JP2006111848A - Thermally conductive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily reduce the thickness during heating, to have excellent moldability, to have high thermal conductivity, to have sufficient strength, to be easy to handle, and to be suitable as a phase change type heat transfer / heat radiation material for heat-generating parts. To provide a thermally conductive resin composition.
A thermally conductive resin composition comprising a combination of (a) a crystalline higher α-olefin copolymer of 5 to 95% by mass and (b) 95 to 5% by mass of a thermally conductive filler, and the thermal conductivity thereof. It is a heat-transfer / heat-dissipation material consisting of a conductive resin composition.
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Description

  The present invention relates to a thermally conductive resin composition, and more specifically, it is easy to thin during heating and has excellent moldability, high thermal conductivity, sufficient strength, excellent handleability, and exothermic properties. The present invention relates to a heat conductive resin composition suitable as a phase change type heat transfer / heat dissipation material for electronic components.

In recent years, heat removal from a heating element has been performed in various fields. For example, in electronic components and electronic devices, a heat generating electronic component (CPU (Central Processing Unit) incorporated therein). ), IC chips, etc.) and other parts (hereinafter, collectively referred to as “exothermic parts”) is an important issue. This is because, in various exothermic parts, the probability that the part malfunctions increases exponentially as the temperature of the part rises. Recently, the heat-generating parts are becoming more and more compact and the processing speed is also increasing, so that higher heat dissipation characteristics are required.
Currently, as a heat dissipation measure, for example, a heat radiator such as a heat sink or a heat radiating fin is attached to a heat-generating component. Moreover, in order to further improve the heat conduction efficiency between the heat-generating component and the heat radiating body, it is common to interpose a heat transfer spacer between them. As such a heat transfer spacer, for example, there is a heat conductive grease, but since it is liquid, there is a problem in handling. Therefore, attention has been paid to phase change material (PCM) that is solid at room temperature and liquid at the operating temperature of the heat-generating electronic component.
As phase change material (PCM), paraffins, which are heat conductive phase change materials that change phase at the operating temperature of the exothermic component, are filled with boron nitride or alumina particles, which are heat conductive fillers (for example, Patent Documents 1 and 2) are disclosed. The filling factor is 10 to 80% by mass in Patent Document 1 and 65 to 85% by mass in Patent Document 2. However, there are various problems due to the low molecular weight of paraffins. For example, in a resin composition with a high content of paraffins, the resin composition leaks violently from a molding machine or mold during melt molding, and when the paraffin content is low, the strength of the resin composition is low. It was difficult to produce a shaped molded body. If the composition ratio between the paraffins and the heat conductive filler is within a predetermined range, a PCM having a desired shape can be obtained. However, since the strength is still low, there is a problem that the molded body is easily damaged.
Moreover, in order to raise the intensity | strength of a resin composition, adding 20-20 mass% of resin, such as ethylene-vinyl acetate copolymer, is disclosed (for example, refer patent document 3). However, since this resin composition has a high melt viscosity when heated, it cannot be made sufficiently thin. For this reason, there is a problem that the thermal resistance is large although the thermal conductivity is large. Furthermore, it has been proposed to use polyisobutylene in order to achieve both strength and fluidity during heating (see, for example, Patent Document 4), but polyisobutylene is in the form of a syrup at room temperature and is extremely poor in handleability. There was a problem that it was difficult to produce the resin composition.

JP 2001-89756 A JP 2004-75760 A Japanese Patent Laid-Open No. 11-45965 JP 2003-26928 A

  The present invention has been made in view of the above circumstances, and is easy to be thinned during heating, excellent in moldability, high in thermal conductivity, sufficient in strength, excellent in handleability, and in a phase of a heat-generating component. An object is to provide a heat conductive resin composition suitable as a change-type heat transfer / heat dissipation material.

As a result of intensive studies to solve the above problems, the present inventors have achieved the above object by combining a crystalline higher α-olefin copolymer having a narrow molecular weight distribution and a thermally conductive filler. I found out. The present invention has been completed based on such findings.
That is, the present invention provides the following heat conductive resin composition and heat transfer / heat dissipation material.
1. A thermally conductive resin composition comprising a combination of (a) a crystalline higher α-olefin copolymer of 5 to 95% by mass and (b) 95 to 5% by mass of a thermally conductive filler.
2. 2. The thermally conductive resin composition as described in 1 above, wherein the crystalline higher α-olefin copolymer as component (a) contains 50 mol% or more of α-olefin units having 10 or more carbon atoms.
3. The thermal conductive resin composition according to claim 1 or 2, wherein the melting point (Tm) of the component (a) observed from a melting endothermic curve obtained by using a differential scanning calorimeter (DSC) is 30 to 120 ° C. object.
4). (A) The heat conductive resin composition in any one of said 1-3 which replaced 80 mass% or less of components with resin softened at 40-130 degreeC.
5). The heat-transfer / heat radiation material which consists of a heat conductive resin composition in any one of said 1-4.
6). 6. The heat transfer / heat dissipating material as described in 5 above, which is a sheet or film having a thickness of 0.02 to 3 mm.

