymerization method.

  The tenth aspect of the present invention relates to 10) the heat conducting material according to any one of 1) to 9), wherein the crosslinkable (meth) acryloyl group of the vinyl polymer (I) is at the molecular chain end. .

  The eleventh of the present invention is 11) the thermally conductive filler (II) is a carbon compound, metal oxide, metal nitride, metal carbonate, metal carbide, metal hydroxide, crystalline silica, organic polymer fired product, Zn The heat conductive material according to any one of 1) to 10), which is at least one selected from composite ferrite with ferrite, Fe—Al—Si ternary alloy, and metal powder.

  In the twelfth aspect of the present invention, 12) the thermally conductive filler (II) is graphite, diamond, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium carbonate, crystallized silica, Fe-Al It is related with the heat conductive material as described in 11) which is 1 or more types chosen from -Si type | system | group ternary alloy and carbonyl iron.

  The thirteenth aspect of the present invention relates to the heat conductive material according to any one of 1) to 12), wherein the volume ratio of the heat conductive filler (II) is 25% by volume or more in the total composition. .

    The heat conductive material obtained by curing the heat conductive composition which can be cured by applying heat according to the present invention has excellent heat resistance and durability, and has been regarded as a problem in the prior art. It is characterized in that the problems of contact failure due to the above, the handling properties due to the high viscosity before curing of the conventional product, the problem of poor bubble removal in the heat conducting material are improved, and the heat dissipation effect is improved.

Below, the structure of the heat conductive composition of this invention is explained in full detail.
<< Vinyl polymer (I) >>
In the present invention, in order to obtain a composition that has fluidity at room temperature and can be cured by applying heat, a vinyl-based polymer having at least one crosslinkable (meth) acryloyl group on average in the molecule. Use coalescence (I). The amount of the vinyl polymer (I) used is preferably 0.1% by weight to 90% by weight in the total composition from the viewpoint of the balance between viscosity before curing, curability and thermal resistance after curing, It is more preferably 1% to 60% by weight, and particularly preferably 5% to 35% by weight.

The component (I) is represented by the general formula (1): —OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ 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 above general formula (1) in the component (I) 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 (I) is produced, the average value of the 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 (I). That is, as the component (I), 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. 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, since the distance between cross-linking points can be increased and a flexible sheet can be easily obtained, the component (I) is a group represented by the general formula (1) at both ends of the molecule (I-1). It is preferable to contain the vinyl polymer which has and (I-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 (I-1) to (I-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 (I) is produced, the produced vinyl polymer mixture may contain a small amount of a resin having no (meth) acryloyl group. is there. The component (I) is (I-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 (I-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 (I-3) a vinyl polymer 0 having no group represented by the general formula (1) in the molecule. It may be 20% by weight (provided that the total of (I-1), (I-2), and (I-3) is 100% by weight).

  Furthermore, the component (I) is a vinyl polymer having groups represented by the general formula (1) at both ends of the molecule (I-1), 50 to 10% by weight, and (I-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 (I-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 (I-1), (I-2), and (I-3) is 100% by weight) is preferable because a more flexible heat dissipation sheet can be obtained.

R ¹ 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. Preferable specific examples of R ¹ 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 .

