WO2008044523A1

WO2008044523A1 - Low-hardness thermally conductive resin composition and sheet-form radiating member made therefrom

Info

Publication number: WO2008044523A1
Application number: PCT/JP2007/069186
Authority: WO
Inventors: Junichi Matsumoto; Matsunori Yasuyoshi; Takio Homma
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2006-10-13
Filing date: 2007-10-01
Publication date: 2008-04-17
Also published as: TW200829650A; JP5265885B2; JP2008115356A

Abstract

A low-hardness thermally conductive resin composition which is a non-silicone thermally conductive composition having excellent flexibility although a filler is contained therein in a large amount. It is suitable for use in various applications where thermal conductivity is required. The low-hardness thermally conductive resin composition is characterized by comprising (A) one or more polyol compounds comprising (a-1) 10-100 mass% product of the hydrogenation of a hydroxylated polyisoprene and (a-2) 90-0 mass% product of the hydrogenation of a hydroxylated polybutadiene, (B) at least one thermally conductive filler selected among metal hydroxides, metal oxides, and metal nitrides, and (C) a hardener, the amount of the ingredient (B) being 100-5,000 parts by mass per 100 parts by mass of the ingredient (A) and the amount of the ingredient (C) being such that the molar ratio of the reactive groups as the hardener in the ingredient (C) to the hydroxy groups contained in the ingredient (A) is 0.5-2.5.

Description

Specification

Low hardness heat conductive resin composition and sheet-like heat radiation member using the same

The present invention relates to a low-hardness heat conductive resin composition and a sheet-like heat radiating member using the same. More specifically, the present invention relates to a low-hardness heat conductive resin composition suitably used for various uses as a heat conductive material, in particular, a sheet-shaped heat radiation member excellent in heat dissipation, tackiness, and flexibility, and the resin composition. The present invention relates to a sheet-like heat release member having the above-mentioned properties, which is obtained by molding and curing a product.

Background art

[0002] Heat transfer materials with high heat transfer efficiency, adhesives, sealing materials, etc. are required for cooling or radiating heat sources in various fields including the automotive field, home appliance field, electrical and electronic field, and communication field. Yes. In particular, in the semiconductor field, removal of heat generated by integration and higher frequency is an issue. Therefore, a heat-dissipating sheet is generally used to dissipate heating elements such as ICs and CPUs used in electrical equipment and electronic parts such as plasma displays, transistors, capacitors, and personal computers. The high

V, thermal conductivity, flexibility and panel retention are required! /

On the other hand, in the field of electronic materials, light weight and good insulation properties / plastics and rubbers have come to be used in many cases. However, these materials have a problem that it is difficult to conduct heat compared to metals and the like. Etc. have been improved. However, increasing the amount of filler added to increase thermal conductivity will cause problems such as being hard and fragile.

In order to solve such problems, heat dissipation materials using silicone have been widely used so far. However, it has been pointed out that low molecular weight silicone contained in silicone evaporates and adheres to contacts, resulting in poor contacts. On the other hand, urethane-based heat radiating materials are also disclosed, and polyether polyols and polyester polyols have poor electrical insulation. In addition, polybutadiene-based polyols have many double bonds and thus have low heat resistance. In addition, silicone and polyether polyol-based or polyester polyol-based polyurethane have drawbacks such as low moisture resistance, and the heat dissipation filler absorbs water. There is a possibility that long-term stability may be a problem.

A polybutadiene polyol hydrogenated product that improves the disadvantages of polybutadiene polyurethane is also disclosed, but it is difficult to form a film when a large amount of hardened filler is added, and adhesion to heating elements, heat sinks, etc. However, there are problems such as the formation of bad gaps and reduced thermal conductivity.

For example, a urethane-based heat dissipation material composition containing a hydrogenated product of a polyhydroxybutadiene polymer as a main component is disclosed (for example, see Patent Document 1). However, in this composition, there is a problem in that the Shore A hardness (25 ° C) when blended with about 80% by mass of the filler is as high as about 90/25.

In addition, (1) high heat obtained by laminating a sheet made by impregnating or applying a thermosetting resin with a heat deformation temperature in the range of -130 ° C to 130 ° C on a cloth woven with metal fibers. Conductive laminate (see, for example, Patent Document 2), (2) A gel composed of an elastomer material that can be deformed flexibly and can be brought into close contact with the heating element, the elastomer material strength being a urethane resin and a plasticizer as main components. Heat-dissipating material in which fine particles of ceramic material are dispersed as a heat-conducting filler (for example, refer to Patent Document 3), (3) polyol, and inorganic filler having a particle size of 0.157 mm or less A polyol composition for a heat dissipating polyurethane resin composition, wherein the inorganic filler is contained in an amount of 100 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the polyol. Heat dissipation material containing polyurethane resin composition ( For example, see Patent Document 4), (4) A heat-dissipating sheet in which aluminum hydroxide is dispersed and contained as a granular filler in a polyurethane composed of castor oil-modified polyol and isocyanate, and has a thermal conductivity by a steady parallel plate method. A heat-dissipating sheet (see, for example, Patent Document 5) having a flame retardance level of UL94 of better than V-2 of 0.5 to 1.0 W / mK is disclosed.