  According to the present invention, thinning during heating is easy, excellent formability, high thermal conductivity, sufficient strength, excellent handleability, and heat-generating component phase change type heat transfer / heat dissipation material As such, it is possible to provide a suitable heat conductive resin composition.

In the thermally conductive resin composition of the present invention, the crystalline higher α-olefin copolymer used as the component (a) is a higher α-olefin of two or more carbon atoms having 10 or more carbon atoms or a higher α-olefin having 10 or more carbon atoms. It is a copolymer obtained by copolymerizing one or more olefins and one or more other olefins.
As the higher α-olefin having 10 or more carbon atoms, an α-olefin having 10 to 35 carbon atoms can be preferably used. For example, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like. These can be used individually by 1 type or in combination of 2 or more types.
Moreover, as another olefin, a C2-C30 olefin can be used and an alpha olefin is preferable. Examples of the α-olefin include those having 2 to 9 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. These can be used individually by 1 type or in combination of 2 or more types.

When the higher α-olefin used for copolymerization has 10 or more carbon atoms, the higher α-olefin copolymer obtained by copolymerization has a high crystallinity and is a composition with a thermally conductive filler. Strength is improved.
Moreover, when the carbon number of the higher α-olefin used for copolymerization is 35 or less, there is little unreacted monomer, and a uniform composition having a narrow melting and crystallization temperature range tends to be obtained. That is, by raising the temperature slightly above the melting point, the solid components disappear completely and all the components become liquid, and the melt viscosity becomes very small. Therefore, the PCM is sufficiently thinned at the operating temperature of the CPU, and the heat is reduced. The conductivity can be greatly improved.
The content of the higher α-olefin unit having 10 or more carbon atoms in the crystalline higher α-olefin copolymer is usually 50 mol% or more, preferably 70 to 100 mol%, more preferably 85 to 100 mol%. . Particularly preferred is a copolymer consisting only of a higher α-olefin having 10 or more carbon atoms. When the content of the higher α-olefin unit having 10 or more carbon atoms is 50 mol% or more, a crystalline copolymer is obtained and the melting point is low, so that the compatibility with the heat conductive filler is improved.

The crystalline higher α-olefin copolymer used in the present invention preferably satisfies the following requirements.
(1) Using a differential scanning calorimeter (DSC), the crystalline higher α-olefin copolymer was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and −10 The melting point (Tm) defined as the peak top of the melting peak observed from the melting endotherm curve obtained by holding at 5 ° C. for 5 minutes and then increasing the temperature to 190 ° C. at 10 ° C./min is 30 to 120 ° C. Is in range.
(2) There is one melting peak observed from the melting endothermic curve, and its half width (Wm) is 10 ° C. or less.
(3) In the wide-angle X-ray scattering intensity distribution, a single peak X1 derived from side chain crystallization observed at 15 ° <2θ <30 ° is observed.
(4) Polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) method is in the range of 1,000 to 10,000,000, and molecular weight distribution (Mw / Mn) is 5. 0 or less.
(5) The stereoregularity index value M2 derived from the higher α-olefin chain portion having 10 or more carbon atoms is 50 mol% or more, M4 is 25 to 60 mol%, and MR is 2.5 mol% or more.

As described in (1) above, the crystalline higher α-olefin copolymer has a melting point (Tm) of preferably 30 to 120 ° C., more preferably 40 to 100 ° C. When the melting point is 30 ° C. or higher, the handling property is usually good because it does not flow at room temperature. Further, when the temperature is 120 ° C. or lower, the resin composition is sufficiently softened at the operating temperature of the CPU, has good thermal conductivity, and is suitable as PCM.
PCM using a crystalline higher α-olefin copolymer having such a melting point is less likely to be sticky at room temperature, is excellent in storage and secondary workability, and melts uniformly at low temperatures. Even better.
As explained in (2) above, in the crystalline higher α-olefin copolymer, the half width (Wm) of the melting peak observed from the melting endothermic curve obtained using a differential scanning calorimeter (DSC). Is preferably 10 ° C. or lower, more preferably 6 ° C. or lower, and further preferably 2 to 4 ° C. Here, the half width (Wm) means a peak width at a height of 50% of the melting peak, and the smaller the half width, the more uniform crystals are formed. It shows the homogeneity of the olefin copolymer.
The half width of 10 ° C. or less indicates that the melting behavior is rapid. For example, even if the temperature is raised slightly above the melting point, the solid components disappear completely, all the components become liquid, and the melt viscosity becomes very small. Therefore, the thermal conductive resin composition can be sufficiently thinned at the operating temperature of the CPU. Thus, the thermal conductivity can be greatly improved.
Since the crystalline higher α-olefin copolymer satisfying the condition (3) has less stickiness compared to the case where X1 derived from side chain crystallization is not observed, this crystalline higher α-olefin copolymer The resin composition in which the coalescence is blended is excellent in strength. In addition, when a copolymer having a single peak derived from side chain crystallization is used, the crystal component of the copolymer is widened, resulting in a resin composition having a lot of stickiness and low strength. In particular, when the peak is not sharp, storability and secondary workability deteriorate. A method for measuring the wide-angle X-ray scattering intensity distribution will be described later.