  The vinyl monomer constituting the main chain of component (I) is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and their salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyl Silicon-containing vinyl monomers such as trimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as reimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of oil resistance and the like, it is particularly preferable that the vinyl monomer constituting the main chain includes at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate.
In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The molecular weight distribution of component (I) [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)] is not particularly limited, but 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 component (I) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40,000. 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 (I) Component> The production method of the (I) component 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 (I) 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, for example, Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 79.
Using cobalt porphyrin complex as shown on page 43, Macromolecules, 1994, 27, 7228
Examples include those using radical scavengers such as nitroxide compounds as shown on the page, “Atom Transfer Radical Polymerization (ATRP)” using organic halides as initiators and transition metal complexes as catalysts. Can be mentioned.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the 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)
(Wherein 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 and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group ) Or o-, m-, p-phenylene group)
The compound shown by these is mentioned.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), but 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 or a phenylene group 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-a (Y) a O] m -Si (R 12) 3- _n (Y) _n (8)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as defined above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, 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; and Y represents two or more When present, they may be the same or different, n is 0, 1, 2 or 3, a is 0, 1 or 2, m is an integer from 0 to 19, provided that n + ma ≧ 1 Satisfy)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
XCH ₂ C (O) O (CH ₂ ) _n Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formula, X is a chlorine atom, bromine atom, iodine atom, n is an integer of 0-20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ ,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(Wherein X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (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-n (}} Y) n Si- [OSi (R 11) 2-a (Y) a] 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 , n, a, 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 (RuCl2 (PPh3) 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 (FeCl2 (PPh3) 2), a divalent nickel bistriphenylphosphine complex (NiCl2 (PPh3) 2), a divalent nickel bistributylphosphine complex (NiBr2 (PBu3)) 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 (I) 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 converted to 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 ³ ) ═CH ₂ (2)
(Wherein R ³ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M + represents an alkali metal ion or a quaternary ammonium ion)
The 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 the 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 ⁴ ) ═CH ₂ (4)
(Wherein R ⁴ 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 ⁵ ) ═CH ₂ (5)
(Wherein R ⁵ 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 ³ in the 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 ⁴ in the 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)
Wherein 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 above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like. Specific examples of R ¹⁶ are the same as the specific examples 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)
(Wherein, R ¹⁶ and M ⁺ are as defined above, R ^17, R ¹⁸ together carbanion C ^- with an electron withdrawing group or one of the electron-withdrawing group stabilizing, the other is a hydrogen atom, C1-10 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).

As the electron-withdrawing group, -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 general formula (13): HO—R ¹⁶ —OM— (13) (Wherein R ¹⁶ and M + are the same as above) and the like, and the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above), and the like, and the halogen atom is substituted 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 (a) is more preferable from the viewpoint of easier control.
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. 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 ⁵ ) ═CH ₂ (5)
(Wherein R ⁵ 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 ⁵ in the 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.

<< Thermal conductive filler (II) >>
As the heat conductive filler of the present invention, a commercially available general heat conductive filler can be used. Among them, carbon compounds such as graphite, diamond, etc .; aluminum oxide, magnesium oxide from the viewpoint of being able to impart specific electrical characteristics such as thermal conductivity, availability, insulation, electromagnetic shielding, and electromagnetic absorption , Metal oxides such as beryllium oxide, titanium oxide, zirconium oxide, and zinc oxide; metal nitrides such as boron nitride, aluminum nitride, and silicon nitride; metal carbides such as boron carbide, aluminum carbide, and silicon carbide; aluminum hydroxide, water Metal hydroxides such as magnesium oxide; metal carbonates such as magnesium carbonate and calcium carbonate; crystalline silica: calcined acrylonitrile polymer, calcined furan resin, calcined cresol resin, calcined polyvinyl chloride, calcined sugar Baked organic polymer such as fired charcoal; composite with Zn ferrite Ferrite; Fe-Al-Si ternary alloy; metal powders, and the like preferably.

  Further, from the viewpoint of availability and thermal conductivity, graphite, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium carbonate, and crystallized silica are more preferable, graphite, α-alumina, hexagonal More preferred are crystalline boron nitride, aluminum nitride, aluminum hydroxide, Mn—Zn soft ferrite, Ni—Zn soft ferrite, Fe—Al—Si ternary alloy (Sendust), carbonyl iron, iron nickel alloy (Permalloy) Spheroidized graphite, round or spherical α-alumina, spheroidized hexagonal boron nitride, aluminum nitride, aluminum hydroxide, Mn—Zn soft ferrite, Ni—Zn soft ferrite, spherical Fe—Al—Si three Original alloy (Sendust), Carbo Nyl iron is particularly preferred.

  When carbonyl iron is used in the present invention, reduced carbonyl iron powder is desirable. The reduced carbonyl iron powder is not a standard grade but a carbonyl iron powder classified into a reduced grade, and is characterized by a lower carbon and nitrogen content than the standard grade.

  In addition, these thermally conductive fillers are silane coupling agents (vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, chloro silane, amino silane from the viewpoint of improving dispersibility with respect to the vinyl polymer (I). Etc.), titanate coupling agents (alkoxy titanate, amino titanate, etc.), or fatty acids (caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and other saturated fatty acids, sorbic acid , Elaidic acid, oleic acid, linoleic acid, linolenic acid, erucic acid and other unsaturated fatty acids) and resin acids (abietic acid, pimaric acid, levopimaric acid, neoapitic acid, parastrinic acid, dehydroabietic acid, isopimaric acid, sandaracopi Maric acid, cormic acid, secodehydride Abietic acid, the dihydroabietic acid, etc.) or the like, it is preferable that the surface has been treated.