However, the above (1) to (4) are all technologies related to polyurethane-based heat dissipation materials, but do not use polyisoprene-based polyol hydrogenated products as the main agent.

Yes

On the other hand, a technique of adding process oil has been disclosed as an attempt to lower the hardness of the heat-dissipating composition and improve the thermal conductivity (see, for example, Patent Document 6). This force The technology uses a non-crosslinked styrenic thermoplastic elastomer as the matrix and is not a cured product of a polyisoprene polyol hydrogenated product as the main ingredient.

[0004] Patent Document 1: JP-A-58-122912

Patent Document 2: JP-A-5-16275

Patent Document 3: Japanese Patent Laid-Open No. 11-111899

Patent Document 4: Japanese Patent Laid-Open No. 2000-226426

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-342758

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2006-193626

Disclosure of the invention

Problems to be solved by the invention

[0005] Under such circumstances, the present invention is a non-silicone-based heat conductive compound having excellent flexibility in spite of containing a large amount of filler, and various applications that require heat conductivity. Particularly, a low-hardness heat conductive resin composition suitably used for a sheet-like heat radiation member excellent in heat dissipation, tackiness, and flexibility, and a sheet shape having the above-mentioned properties formed by molding and curing the resin composition. The object is to provide a heat dissipation member.

Means for solving the problem

[0006] As a result of intensive studies to achieve the above object, the inventors of the present invention have obtained a predetermined ratio of hydrogenated hydroxyl-containing polyisoprene and hydrogenated hydroxyl group-containing polybutadiene. In addition, at least one selected from metal hydroxides, metal oxides and metal nitrides as a heat conductive filler, and preferably a polyisocyanate compound as a curing agent are blended in a predetermined ratio, respectively. Thus, it has been found that the object can be achieved by a resin composition obtained by blending a plasticizer, particularly a hydrocarbon plasticizer, in a predetermined ratio. The present invention has been completed on the basis of power and knowledge.

That is, the present invention

[1] (A) (a-1) Hydrogenated polyisoprene containing hydroxyl group 10 to 100% by mass

And (a-2) a polyol compound consisting of 90 to 0% by mass of a hydrogenated hydroxyl group-containing polybutadiene, and (B) a small amount selected from metal hydroxides, metal oxides and metal nitrides. At least one heat conductive filler and (C) a curing agent, and the content of component (B) is 100 to 5000 parts by mass with respect to 100 parts by mass of (A) component, and The content of the component (C) is such that the molar ratio of the reactive group as the curing agent in the component (C) / the hydroxyl group in the component (A) is 0.5 to 2.5. Low hardness heat conductive resin composition,

[2] The low-hardness heat conductive resin composition according to the above [1], further comprising a plasticizer as the component (D) at a ratio of 1000 parts by mass or less with respect to 100 parts by mass of the component (A).

[3] The above-mentioned (a-1) component-containing polyisoprene having a hydrogenation power S, a number average molecular weight of 200 to 20000, and having a 1,4 bond of 50 mol% or more in the microstructure [1] Or the low hardness heat conductive resin composition according to [2],

[4] The hydrogenated hydroxyl-containing polybutadiene component (a-2) has a number average molecular weight of 200 to 20000 and has a mono-ratio of 1,2—bonds and 1,4 bonds in its microstructure. The low-hardness heat conductive resin composition according to any one of [1] to [3], wherein is 50:50 to 95: 5,

[5] The low-hardness heat conductive resin composition according to any one of the above [1] to [4], which is a curing agent power S of the component (C) and a polyisocyanate compound,

[6] The low-hardness heat conductive resin composition according to any one of the above [2] to [5], wherein the plasticizer of component (D) is a hydrocarbon plasticizer, and

[7] A sheet-like heat dissipation member formed by molding and curing the low-hardness heat conductive resin composition according to any one of [1] to [6] above,

Is to provide.

The invention's effect

[0007] According to the present invention, a non-silicone-based heat conductive compound having excellent flexibility in spite of containing a large amount of filler, and for various uses that require heat conductivity, particularly heat dissipation. A low-hardness heat conductive resin composition suitably used for a sheet-like heat dissipation member having excellent properties, tackiness, and flexibility, and a sheet-like heat dissipation member having the above-mentioned properties formed by molding and curing the resin composition Can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] First, the low hardness heat conductive resin composition of the present invention will be described. The low-hardness heat conductive resin composition of the present invention (hereinafter sometimes simply referred to as a resin composition) includes: (A) (a-1) Hydrogenated polyisoprene containing hydroxyl group 10 to 100% by mass; (A-2) a polyol compound comprising 90 to 0% by mass of a hydrogenated hydroxyl-containing polybutadiene, and (B) at least one selected from metal hydroxides, metal oxides and metal nitrides A resin composition comprising a thermally conductive filler, (C) a curing agent, and optionally (D) a plasticizer.