As explained in (4) above, the crystalline higher α-olefin copolymer according to the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by GPC method of 1,000 to 10,000,000. It is preferable that it exists in the range, More preferably, it is 10,000-10,000,000. When the Mw is 1,000 or more, the strength of the heat conductive resin composition is improved, and when the Mw is 10,000,000 or less, kneading and molding become easy.
The crystalline higher α-olefin copolymer preferably has a molecular weight distribution (Mw / Mn) of 5.0 or less, more preferably 1.5 to 3.5, and still more preferably 1.5 to 3. .0. When the molecular weight distribution (Mw / Mn) is 5.0 or less, the composition distribution of the crystalline higher α-olefin copolymer is narrow, so that the heat conductive resin composition is not sticky and leads to an improvement in strength. In addition, the measuring method of a weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) is mentioned later.
Describing the above (5), the crystalline higher α-olefin copolymer has an isotactic structure and a stereoregularity index value M2 derived from a higher α-olefin chain having 10 or more carbon atoms is 50. It is preferably at least mol%. More preferably, it is 50-90 mol%, More preferably, it is 55-85 mol%, Most preferably, it is 55-75 mol%.
If the stereoregularity index value M2 is 50 mol% or more, the copolymer has an isotactic structure, the crystallinity of the copolymer is improved, and thus the stickiness of the heat conductive resin composition is suppressed, It leads to strength improvement. As described above, the effect of the present invention can be sufficiently obtained by controlling the stereoregularity preferably at a medium level or more, more preferably at a medium level. Also, the stereoregularity index value M4 (mol%), which is the same index as pentad isotacticity, is preferably 25 to 60 mol%, more preferably 25 to 40 mol%.
Further, the stereoregularity index value MR (mol%), which is an index of disorder of stereoregularity, is preferably 2.5 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more. .
The method for measuring the stereoregularity index values M2, M4 and MR will be described later.

Crystalline higher α- olefin copolymers, can be produced using a metallocene catalyst described below, and especially the ability to synthesize isotactic polymers, the transition of C ₂ symmetric and C ₁ symmetry it is preferable to use a metal compound, it is preferred to employ a transition metal compound of C ₂ symmetry.
That is, (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) a transition metal compound of component (A) or a derivative thereof to react with an ionic complex Two or more higher α-olefins having 10 or more carbon atoms or higher α having 10 or more carbon atoms in the presence of a polymerization catalyst containing a compound that can be formed and (B-2) an aluminoxane. -A method of copolymerizing one or more olefins with one or more other olefins.

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y.
Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other.
q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) And a crosslinked structure is formed via A ¹ and A ² .
E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. .
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X.
Specific examples of the Lewis base of Y include amines, ethers, phosphines and thioethers.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —CR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. Examples of such a crosslinking group include a general formula

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure. (E may represent an integer of 1 to 4)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, a diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.
q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I). X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.
Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , groups containing heteroatoms such as oxygen, halogen and silicon are preferred from the viewpoint of increasing the polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)- (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene ) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) Zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -Bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-me Len) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilyl) ) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-di-i-propylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethyl Silylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirco Nium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) Ridene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zyl Nium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1, 2'-diphenylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichrome (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1'-dimethylsilylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Lucylylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3 -Methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'- Methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1, 2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium Chloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 '-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2 1'-methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) ( 3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3,4-dimethylcyclopenta Dienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′ , 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadiene) Enyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) ( 3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3 '-Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-Methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene ) (3-Methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, ( , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopen Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclo) Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'- -Propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5 ' -N-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5 ' -Phenylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'- i-propylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadi) Nyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopenta Dienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-i-propyl) Cyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'-Diisopropylsilylene) (2,1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'-diisopropyl Rylene) (2,1′-diisopropylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, 1,2′-diphenylsilylene) (2,1′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-dimethylsilylene) (indenyl) ) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diisopropylsilylene) ) (2,1'-Dimethylsi Len) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2 '-Diisopropylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) (3 -Trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2 1'-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2'-Diisopropylsilylene) (2,1'-Dimethylsilylene) (Indenyl) (3-Trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-Dimethylsilylene) (2,1'-Diisopropyl Silylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diisopropylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride And those obtained by replacing zirconium in these compounds with titanium or hafnium, but are not limited thereto.
Further, it may be an analogous compound of another group or a lanthanoid series metal element.
In the above compound, (1,1 '-) (2,2'-) may be (1,2'-) (2,1'-) or (1,2 '-) (2,1 '-) May be (1,1'-) (2,2'-).