  Among these, some of the thermal conductivities are, for example, 1.5 W / mK for silica, 20 W / mK for alumina, 40 W / mK for magnesium oxide, 60 W / mK for boron nitride, and 70 W / mK for aluminum nitride. , Copper has a good thermal conductivity of 398 W / mK, aluminum has a thermal conductivity of 237 W / mK, and the like.

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

Here, the volume fraction (%) of the thermally conductive filler is calculated from the weight fraction and specific gravity of the resin component and the thermally conductive filler, and is obtained by the following equation. In the following formula, the 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 means all components excluding the heat conductive filler, and specifically, various types such as vinyl polymer (I), initiator (III), plasticizer (IV) and other tackifying resins. Refers to an additive.

  Further, as one method for increasing the filling rate of the thermally conductive filler with respect to the vinyl polymer (I), it is preferable to use two or more kinds of thermally conductive fillers having different particle diameters in combination. In this case, it is preferable that the heat conductive filler having a large particle diameter exceeds 10 μm, and the heat conductive filler having a small particle diameter is 10 μm or less.

  Moreover, these heat conductive fillers can use not only the same kind of heat conductive filler but also two or more kinds of different kinds in combination. Moreover, you may use various fillers other than a heat conductive filler as needed to such an extent that the effect of this invention is not prevented. Various fillers other than the heat conductive filler are not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, diatomaceous earth, white clay, silica (Fumed silica, precipitated silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, amorphous spherical silica, etc.), reinforcing filler such as carbon black; diatomaceous earth, calcined clay, clay, talc, Titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, activated zinc white, zinc powder, zinc carbonate and shirasu balloon, glass microballoon, organic microballoon of phenol resin and vinylidene chloride resin, PVC powder Fillers such as resin powder such as PMMA powder; asbestos, glass fiber and glass filament, Carbon fiber, Kevlar fiber, fibrous fillers such as polyethylene fiber and the like. Of these fillers, precipitated silica, fumed silica, fused silica, dolomite, carbon black, titanium oxide, talc and the like are preferable. Some of these fillers have a slightly function as a heat conductive filler, and the composition, such as carbon fiber, various metal powders, various metal oxides, various organic fibers, Some synthesis methods, crystallinity, and crystal structures can be used as excellent heat conductive fillers.

<< Initiator (III) >>
The initiator of the component (III) 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 particularly 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.

  (III) 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 (I) component from the point of sclerosis | hardenability and storage stability. Part by weight is preferred, more preferably 0.025 to 7 parts by weight.

  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 (III), 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 (III) 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 0.001 to 10 parts by weight, more preferably about 0.025 to 7 parts by weight.

  Furthermore, the redox (redox) initiator that can be used as the component (III) 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 0.001 to 10 parts by weight, more preferably about 0.025 to 7 parts by weight.

<< Plasticizer (IV) component >>
You may use various plasticizers for the heat conductive material of this invention as needed. When a plasticizer is used in combination with a filler to be described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed, but it is not necessarily added. Although it does not specifically limit as a plasticizer, For purposes, such as adjustment of physical properties and adjustment of properties, for example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate Non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; diethylene glycol dibenzoate, triethylene glycol di Polyalkylene glycol esters such as benzoate and pentaerythritol ester; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrenes such as re-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; Polyether glycol such as polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, polytetramethylene glycol, etc., one end or both ends or all ends of the hydroxyl groups of these polyether polyols to alkyl ester groups or alkyl ether groups Polyethers such as converted alkyl derivatives; Epoxy group-containing plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, E-PS; sebacic acid, adipic acid, azela Polyester plasticizers obtained from dibasic acids such as inic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; vinyl plastics including acrylic plasticizers Examples thereof include vinyl polymers obtained by polymerizing monomers by various methods.

  In particular, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition are obtained. Mechanical properties such as strength and elongation can be adjusted, and the initial physical properties are maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It is possible to improve the drying property (also referred to as paintability) when an alkyd paint is applied. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the polymer plasticizer was described as 500 to 15,000 above, it is preferably 800 to 10,000, and more preferably 1,000 to 8,000. If the molecular weight is too low, the plasticizer flows out over time due to heat, the initial physical properties cannot be maintained for a long time, and the alkyd paintability may not be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen.