[Polyol compound]

In the resin composition of the present invention, the polyol compound used as the component (A) includes (a 1) a hydrogenated polyisoprene 10 to 100% by mass; and (a-2) hydrogen of a hydroxyl-containing polybutadiene. It is a polyol compound comprising 90 to 0% by mass of an additive, and is a component that forms a flexible matrix by reacting with a curing agent that is a component (C) described later.

In the present invention, by using a hydrogenated product of (a-1) hydroxyl group-containing polyisoprene as the polyol compound, the intended low-hardness heat conductive composition can be obtained. Hydrogenation of this hydroxyl group-containing polyisoprene The number average molecular weight Mn of the product is preferably in the range of 200-20000. If this number average molecular weight Mn is 200 or more, the cured product will have an appropriate rubber elasticity that will not be too hard, and if it is 20000 or less, it will have an appropriate viscosity and can be uniformly blended. . A more preferred number average molecular weight Mn is in the range of 500 to 10000, and particularly preferably in the range of 1000 to 5000. The number average molecular weight Mn is a value in terms of polystyrene measured by a gel permeation chromatography method (GPC method).

In the hydroxylated polyisoprene hydrogenated product, the number of hydroxyl groups in one molecule is preferably in the range of 1.7 to 4.0 on average. If the number of hydroxyl groups is 1.7 or more, curing is sufficiently performed and stickiness of the cured product is suppressed, while if it is 4.0 or less, the cured product has an appropriate crosslinking density. In addition, the gelation of the compound and the compound is suppressed, and a product with good quality can be obtained. The number of hydroxyl groups is more preferably 1.8 to 3.0 on average, and 1.9 to 2.5 is particularly preferable. In the hydrogenated product of the hydroxyl group-containing polyisoprene In this case, the position of the hydroxyl group may be either at the end of the molecular chain or inside the molecular chain, but the one at the end of the molecular chain is preferred.

Furthermore, in the hydrogenated product of the hydroxyl group-containing polyisoprene, in the microstructure, 1, 4 bonds are usually 50 mol% or more, preferably 70 mol% or more, from the viewpoint of rubber elasticity.

In addition, other copolymerizable monomer units such as styrene, ethylene, propylene, and a gen compound can be included as long as the characteristics are not impaired.

[0010] <Hydrogenated product of hydroxyl-containing polybutadiene>

In the present invention, in order to obtain a resin composition having a large amount of the heat conductive filler of component (B) and high heat conductivity, the hydroxyl group of component (a-1) is used. In addition to the hydrogenated polyisoprene, a hydrogenated hydroxyl-containing polybutadiene can be used in combination as the component (a-2).

The number average molecular weight Mn in the hydroxylated polybutadiene hydrogenated product and the number and position of hydroxyl groups in one molecule are the same as those of the hydroxylated polyisoprene hydrogenated product described above.

In the hydroxylated polybutadiene hydrogenated product, the molar ratio of the 1,2 bond and the 1,4 bond is preferably 50:50 to 95: 5 in the microstructure. When the molar ratio is within the above range, the cured product is liquid at room temperature and is easy to handle, and the cured product has moderate flexibility, and is less sticky and has good mechanical strength. More preferred for 1, 2—bonds and 1,4 bonds! / ヽ Monolayers (between 50:50 and 85:15, especially 50: 50—75: 25 forces.

Furthermore, the hydrogenated product of the hydroxyl group-containing polybutadiene may contain other copolymerizable monomer units such as styrene, ethylene, propylene, and a gen compound as long as the characteristics are not impaired.

[0011] In the resin composition of the present invention, when the hydrogenated hydroxyl-containing polybutadiene component (a-2) is used in combination with the hydroxylated polyisoprene hydrogenated component (a-1), The blending ratio of the (a-1) component and the (a-2) component is 10 to 80% by mass of the (a-1) component from the viewpoint of the blending effect of the (a-2) component. The component is 90-20% by mass And force S, preferably (a-1) component is 25 to 75% by mass and (a-2) component is 75 to 25% by mass.

In the resin composition of the present invention, a raw material for the hydrogenated hydroxyl-containing polyisoprene used as the component (a-1) and, if necessary, the hydrogenated hydroxyl-containing polybutadiene used as the component (a-2) A certain hydroxyl group-containing polyisoprene and hydroxyl group-containing polybutadiene can be easily produced by a conventionally known method, for example, radical polymerization or anion polymerization, which is not particularly limited in its production method.