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (III) and (IV) can be used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ^3. )
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is An anion in which a plurality of groups are bonded to an element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5 to 15 element in the periodic table, preferably 13 to 13 in the periodic table. Indicates a group 15 element.
G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , Aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms A group, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. Two or more of G ^{1 to} G ^f may form a ring.
f represents an integer of [(valence of central metal M ¹ ) +1]. ), [Z ^{2] -} is the logarithm of the reciprocal of the acid dissociation constant (pKa) -10 below Bronsted acid alone or Bronsted acid and Lewis acid combination of conjugate base, or a general superacid defined The conjugate base of the acid to be produced is shown. In addition, a Lewis base may be coordinated.
R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group or fluorenyl group, R ¹³ represents an alkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include a hydrogen atom, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include a cyclopentadienyl group, methylcyclopentadi Examples thereof include an enyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
Specific examples of R ¹³ include phenyl group, p-tolyl group, p-methoxyphenyl group, and specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. it can.
Specific examples of M ² include Li, Na, K, Ag, Bu, Br, I, I 3 and the like. Specific examples of M ³ include Mn, Fe, Bo, Ni, Zn, and the like. Can be mentioned.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As and Sb, preferably B and Al is mentioned.
Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group and the like as an alkoxy group or an aryloxy group, Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Chill) phenyl group, bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, diphenyl boron, and the like.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acids and Lewis acids include trifluoromethanesulfonic acid anions (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ BO ₂₎ ^-, hexafluoroantimony anion (SbF ₆₎ ^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / SbF ₅ ) ^-, fluorosulfonic acid Ani On / 5- fluoride arsenic ^{_{(CSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - , and the like.

Specific examples of such an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, (B-1) component compounds include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Dimethylanilinium trakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrapheni Silver ruborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Tetraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, tri Examples thereof include silver fluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. In general, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (a) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (b) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (c) a metal There is a method of reacting water adsorbed on salts, etc., water adsorbed on inorganic substances and organic substances with organoaluminum compounds, (d) a method of reacting tetraalkyldialuminoxane with trialkylaluminum, and further reacting with water. . The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably the range of 2: 1 to 1:10 is desirable, and if it is in the above range, the catalyst cost per unit mass polymer does not increase and is practical.
When the compound (B-2) is used, the molar ratio is preferably in the range of 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical.
Moreover, as a catalyst component (B), (B-1) and (B-2) can also be used individually or in combination of 2 or more types.

The polymerization catalyst for producing the higher α-olefin copolymer (3) according to the present invention uses an organoaluminum compound as the component (B) in addition to the components (A) and (B). be able to.
Here, as the organoaluminum compound of component (B), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used alone or in combination of two or more.

The use ratio of the catalyst component (A) to the catalyst component (B) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is preferable.
By using the catalyst component (B), the polymerization activity per transition metal can be improved. However, if it is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
In the production of the crystalline higher α-olefin copolymer according to the present invention, at least one catalyst component can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.

The inorganic oxide support, _{specifically, SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, Fe 2 O 3, B 2 O 3, BaO, ZnO, BaO and ThO ₂ and mixtures thereof Examples thereof include silica alumina, zeolite, ferrite and glass fiber.
Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as a carrier other than the above, a magnesium compound represented by the general formula MgR ¹⁷ _x X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ or the like, or a complex salt thereof can be exemplified. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, polyarylate, starch, carbon, and the like.

The catalyst carrier used in the production of the crystalline higher α-olefin copolymer according to the present invention includes MgCl ₂ , MgCl (OC ₂ H ₃ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O. ₃ etc. are preferable.
Moreover, although the property of a support | carrier differs with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers. When the particle size is small, fine powder in the copolymer increases, and when the particle size is large, coarse particles in the copolymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.

If both the specific surface area and the pore volume are within the above ranges, the catalytic activity does not decrease. The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method [J. Am. Chem. Soc. , 60, 309 (1983)].
Further, when the carrier is an inorganic oxide carrier, it is usually preferred to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.