  Among these polymer plasticizers, polyether plasticizers and (meth) acrylic polymer plasticizers are preferable from the viewpoint of high elongation characteristics or high weather resistance. Examples of the synthesis method of the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer is prepared by a high temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-313522, USP 5010166) without using a solvent or a chain transfer agent. More preferred for the purposes of the present invention. Examples thereof include, but are not particularly limited to, for example, ARUFON UP series (UP-1000, UP-1021, UP-1110, UP-2000, UP-2130) (referred to as SGO) of Toagosei Co., Ltd. (waterproof journal 2002) June issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow from the viewpoint of viscosity, and preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  From the viewpoint of viscosity, it is preferable to have a branched structure in the main chain because the viscosity becomes lower at the same molecular weight. The high temperature continuous polymerization method mentioned above is mentioned as this example.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties. In addition, for example, in the case of a composition in which the vinyl polymer of the present invention and a polyether polymer which is one of optional polymers having a crosslinkable functional group are mixed, from the point of compatibility of the mixture Phthalic acid esters and acrylic polymers are particularly preferred.

  These plasticizers can also be blended at the time of polymer production.

  Although the usage-amount in the case of using a plasticizer is not limited, 5-150 weight part is preferable with respect to 100 weight part of polymers which have a crosslinkable (meth) acryloyl group, 10-120 weight part is more preferable, 20-20 weight part. More preferably, 100 parts by weight. If the amount is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<< Other ingredients >>
Moreover, in the heat conductive material of this invention, you may add various compounding agents according to the target physical property.

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

  As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (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 the viewpoint of workability due to improved surface curability, imparting toughness, and reducing viscosity, to 100 parts by weight of component (hereinafter, also simply referred to as part). 1 to 200 parts is preferable, and 5 to 100 parts is more preferable.

  <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 amount of other components used is preferably 0.025 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, based on 100 parts by weight of component (I), 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 component (I) 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 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 said various antioxidants including a monoacrylate phenolic antioxidant is not specifically limited, For the purpose of giving a good effect on the mechanical physical property of the obtained heat-radiation sheet, (I) 100 parts of 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.

  <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 (I) from the viewpoint of the finish of the heat dissipation sheet, workability, and drying balance.

  <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 (I).

<< Viscosity before curing >>
In the heat conductive material of the present invention, a composition that can be cured at room temperature and has a fluidity of 6000 Pa · s or less before curing is applied to a thickness of 0.5 mm or less between a heating element and a radiator. Then, it is obtained by curing between the heating element and the radiator. By keeping the viscosity before curing as low as 6000 Pa · s or less, it is possible to reduce the thermal resistance after solidification by allowing the composition before curing to enter all the gaps between the heating element and the radiator. If the viscosity before curing exceeds 6000 Pa · s, the effect of filling the gap between the heat generator and the heat radiator will be low. The viscosity before curing is preferably 4000 Pa · s or less, more preferably 2500 Pa · s or less, and most preferably 2000 Pa · s or less. The viscosity before curing was 23 ° C. and 50% R.D. H. A value measured under the condition of 2 rpm using a BS type viscometer in an atmosphere is used. The lower limit of the viscosity before curing is not particularly limited. However, if the viscosity is too low, there is a concern that the viscosity may be lost between application and curing, so generally 0.1 Pa · s. The above is used.

<< Thickness after curing >>
The heat conductive material of this invention shows the outstanding thermal resistance reduction effect by making thickness after hardening less than 0.5 mm. If the thickness after curing is 0.5 mm or more, the thermal resistance of the heat conducting material itself increases, so the effect of reducing the thermal resistance is lowered, which is not preferable. The thickness after curing is measured by measuring the overall dimensions from the heating element to the heat dissipation element, after the heating element and the heat dissipation element are in close contact with each other without applying the composition before curing. The composition before curing is thinly applied, and the heating element and the radiator are adhered and cured, and after curing, the overall dimensions from the heating element to the radiator are measured again, and the dimensional change between before and after curing Can be measured from The thickness of the heat conductive material after curing is preferably 0.4 mm or less, more preferably 0.3 mm or less, and most preferably 0.2 mm or less. The lower limit of the thickness of the heat conductive material after curing is not particularly limited, but is generally 0.01 mm or more.