For example, in the case of radical polymerization of isoprene or butadiene which is a gen monomer, hydrogen peroxide, an azo compound having a hydroxyl group (for example, 2, 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide, etc.] Alternatively, a hydroxyl group-containing liquid polyisoprene or polybutadiene can be obtained by radical polymerization using a hydroxyl group-containing peroxide (such as cyclohexanone peroxide) as a polymerization initiator. For example, 1.0 to 50 g when using HO, 5.0 to when using 2,2′azobis [2-methyl-N- (2-hydroxyethyl) propionamide];! OOg, cyclohexa When non-peroxide is used, 5.0 ~;! OOg force S is appropriate for each.Polymerization can be performed without solvent. It is preferable to use a solvent for ease of control, etc. Ethanol, isopropanol, n-butanol, etc. are usually used as the solvent, the reaction temperature is 80 to 150 ° C, the reaction time is 0.5 to 15 hours. Is appropriate.

In addition, when anion polymerization of isoprene or butadiene is carried out, a dilithium compound such as naphthalene dilithium is used as a catalyst, a living monomer is produced by anionic polymerization of a gen monomer, and a hydroxyl group can also be reacted with a monoepoxy compound or the like. Liquid-containing polyisoprene or polybutadiene can be obtained. Polymerization can be carried out without solvent It is preferable to use a solvent from the same viewpoint as in the case of radical polymerization. As the solvent, saturated hydrocarbons such as hexane and cyclohexane are preferably used. The reaction temperature is 50 to 100 ° C, the reaction time is 1 to 10 hours. As the monoepoxy compound, for example, ethylene oxide or propylene oxide can be used. Using such a dilithium compound as a catalyst, living polymer is produced by anionic polymerization. The method of producing the compound and reacting the monoepoxy compound and the like is usually a preferable method because a polyol compound having a hydroxyl group at both ends of the molecular chain can be obtained and the microstructure can be controlled.

In both the radical polymerization method and the anion polymerization method, if desired, another copolymerizable monomer, for example, styrene, ethylene, propylene, a gen-based compound, or the like can be appropriately copolymerized.

The hydroxyl group-containing polyisoprene and the hydroxyl group-containing polybutadiene thus obtained are subjected to hydrogenation treatment by a conventionally known method to obtain a desired hydroxyl group-containing polyisoprene hydrogenated product and a hydroxyl group-containing polybutadiene hydrogenated product. Can do. The hydrogenation treatment is performed, for example, in an organic solvent under hydrogen pressure and in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, for example, palladium carbon, reduced nickel, rhodium-based heterogeneous catalyst, Ziegler-based homogeneous catalyst, or the like can be used.

Yes

In the case of using a heterogeneous catalyst, the hydrogenation reaction is performed in a suitable organic solvent at a reaction temperature of from room temperature to about 200 ° C. and under a hydrogen pressure of from about normal pressure to about 1 LOMPa. The reaction time is about! -48 hours.

On the other hand, when a homogeneous catalyst is used, the hydrogenation reaction is carried out in a suitable solvent at a reaction temperature of from room temperature to about 150 ° C. under a hydrogen pressure of from about normal pressure to about 5 MPa. The reaction time is about 1 to 24 hours.

Conductive filler]

In the resin composition of the present invention, at least one particle selected from metal hydroxide particles, metal oxide particles, and metal nitride particles is used as the thermal conductive filler of component (B).

Here, examples of the metal hydroxide particles include particles such as aluminum hydroxide and magnesium hydroxide, and examples of the metal oxide particles include particle forces such as aluminum oxide, titanium oxide, magnesium oxide, and silicon oxide. Examples of the nitride particles include boron nitride, silicon nitride, and aluminum nitride particles. In addition, as the thermal conductive filler of this component (B), metal particles such as copper, aluminum, iron, carbon carbide, etc. It is also possible to use materials and materials that easily conduct heat, such as metal carbide particles.

These may be used alone or in combination of two or more. Among them, alumina particles, aluminum nitride particles, aluminum hydroxide particles, boron nitride particles, heat conductivity with good dispersibility It is preferable because the properties can be increased. Especially in applications that require electrical insulation, alumina particles, aluminum nitride particles, and boron nitride particles are preferred because of their high electrical insulation and high thermal conductivity, and metal oxide particles and metal nitride particles are preferred as materials. Good. In these heat conductive fillers, the particle size and particle size distribution can be appropriately selected according to applications such as high filling properties and thin film formability, which may be powdery, granular, spherical or needle-like. Moreover, the surface treatment may be performed for the purpose of improving the wettability of the matrix and the filler.

In the resin composition of the present invention, the thermal conductive filler of the component (B) is blended at a ratio of 100 to 5000 parts by mass with respect to 100 parts by mass of the component (A). If this blending amount is 100 parts by mass or more, good thermal conductivity can be obtained, and if it is 5000 parts by mass or less, appropriate flexibility can be secured and a homogeneous molded body can be produced. Can do. The preferred blending amount of the component (B) is 200 to 4000 parts by mass, and particularly preferably 800 to 2500 parts by mass.