When at least one type of catalyst component is supported on the carrier, it is preferable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .
The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, the carrier is mixed with at least one of the components (a) (A) and (B). (B) a method in which the carrier is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (c) the carrier and (A ) Component and / or (B) component and organoaluminum compound or halogen-containing silicon compound, (d) (A) component or (B) component is supported on the carrier, (B) component or ( A) a method of mixing with the component, (e) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (f) in the contact reaction of the component (A) with the component (B). A method of allowing a carrier to coexist can be used. In the methods (d), (e), and (f), an organoaluminum compound as the component (C) can also be added.

The catalyst thus obtained may be used for copolymerization after removing the solvent once as a solid and may be used for copolymerization as it is.
In the production of the crystalline higher α-olefin copolymer according to the present invention, the catalyst is produced by carrying the supporting operation on at least one of the carrier (A) and the component (B) in the polymerization system. be able to. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (B) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa (gauge), and -20 to 20 A method of preliminarily polymerizing at 200 ° C. for about 1 minute to 2 hours to produce catalyst particles can be used.

The use ratio of the component (B-1) and the carrier in the catalyst used for the production of the crystalline higher α-olefin copolymer according to the present invention is preferably 1: 5 to 1: 10000, more preferably by mass ratio. The ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1 in terms of mass ratio. : 50 is preferable.
When using 2 or more types as a component (B), it is preferable that the usage ratio of each (B) component and a support | carrier is in the said range by mass ratio. In addition, the ratio of the component (A) to the carrier is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.

If the use ratio of component (B) [component (B-1) or (B-2)] and the carrier and the use ratio of component (A) and the carrier are within the above ranges, the activity may be reduced. Absent.
The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50-500 m ² / g.
When the average particle size is 2 μm or more, fine powder in the copolymer does not increase, and when it is 200 μm or less, coarse particles in the copolymer do not increase. When the specific surface area is 20 m ² / g or more, the activity does not decrease, and when it is 1000 m ² / g or less, the bulk density of the copolymer does not decrease.
When the amount of transition metal is within the above range, the activity is good. In this way, a copolymer having an industrially advantageous high bulk density and excellent particle size distribution can be obtained by supporting it on a carrier.

In the crystalline higher α-olefin copolymer according to the present invention, the copolymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, etc. However, a slurry polymerization method and a gas phase polymerization method are particularly preferable.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably from raw material monomer / component (A) (molar ratio).
The polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).

In the method for producing a crystalline higher α-olefin copolymer according to the present invention, it is preferable to add hydrogen since polymerization activity is improved. When hydrogen is used, it is usually from normal pressure to 5 MPa (gauge), preferably from normal pressure to 3 MPa (gauge), more preferably from normal pressure to 2 MPa (gauge).
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane Halogenated hydrocarbons such as chloroform and dichloromethane can be used.
These solvents may be used alone or in combination of two or more. A monomer such as α-olefin may be used as a solvent. Depending on the copolymerization method, it can be carried out without solvent.

In the copolymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used.
The olefin used in the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used in the copolymerization.

The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 130 ° C, more preferably 0 to 80 ° C.
In the prepolymerization, aliphatic hydrocarbons, aromatic hydrocarbons, monomers and the like can be used as solvents. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the limiting viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.1 deciliter / g or more, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1. It is preferable to adjust conditions so that it may become -10000g, especially 10-1000g.
As a method for adjusting the molecular weight of the copolymer, there are selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen. An inert gas such as nitrogen may be present.
By the above method, the crystalline higher α-olefin copolymer according to the present invention can be efficiently produced. The obtained crystalline higher α-olefin copolymer is excellent in low-temperature characteristics, rigidity, heat resistance, and compatibility with a thermally conductive filler.

  In the thermally conductive resin composition of the present invention, specific examples of the thermally conductive filler used as the component (b) include zinc oxide, magnesium oxide, beryllium oxide, alumina, silicon dioxide, titanium dioxide, mica, potassium titanate, Examples thereof include oxide particles such as iron oxide and talc, nitride particles such as aluminum nitride, boron nitride and silicon nitride, carbide particles such as silicon carbide, and metal particles such as copper and aluminum. You may use these in mixture of 2 or more types.