<< Usage and usage >>
The composition of the present invention is used after being thinly applied between the heat generating body and the heat radiating body and then cured to a thickness of less than 0.5 mm between the heat generating body and the heat radiating body.

  The composition of the present invention can be used as a thermal interface that transfers heat between the heat generating material and the heat spreader, or between the heat spreader and the cooling member. It can also be used as a heat spreader itself. Although it does not specifically limit as a heat-generating material, Electronic components, such as a heater with a heat_generation | fever, a temperature sensor, an arithmetic element, a transistor, and a light emitting element, etc. are mentioned. The cooling member is not particularly limited, and examples of the heat radiating material include a heat sink such as a heat radiating fin, a graphite sheet (graphite film), liquid ceramics, a Peltier element, and the like. It is preferably used as a thermally conductive material that dissipates heat from these heat generating materials to a cooling member or the like, and may be used as the heat radiating material itself. Moreover, you may serve as a heat spreader and a cooling member.

  Since the composition of the present invention uses a vinyl polymer as a base resin, it is excellent in heat resistance, weather resistance, chemical resistance and water resistance, and can withstand severe use. In addition, when an electrically insulating filler is mainly used, it is excellent in electrical insulation and can be used in a site where electrical insulation is required. On the other hand, when an electrically conductive filler is mainly used, it is excellent in electrical conductivity and can also be used in a site where electrical conductivity is required.

  Furthermore, since the composition of the present invention is applied between the heat generating body and the heat radiating body and then cured between the heat generating body and the heat radiating body, it is in close contact with these heat generating materials and heat radiating materials. It has excellent properties and can sufficiently transfer heat even with some unevenness.

  Although it is not limited as a use utilizing thermal conductivity, it is particularly suitable for a small electronic device such as a mobile phone or a personal computer because a contact failure due to cyclic siloxane does not occur. Furthermore, it can be used for various applications such as electric and electronic component materials such as automobiles and home appliances, electric insulating materials such as insulating coating materials for electric wires and cables, and potting agents for electric and electronic devices.

  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 synthesis examples, examples and comparative examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

  Synthesis examples of the polymer in the present invention are shown below.

  In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) and chloroform as a GPC solvent were used.

  (Synthesis example 1) Synthesis example of poly (n-butyl acrylate) copolymer having crosslinkable (meth) acryloyl group: cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5 -N-butyl acrylate was polymerized using dibromoadipate as an initiator to obtain a terminal bromine group poly (n-butyl acrylate) having a number average molecular weight of 22500 and a molecular weight distribution of 1.15. 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.

  (Synthesis example 2) Synthesis example of poly (n-butyl acrylate) copolymer having crosslinkable (meth) acryloyl group: cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, ethyl 2-bromobutyrate Was used as an initiator to polymerize n-butyl acrylate to obtain a one-terminal bromine group poly (n-butyl acrylate) having a number average molecular weight of 11800 and a molecular weight distribution of 1.08. 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 in a nitrogen atmosphere to give poly (acrylic acid n-acrylate) with a acryloyl group at one end. 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.

Example 1
Polymer [1] obtained in the synthesis example, thermal conductive filler: AS-40 (rounded alumina, manufactured by Showa Denko), initiator: perbutyl I (t-butyl peroxyisopropyl monocarbonate, manufactured by NOF Corporation) , Plasticizer: UP-1021 (acrylic plasticizer, manufactured by Toagosei Co., Ltd.), antioxidant: Adeka Stub AO-60 (manufactured by Adeka), mixed thoroughly according to the formulation table in Table 1, and further added to 3 paint rolls. The mixture was circulated and kneaded to obtain a thermosetting composition. The obtained mixture was coated on a 15 mm square ceramic heater as a heating element in the form of a 0.2 mm thick film and sandwiched between metallic heat sinks of the same size as a radiator, and then placed in an atmosphere at 180 ° C. For 15 minutes and cured to obtain a heat conductive material.

  In addition, the obtained mixture was separately applied on the entire surface of a standard nickel disk plate (purity: 99.9%, diameter: about 12.7 mm, thickness: about 1.0 mm) to a thickness of about 0.2 mm, On top of that, another standard nickel disk-shaped plate was overlaid, and with a 2 kg weight placed on the plate, it was allowed to stand for 15 minutes in an atmosphere at 180 ° C. and cured to obtain a sample for measuring thermal resistance. . After measuring the thickness of the entire sample, the thickness of the heat conductive material was calculated by subtracting the thickness of a known standard nickel disc plate.