[Curing agent]

In the resin composition of the present invention, as the component (C), a curing agent that reacts with the hydroxyl group of the polyol compound of the component (A) to crosslink and cure the component (A) is used. As this curing agent, a polyisocyanate compound is suitable from the viewpoint of the physical properties of the resulting cured product. This polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and the kind thereof is not particularly limited.

As this polyisocyanate compound, known aromatic, aliphatic and alicyclic compounds can be listed. Specifically, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4,1 and 2,2, -diphenylmethane diisocyanate (All MDI), tolylene diisocyanate (TDI), carpositimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, phenylene diisocyanate, naphthalene 1,5-diisocyanate, Isocyanate, Aromatic polyisocyanates such as triphenylmethane triisocyanate, tris (isocyanate phenole) thiophosphate, isopropylbenzene-2,4-diisocyanate; xylylene diisocyanate (XDI), tetramethylxylylene diene Aliphatic and aromatic polyisocyanates such as isocyanate (TMXDI) (polyisocyanates in which the isocyanate group is bonded to the aromatic ring via the aliphatic hydrocarbon group, that is, directly with the aromatic ring in the molecule) Polyisocyanate having no attached isocyanate group); hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1, 6, 11 Decantlyisocyanate, 1,8-Diisocyanate 4 Isocyanate methyloctane, 1, 3, 6— Aliphatic polyisocyanates such as hexamethylene triisocyanate and trimethylhexamethylene diisocyanate; transcyclohexane 1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexane Examples include alicyclic polyisocyanates such as hexylmethane diisocyanate (hydrogenated MDI) and hydrogenated tolylene diisocyanate.

In addition, cyclized trimers (isocyanurate-modified products), biuret-modified products of the above polyisocyanate compounds, ethylene glycol, 1,4 butanediol, propylene glycolone, dipropylene glycolanol, trimethylololepropane, Polyolene polyol, Polymer polyol, Polytetramethylene etherol glycol, Polyesterol polyol, Acrylic polyol, Polyalkadiene polyol, Hydrogenated polyalkadiene polyol, Partially cured ethylene, Acetic acid butyl An addition reaction product of a polyol compound such as a polymer or castor oil-based polyol and the polyisocyanate compound is used. These polyisocyanate compounds can also be used as a mixture of two or more. Furthermore, the isocyanate groups of these polyisocyanate compounds are phenols, oximes, imides, mercaptans, alcohols, ε-force A so-called blocked isocyanate compound blocked with a blocking agent such as prolatatam, ethyleneimine, α-pyrrolidone, jetyl malonate, sodium bisulfite, boric acid or the like can also be used.

In the resin composition of the present invention, the content of the curing agent as the component (C) is such that the degree of crosslinking (curing degree), the balance between the physical properties of the cured product and the economic efficiency, etc. Cure Reactive group as agent / Molar specific force of hydroxyl group in component (A) S, 0.5 to 2.5, preferably 0.7 to 1.5, more preferably 0.9 to 1.2 Is the amount to be. As the reactive group as the curing agent in the component (C), when the curing agent is a polyisocyanate compound, an isocyanate group (NCO) can be mentioned.

As will be described later, when using a single-chain diol diamine, which is a chain extender, and a polyol other than the component (A) as an optional component, the amount of hydroxyl group or amino group in these compounds In consideration of the above, it is important to determine the amount of curing agent for component (C).

[0016] [Plasticizer]

In the resin composition of the present invention, a plasticizer can be contained as the component (D) as necessary in order to increase flexibility. There is no particular restriction on the type of plasticizer. The ability to use ordinary plasticizers S, excellent heat resistance, and hydrocarbon plasticizers are preferred as compounds with excellent bleed, such as α-olefin oligomers. And hydrogenated products thereof, paraffinic oils and the like can be preferably used.

These may be used alone or in combination of two or more. Examples of the paraffinic oil include liquid paraffin, paraffinic process oil, and mixed oils thereof.

In the present invention, when the plasticizer of component (D) is used, the blending amount thereof is 100 parts by mass with respect to 100 parts by mass of component (ii) from the viewpoint of properties of the cured product and suppression of bleeding. 100 to 500 parts by mass, more preferably 150 to 350 parts by mass, is even more preferable.

[0017] [Optional components]

In the resin composition of the present invention, physical properties are improved (improvement of processability by lowering viscosity, improvement of mechanical strength, heat resistance, weather resistance, chemical resistance, etc.) and cost within the range where the object of the present invention is not impaired. For down and other purposes, if necessary, as an optional component, a polyol other than the component (、), a short-chain diol as a chain extender, a diamine, an inorganic filler other than a heat conductive filler, or an organic filler , Antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, colorants such as pigments and dyes, and the like.

The type of polyol other than the component (ポリオール) is not particularly limited! /, But the polyol of component (Α) Those having good compatibility with the copper compound are preferred. In addition, the short chain dinoles as chain extenders include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4 butanediol, 1,6-hexanediol, and the like. For example, trimethylenediamine, tetramethylenediamine, hexamethylenediamine and the like can be mentioned.