The thermally conductive resin composition of the present invention includes a combination comprising (a) 5 to 95% by mass of a crystalline higher α-olefin polymer and (b) 95 to 5% by mass of a thermally conductive filler. (A) It is 15-90 mass% of components, (b) It is 85-10 mass% of components. When the content of the thermally conductive filler of component (b) is 5% by mass or more, sufficient thermal conductivity is obtained, and when it is 95% by mass or less, molding becomes easy.
The heat conductive resin composition of this invention can be manufactured by dry-blending (a) component and (b) component previously, and knead | mixing this with a universal mixing stirrer, a kneader, etc.
By molding the heat conductive resin composition of the present invention, a phase change type heat transfer / heat radiation material having high heat conductivity can be obtained. The shape of the heat transfer / heat dissipation material can be a sheet or a film. This sheet or film preferably has a thickness of 0.02 to 3 mm, more preferably 0.05 to 1 mm. When the thickness is 0.02 mm or more, the handleability is excellent, and when it is 3 mm or less, sufficient thermal conductivity is obtained.

Although the heat conductive resin composition of this invention has sufficient intensity | strength by the mixing | blending of the said (a) component and (b) component, in order to raise intensity | strength further, a softening point is 40-130 degreeC. The resin can be replaced with part of the component (a). Examples of such resins include polyethylene, ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, and the like can be used alone or in combination of two or more. The amount added is 80% by mass or less, preferably 50% by mass or less of the component (a). The softening point here is a melting point measured by DSC.
When a softening agent is added to the heat conductive resin composition of the present invention, the fluidity of the heat conductive resin composition is improved, so that the adhesion between the heat-generating component and the radiator is improved. Further improve. Softeners include vegetable softeners (cotton seed oil, linseed oil, rapeseed oil, etc.), mineral softeners (paraffinic oil, naphthenic oil, aromatic oil, etc.), synthetic plasticizers (dioctyl phthalate, dibutyl phthalate) , Dioctyl adipate, isodecyl adipate, dioctyl sebacate, dibutyl sebacate, etc.) can be used. These can be used individually by 1 type or in combination of 2 or more types. Of these, paraffinic oil and naphthenic oil are particularly preferred. The addition amount is 0 to 50% by mass, preferably 0 to 10% by mass, based on the thermally conductive resin composition.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 (Production of crystalline higher α-olefin copolymer)
(1) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium chloride (catalyst) In a nitrogen stream, into a 200 ml Schlenk bottle (1, 2.5 g (7.2 mmol) of 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 ml of ether were added. After cooling to −78 ° C., 9.0 ml (14.8 mmol) of a hexane solution (1.60 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane and dried under reduced pressure to obtain a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indene). Obtained quantitatively as a white solid.
6.97 mmol of the obtained lithium salt was dissolved in 50 ml of THF (tetrahydrofuran) in a Schlenk bottle, and 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise at room temperature, followed by stirring for 12 hours. did.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated aqueous ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was distilled off to obtain 3.04 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) (5. 9 mmol) was obtained (yield 84%).
Then, under a nitrogen stream, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above and ether 50 milliliters was added to the Schlenk bottle. After cooling to −78 ° C., 7.4 ml (11.8 mmol) of a hexane solution (1.60 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 40 ml of hexane to obtain 3.06 g of a lithium salt as an ether adduct. When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (90 MHz, THF-d ₈ ): δ 0.04 (s, -SiMe ₃ , 18H), 0.48 (s, -Me ₂ Si-, 12H), 1.10 (t, -CH ₃ , 6H), 2.59 (s, -CH 2 -, 4H), 3.38 (q, -CH 2 -, 4H), 6.2-7.7 (m, Ar-H, 8H)

Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene. This was cooled to −78 ° C., and 1.2 g (5.1 mmol) of zirconium tetrachloride suspended in 20 ml of toluene in another Schlenk bottle and cooled to −78 ° C. in advance was added dropwise thereto. After completion of dropping, the mixture was stirred at room temperature for 6 hours.
After the solvent of the reaction solution was distilled off, the residue was recrystallized with dichloromethane to obtain (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium chloride. Of 0.9 microgram (1.33 mmol) of yellow fine crystals (yield 26%). When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (90 MHz, CDCl ₃ ): δ0.0 (s, -SiMe ₃ , 18H), 1.02, 1.12 (s, -Me ₂ Si-, 12H), 2.51 (dd,- _{CH 2 -, 4H), 7.1-7.6} (m, Ar-H, 8H)

(2) Production of Crystalline Higher α-Olefin Copolymer 140 g of “Linearene 2024” (mainly a mixture of α-olefins having 20, 22, and 24 carbon atoms) manufactured by Idemitsu Kosan Co., Ltd. in a heat-dried 1 liter autoclave. And 200 ml of heptane were added to bring the temperature to 50 ° C., and then 1 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride. 5 micromoles, dimethylanilinium tetrakispentafluorophenylborate 25 micromoles were added, hydrogen 0.03MPa was introduce | transduced, and it copolymerized for 1 hour.
After completion of the copolymerization reaction, the reaction product was precipitated with acetone and then dried under heating and reduced pressure to obtain 80 g of a crystalline higher α-olefin copolymer. The physical property measurement results of the obtained copolymer are shown in Table 1. In addition, when the melting point (Tm) was measured by the following measuring method, one peak was observed.