(Examples 2-8, Comparative Examples 2-3)
A heat conductive material was obtained in the same manner as in Example 1 except that the following materials were used for the polymer, the heat conductive filler, the initiator, the plasticizer, and other additives and mixed at the ratio shown in Table 1.

(Comparative Example 1)
The same composition as that obtained in Example 1 was applied to a protective film so as to have a thickness of 1.2 mm, thereby being cured into a flexible sheet having a thickness of about 1.2 mm. A heat conductive material was obtained in the same manner as in Example 1 except that this was sandwiched between a heat generator and a heat radiator to obtain a heat conductive agent.
Thermally conductive filler:
BF083 (Aluminum hydroxide, Nippon Light Metal)
1 type of zinc oxide (Zinc oxide manufactured by Sakai Chemical Industry)

[Viscosity before curing]
The viscosity of the obtained composition before curing was measured at 23 ° C. using a BS viscometer at 2 rpm.

[Thermal conductivity]
A 12.7 mmφ disk-shaped sample is cut out from the obtained 0.2 mm thick heat conductive material, and a laser light absorbing spray (Black Guard Spray FC-153 manufactured by Fine Chemical Japan Co., Ltd.) is applied to the sample surface and dried. Then, based on ASTM E1461, the thermal diffusivity of the thickness direction was measured using Xe flash analyzer LFA447Nanoflash made from NETZSCH. In addition, the specific heat of the sample was calculated from comparison with a reference standard having a known heat capacity. Further, the thermal conductivity in the thickness direction was calculated from the density measured separately by the water displacement method according to the following formula.

  [Thermal conductivity] = [thermal diffusivity] x [density] x [specific heat]

[Thermal resistance]
Using the obtained sample for measuring thermal resistance, the thermal resistance (K / W) of the cured product per unit area in the obtained sample thickness was measured with a Xe flash analyzer LFA447 Nanoflash manufactured by NETZSCH.

  As can be seen from the results of Examples 1 to 8 in Table 1, any of the examples was able to keep the thermal resistance low.

Claims (13)

  Contains vinyl polymer (I) having at least one crosslinkable (meth) acryloyl group on average and thermally conductive filler (II), and has a viscosity before curing of 6000 Pa · s or less and flows at room temperature. The composition is cured between the heating element and the heat radiating body after being applied with a composition that can be cured by applying heat, and the thickness after curing is 0. Thermally conductive material less than 5 mm.   The heat conductive material according to claim 1, further comprising an initiator (III) of the vinyl polymer (I). The heat conductive material according to claim 1, wherein the heat conductive material contains a plasticizer (IV).   The heat conductive material according to claim 1, comprising a vinyl polymer (I) having a molecular weight distribution of less than 1.8. Crosslinkable (meth) acryloyl group is represented by General formula (1), The heat conductive material in any one of Claims 1-4 characterized by the above-mentioned.
—OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)   The main chain is produced by mainly polymerizing a monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The heat conductive material according to claim 1, comprising a vinyl polymer (I).   The heat conductive material according to claim 6, wherein the main chain contains a vinyl polymer (I) which is a (meth) acrylic acid ester polymer.   The heat conductive material according to any one of claims 1 to 7, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method.   The heat conductive material according to claim 8, wherein the main chain of the vinyl polymer (I) is produced by an atom transfer radical polymerization method.   The heat conductive material according to any one of claims 1 to 9, wherein the crosslinkable (meth) acryloyl group of the vinyl polymer (I) is at a molecular chain terminal. Thermally conductive filler (II) is carbon compound, metal oxide, metal nitride, metal carbonate, metal carbide, metal hydroxide, crystalline silica, fired organic polymer, composite ferrite with Zn ferrite, Fe- The heat conductive material according to claim 1, which is at least one selected from an Al—Si ternary alloy and metal powder. Thermally conductive filler (II) is graphite, diamond, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium carbonate, crystallized silica, Fe-Al-Si based ternary alloy, and It is 1 or more types chosen from carbonyl iron, The heat conductive material of Claim 11 characterized by the above-mentioned. The heat conductive material according to claim 1, wherein the volume fraction of the heat conductive filler (II) is 25% by volume or more in the total composition.