Examples of inorganic fillers other than thermal conductive fillers include zinc, aluminum, copper, nickel, glass spheres, glass flakes, glass fibers, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fibers. , Graphite, asbestos, kaolin clay, wax stone clay, talc, cassiteite, cryolite, keystone, kieselguhr, slate powder, whiting, feldspar powder, my strength, gypsum, quartz powder, fine silica, attabargite Sericite, volcanic ash, meteorite, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitrite, molybdenum disulfide and the like.

On the other hand, organic fillers include, for example, natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, silk, nylon, polyester, vinylon, acetate, acrylic Synthetic fiber such as polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polychlorinated butyl, epoxy resin, phenol resin, etc. Can be mentioned.

In the preparation of the low hardness heat conductive resin composition (liquid gen-based polymer composition) of the present invention, the (A) polyol compound, (B) heat conductive filler, (C) curing agent and desired (D) The plasticizer and various optional components used in the above are mixed using a mixing device, a kneading device, etc., at about 0 to 120 ° C, preferably 15 to; at a temperature of 100 ° C, 0.5 seconds to 8 hours A liquid gen-based polymer composition is prepared by stirring and mixing for about 1 second to 5 hours. Under the present circumstances, when using a polyisocyanate compound as (C) hardening | curing agent, the one-shot method or the prepolymer method shown below is normally employ | adopted for preparation of a composition. First, add the ingredients except The mixture is obtained at a temperature and for a time to obtain a mixture. A polyisocyanate compound and optional components not used in the previous mixing are added to this mixture and mixed at the above temperature and time to obtain a liquid gen-based polymer composition. A preferable molar ratio NCO / (OH + NH) at this time is 0.5 to 2.5.

At a given molar ratio NCO / OH, NCO / NH or NCO / (OH + NH) in the range of about 1-7 to 25, at least one of a hydroxyl group-containing compound and a diamine compound and a polyisocyanate compound are added. Prebolimer is obtained by reaction in the presence or absence of some or all of the additives. The reaction temperature is the same as above, and the time is usually from 0.;! To 10 hours, preferably from 0.5 to 8 hours. The remaining components are mixed with the prepolymer at the above temperature and time to obtain a liquid gen-based polymer composition. The preferred molar ratio NCO / (ΟΗ + ΝΗ) at this time is 0 · 5 to 2.5 ·.

In addition, as described below, it is possible to prepare a prepolymer and adopt a method of reacting with moisture (water) in the air.

In a molar ratio NCO / (OH + NH) in the range of about 1.7 to 5.0, all the ingredients are blended and reacted to obtain a prepolymer. The reaction temperature is the same as above, and the time is usually from 0.;! To 10 hours, preferably from 0.5 to 8 hours. This prepolymer reacts with moisture (water) in the air.

[0019] The low-hardness heat conductive resin composition (liquid gen-based polymer composition) prepared in this way is used for various applications and is cured to give various forms of cured products. The power S

The low-hardness heat conductive resin composition of the present invention is, for example, a heat release film for cooling various electronic / electrical equipment sheets, a heat conductive insulating material, a potting material, a sealing material, a vibration isolating material, a heat conductive adhesive, Thermal conductive grease, thermal conductive paint, thermal conductive tape, anti-condensation and anti-fogging-Can be used as anti-freezing applications, various types of thermal conductive materials such as snow removal and heating. In particular, it is suitably used for producing a sheet-like heat radiating member having excellent heat dissipation, tackiness and flexibility.

[0020] Next, the sheet-like heat radiation member of the present invention will be described.

The sheet-like heat radiating member of the present invention has the low hardness heat conduction of the present invention obtained as described above. The resin composition is obtained by molding and curing by a conventionally known method. The sheet-like heat radiating member of the present invention has a strength capable of producing various hardnesses depending on the application, and preferably has a Shore E hardness of 10 to 80, particularly preferably in the range of 20 to 50. High hardness increases mechanical strength. Adhesion to the heating element deteriorates, and heat transfer may deteriorate. On the other hand, if the hardness is too low, it is difficult to keep the shape stable for a long time because of its softness. Furthermore, the higher the thermal conductivity, the better, but various adjustments can be made with the amount of heat-dissipating filler added depending on the application, from the balance with hardness and other physical properties. A range of 0.5 to 10 W / m′K, particularly 0.8 to 5. OW / mK is preferable as the sheet-like heat radiation member.

The thickness of the sheet-like heat radiating member of the present invention varies depending on the application, and is usually about 10 111 to 20111111, preferably 50 nm to 5 mm.