(1) DSC measurement Using a differential scanning calorimeter (Perkin Elmer, DSC-7), 10 mg of a sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to −10 ° C. at 5 ° C./min. After maintaining at −10 ° C. for 5 minutes, the melting point (Tm) of the peak top of the melting peak observed from the melting endothermic curve obtained by raising the temperature to 190 ° C. at 10 ° C./min was measured.
(2) Wide-angle X-ray scattering intensity distribution Using an anti-cathode type rotor flex (Rigaku Corporation, RU-200), a monochromatic light of 30 kV, 100 mA output CuKα ray (wavelength = 0.154 nm) is 1.5 mm. Then, using a position sensitive proportional counter, wide-angle X-ray scattering (WAXS) intensity distribution was measured with an exposure time of 1 minute.
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
It measured with the following apparatus and conditions by the gel permeation chromograph (GPC) method. For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn), polystyrene-converted values obtained from a standard polystyrene calibration curve were used.
GPC measurement device Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
(4) Stereoregularity index values M2, M4 and MR
T.A. Asakura, M .; Denura, Y .; It was determined according to the method proposed by “Macromolecules, 24, 2334 (1991)” reported by Nishiyama. That is, by using the ¹³ C nuclear magnetic resonance spectrum, the CH ₂ carbon derived from the higher α-olefin is split and reflects the difference in stereoregularity, and is observed. Can be requested. It shows that isotacticity is so high that M2 is large. The measurement was performed with the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Solvent: 1,2,4-trichlorobenzene / heavy benzene = 90/10 mixed solvent (volume ratio)
Temperature: 130 ° C
Pulse width: 45 °
Integration count: 1000 times

The stereoregularity index values M2, M4, and MR were calculated as follows. That is, six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm, and among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift. At this time, an absorption peak based on CH ₂ carbon at the α-position of the side chain is observed in the vicinity of 34 to 37 ppm. At this time, M2, M4, and MR (mol%) are obtained by the following formula.
M2 = [(integral intensity of 36.2 to 35.3 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100
M4 = [(integral intensity of 36.2 to 35.6 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100
MR = [(integral intensity of 35.3 to 35.0 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100

The sheets obtained in the following examples and comparative examples were evaluated by the following methods.
(1) Thermal conductivity It measured by the hot disk method (unsteady surface heat source method) using the hot disk method thermophysical property measuring apparatus (Kyoto Electronics Industry Co., Ltd. make, TPA-501). In this measurement method, a sensor (made of polyimide, diameter: 6.631 mm) is sandwiched between two test pieces (the above sheet), a constant current is passed through the sensor, and a constant heat is generated. This is a method for measuring thermal conductivity. The measurement temperature was 55 ° C., and the sample was tightened to a torque of 30 cN · cm using a torque wrench.
(2) Thermal resistance A resin material thermal resistance measuring device (manufactured by Hitachi, Ltd.) was used to measure the temperature by a temperature of 60 ° C., a constant thickness mode, and a steady method.
(3) Formability at 100 ° C. The thermally conductive resin composition is sandwiched between two aluminum plates, heated at 100 ° C. for 2 minutes, molded with a pressure of 294 N (30 kgf), and molded according to the following evaluation criteria. Evaluated.
○: A good sheet was obtained without breaking.
Δ: A sheet was obtained, but was often broken when peeled from the aluminum plate.
X: A sheet cannot be produced and cannot be evaluated.

Examples 1-3
The crystalline higher α-olefin copolymer obtained in Production Example 1 and aluminum nitride powder (H grade made by Tokuyama Co., Ltd.) are dry blended at a mass ratio shown in Table 2 and put into a batch type lab plast mill. Then, the mixture was kneaded for 5 minutes at a temperature of 150 ° C. and a rotation speed of 50 rpm. During kneading, no leakage from the molding machine cylinder occurred, and the production was extremely easy.
The obtained resin composition was compression molded at a temperature of 100 ° C. for 2 minutes using a tabletop press machine (manufactured by Shindo Metal Industry Co., Ltd.), and 2 sheets of 50 mm length, 50 mm width and 2 mm thickness were obtained. A sheet was produced. The compression molding of the resin compositions of Examples 1 and 2 was extremely good, and the obtained sheets also had sufficient mechanical strength and excellent handleability. Although the resin composition of Example 3 had a slightly high melt viscosity, it could be compression-molded, and the resulting sheet had no problem with the mechanical strength and did not break during handling.
About the obtained sheet | seat, the heat conductivity and the moldability in 100 degreeC were evaluated by said method. The results are shown in Table 2.