The sheet-like heat radiating member of the present invention is excellent in heat dissipation, tackiness, and flexibility, and is used particularly in electrical equipment and electronic parts such as plasma displays, transistors, capacitors, personal computers (notebook PCs, desktop PCs). Effective for heat dissipation of the heating element. In addition to this, the present invention can be applied to products using heat dissipation materials and parts'parts using heat dissipation materials. Products that use heat dissipation materials include TVs (LCD TVs, plasma TVs, OLED TVs, rear projection TVs, CRT TVs), PC peripherals (LCD monitors, inkjet printers, laser printers, hard disk drives, optical disk drives), Video and audio equipment (digital still camera, digital video camera, digital recorder, portable DVD player), communication (mobile phone, home fax machine), home appliances (air conditioner, electric refrigerator, washing machine, clothes dryer, vacuum cleaner, Microwave ovens, rice cookers, dishwashers, dehumidifiers, air purifiers), hobbies (home video game consoles, portable game consoles) and in-vehicle (car navigation systems, car stereos), etc. Use in is preferred.

Parts that use heat dissipation materials include various packages such as IC, CPU, LSI, modules, system boards, lead frames, wiring boards, light sources, planar light sources, LEDs, organic EL, inorganic EL, backlights, Ceramic package, display panel, display, power supply system, AC adapter, transformer device, secondary battery, switching power supply, motor, Heat sinks, heat sinks, heat pipes, heat dissipation systems, fan motors, various automotive control computer ECUs (engine control, power window control, power steering control, brake control, airbag control, etc.) and optical communication devices, etc. It is preferable to use it for planar light sources.

Example

[0021] Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

The physical properties of the thermally conductive cured product obtained in each example were measured according to the following methods.

(1) Shore E hardness

Measured according to JIS K6253.

(2) Thermal conductivity

A 70 mm X 50 mm X lmm test piece was prepared and measured by a hot disk method using a sensor (HTK-14 type) with a thermal conductivity meter [KPA Electronics, TPA-501].

[0022] Production Example 1 (Production of hydrocarbon compounds)

(1) Dimerization of 1-decene using metaguchicene complex

In a three-necked flask with an internal volume of 5 liters purged with nitrogen, 1-decene 3. Okg, bis (cyclopentagenyl) zirconium dichloride (also called zirconocene dichloride) 0.9 g (3 mmol) Then, methylaluminoxane (Albemarle, 8 mmol in terms of A1) was sequentially added, and the mixture was stirred at room temperature (20 ° C or lower). The reaction solution changed from yellow to reddish brown. After 48 hours from the start of the reaction, methanol was added to stop the reaction, and then an aqueous hydrochloric acid solution was added to the reaction solution to wash the organic layer. Next, the organic layer was distilled under vacuum to obtain 2.5 kg of a fraction (decene dimer) having a boiling point of 120-; 125 ° C / 26. 6 Pa (0.2 Torr). When this fraction was analyzed by gas chromatography, the concentration of decene dimer was 99% by mass, and the vinylidene refin ratio in the decene dimer was 97% by mass.

(2) Dimerization and hydrogenation process of vinylidene olefin Three-necked flask 5L purged with nitrogen, the dimer obtained in the previous section 2. 5 kg and Jechirua Honoré 13 mass mini © skeleton chloride ^_0/0 of a toluene solution 4. 3 ml was added, with stirring 50 ° C Immerse in an oil bath and add 10 ml of 35 wt% aqueous hydrogen chloride. After 1 hour, dilute hydrochloric acid was added to stop the reaction, and unreacted raw materials were removed by distillation under reduced pressure from the solution obtained by decomposing and removing the catalyst components. Next, the dimerization reaction product was transferred to an autoclave with an internal volume of 5 L, to which 5 g of 5 mass% palladium / alumina was added, and then purged with nitrogen, further purged with hydrogen and then heated to raise the hydrogen pressure to 0. Hydrogenation reaction was performed at 8 MPa for 8 hours. After confirming that no further hydrogen absorption occurred, the temperature was reduced and the pressure was released, and the hydrogenated product was removed from the autoclave. The catalyst was filtered off with respect to hydrogenated product, and colorless and transparent oily substance 2.2 kg was obtained. When the oily substance was analyzed by gas chromatography, the ratio of saturated hydrogen having 40 carbon atoms was 92.6% by mass.

[0023] Example 1

Hydrogenated polyisoprene polyol [made by Idemitsu Kosan Co., Ltd., trade name “EPOL”, 1,4 bonds 80 mol%, number average molecular weight 2500, average hydroxyl group content 0.90 mol / kg, average number of hydroxyl groups in one molecule 2 3 pieces] In 100 parts by mass, aluminum nitride powder [Made by Tokuyama Co., Ltd., average particle size 1.1 111] 250 parts by mass, and hydrogenated MDI [manufactured by Sumitomo Bayer Urethane Co., Ltd., The product name “Dismo Dieu Nore W” was added so that the NCO / OH molar ratio was 1 · 05, and the mixture was stirred and mixed. Then, 0.01 parts by mass of dibutyltin dilaurate [manufactured by Kyodo Kagaku Co., Ltd.] was added as a reaction catalyst, and after curing in a 1 mm thick mold at 10 MPa, 120 ° C for 1 hour, 70 ° Cured for 15 hours in C. The resulting thermally conductive cured product had a Shore E hardness of 76 and a thermal conductivity of 1.35 W / m.K.

Example 2

In Example 1, a thermally conductive cured product was produced in the same manner as in Example 1 except that the amount of aluminum nitride powder was changed to 160 parts by mass. The resulting thermally conductive cured product had a Shore E hardness of 59 and a thermal conductivity of 1.04 W / m'K.

[0024] Example 3

"EPOL" (supra) 50 parts by mass, hydrogenated polybutadiene polyol [Sartoma, USA, trade name "KRASOL HLBH-P3000", 1,4 bond 35 mol%, number average molecular weight 3100, average hydroxyl group content 0.5 mol / kg, average number of hydroxyl groups in one molecule 1. 9] 50 mass 200 parts by weight of polyalphaolefin [Product name “PAO5010” manufactured by Idemitsu Kosan Co., Ltd.], alumina powder [product name “Alunas CBA-20S” manufactured by Showa Titanium Co., Ltd., average particle size 10 H m] 1250 parts by weight, hydrogenated MDI [manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name “Days Module W”] as a polyisocyanate compound, so that the NCO / OH molar ratio is 1 · 05, Stir and mix. After that, 0.01 parts by mass of dibutyltin dilaurate [manufactured by Kyodo Kagaku Co., Ltd.] was added as a reaction catalyst, and after curing in a 1 mm thick mold at 10 MPa, 120 ° C for 1 hour, 70 Cured for 15 hours at ° C. The resulting thermally conductive cured product had a Shore E hardness of 30 and a thermal conductivity of 1.35 W / mK.

Example 4

In Example 3, 1250 parts by mass of the aluminum nitride used in Example 1 was added instead of alumina, and 200 parts by mass of the hydrocarbon-based compound obtained in Production Example 1 was added instead of “PAO5010”. Produced a thermally conductive cured material in the same manner as in Example 3. The resulting thermally conductive cured product had a Shore E hardness of 26 and a thermal conductivity of 1.88 W / m-K.

Example 5

A composition similar to that of Example 4 was coated on a release paper using a bar coater in a sheet form having a thickness of 200 m, and cured in an oven at 120 ° C for 1 hour. A heat dissipation sheet was prepared by curing at 70 ° C for 15 hours. This heat radiating sheet had good tackiness.

Industrial applicability

The low-hardness heat conductive resin composition of the present invention is suitably used for various uses as a heat conductive material, particularly a sheet-like heat radiating member excellent in heat dissipation, tackiness and flexibility. The sheet-like heat radiating member of the present invention is excellent in heat dissipation, tackiness and flexibility, and is particularly suitable for electric devices and electronic parts such as plasma displays, transistors, capacitors, personal computers (notebook PCs, desktop PCs). It is effective for heat dissipation of the heating element used. In addition to this, the force S can be applied to products that use heat dissipating materials and parts / parts that use heat dissipating materials.

Claims

The scope of the claims

[1] (A) (a-1) Hydrogenated product of hydroxyl group-containing polyisoprene 10 to 100% by weight and (a-2) Hydrogenated product of hydroxyl group-containing polybutadiene 90 to 0% by weight of polyol A compound, (B) at least one heat conductive filler selected from metal hydroxide, metal oxide and metal nitride, (C) a curing agent, and (B) component content is The amount of the component (C) is 100 to 5000 parts by mass with respect to 100 parts by mass of the component (A), and the content of the component (C) is a reactive group as a curing agent in the component (C) / A low-hardness heat conductive resin composition characterized in that the molar ratio of hydroxyl groups is 0.5 to 2.5.

[2] The low-hardness heat conductive resin composition according to claim 1, further comprising a plasticizer as the component (D) at a ratio of 1000 parts by mass or less with respect to 100 parts by mass of the component (A).

[3] The hydrogenated product of the hydroxyl group-containing polyisoprene as component (a-1) has a number average molecular weight of 200

2. The low-hardness heat conductive resin composition according to claim 1, wherein the low-hardness heat-conductive resin composition has a 1,4-bond of 50 mol% or more.

[4] Hydrogenation power of hydroxyl-containing polybutadiene (a-2) component Number average molecular weight 200

The low-hardness heat-conductive resin composition according to claim 1, wherein the molar ratio of 1,2-bond to 1,4-bond is 50: 50-95: 5 in the microstructure. .

[5] The low-hardness heat conductive resin composition according to claim 1, wherein the curing agent of the component (C) is a polyisocyanate compound.

[6] The low-hardness heat conductive resin composition according to claim 2, wherein the plasticizer of component (D) is a hydrocarbon plasticizer.

[7] A sheet-like heat radiation member obtained by molding and curing the low-hardness heat conductive resin composition according to any one of claims 6 to 6.