Example 4
The crystalline higher α-olefin copolymer obtained in Production Example 1 and alumina (Showa Denko Co., Ltd., CB-A50) were dry blended at a mass ratio shown in Table 2, and the same as in Examples 1 to 3 It knead | mixed by the method of. During kneading, no leakage from the forming cylinder occurred, and the production was extremely easy. Sheets were produced in the same manner as in Examples 1 to 3 using the obtained resin composition. The compression moldability of the resin composition was extremely good. The obtained sheet also had sufficient mechanical strength, and there was no problem in handling.
About the obtained sheet | seat, the heat conductivity and the moldability in 100 degreeC were evaluated by said method. The results are shown in Table 2.

Example 5
Table 2 shows the crystalline higher α-olefin copolymer, ethylene-vinyl acetate copolymer (Tm = 59.5 ° C.) and aluminum nitride (H grade manufactured by Tokuyama Co., Ltd.) obtained in Production Example 1. Dry blending was performed at the indicated mass ratio, and kneading was performed in the same manner as in Examples 1 to 3. During kneading, no leakage from the forming cylinder occurred, and the production was extremely easy.
Two sheets having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm were produced in the same manner as in Examples 1 to 3, using the obtained resin composition. The compression moldability of the resin composition was extremely good. The mechanical properties of the obtained sheet were considerably superior to those of Examples 1 to 4, and were not damaged even when bending strain was applied by hand.
About the obtained sheet | seat, the heat conductivity and the moldability in 100 degreeC were evaluated by said method. Further, a sheet having a length of 10 mm, a width of 10 mm, and a thickness of 0.1 mm was produced in the same manner as in Examples 1 to 3. About this 0.1 mm sheet | seat, the thermal resistance was measured by said method.
These results are shown in Table 2.

Comparative Examples 1-3
In Examples 1 to 3, instead of the crystalline higher α-olefin copolymer, the paraffin having physical properties shown in Table 1 (manufactured by Hiroshima Wako Co., Ltd., melting point described in the catalog = 52 to 54 ° C.) is shown in Table 2. Using the indicated mass ratios, dry blending was performed in the same manner as in Examples 1 to 3, and kneading and compression molding were similarly performed to produce sheets, and the same evaluation was performed. The results are shown in Table 2.
The resin composition of Comparative Example 1 has a very poor kneadability and compression moldability, such as leakage from the mold gap during molding, and breakage during mold release. I could not. The resin composition of Comparative Example 2 had no problem in compression moldability, but the obtained sheet was quite brittle, such as cracking unless handled carefully. The resin composition of Comparative Example 3 was not plasticized even when heated to 150 ° C., and a sheet could not be produced.
The thermal conductivity of the sheet of Comparative Example 2 was measured by the same method as in Examples 1 to 3. Since a satisfactory sheet could not be obtained from the resin compositions of Comparative Examples 1 and 3, the thermal conductivity could not be measured.

Comparative Example 4
In Example 5, instead of the crystalline higher α-olefin copolymer, the mass shown in Table 2 is the paraffin having physical properties shown in Table 1 (manufactured by Hiroshima Wako Co., Ltd., melting point = 52 to 54 ° C. described in the catalog). The ratio was used, dry blended in the same manner as in Example 5, and similarly kneaded and compression molded to produce a sheet, and the same evaluation was performed. The compression moldability was very good. The obtained sheet was excellent in mechanical properties and was not damaged even when bending strain was applied by hand. The other evaluation results are shown in Table 2.

A phase change material (PCM) having excellent thermal conductivity can be provided by a thermally conductive resin composition containing a crystalline higher α-olefin copolymer.
This heat conductive resin composition can be suitably used as a phase change type heat transfer / heat dissipation material for heat-generating electronic components.

Claims (6)

  A heat conductive resin composition comprising a combination of (a) a crystalline higher α-olefin copolymer of 5 to 95% by mass and (b) 95 to 5% by mass of a heat conductive filler.   The thermally conductive resin composition according to claim 1, wherein the crystalline higher α-olefin copolymer of component (a) contains 50 mol% or more of α-olefin units having 10 or more carbon atoms.   The thermal conductive resin composition according to claim 1 or 2, wherein the melting point (Tm) of the component (a) observed from a melting endothermic curve obtained by using a differential scanning calorimeter (DSC) is 30 to 120 ° C. object.   The heat conductive resin composition in any one of Claims 1-3 which replaced 80 mass% or less of (a) components with resin softened at 40-130 degreeC.   The heat-transfer / heat radiation material which consists of a heat conductive resin composition in any one of Claims 1-4. The heat-transfer / heat-dissipation material according to claim 5, which is a sheet or film having a thickness of 0.02 to 3 mm.