JPWO2013172429A1 - Elastic heat-dissipating sheet and article to which it is attached - Google Patents

Abstract

The present invention provides a heat release having a tensile elongation of 100% or more obtained from the resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B), and infrared absorbing inorganic particles (C). Stretchable heat dissipation of a two-layer structure composed of a layer and an adhesive layer having a tensile elongation of 200% or more obtained from the resin composition II containing the adhesive resin (D) A sheet is provided. The present invention also provides an article to which the stretchable heat radiation sheet having the above two-layer structure is attached.

Description

  The present invention relates to a stretchable heat dissipation sheet and an article to which the stretchable heat dissipation sheet is attached.

  In recent years, as the performance of electronic parts and optical parts such as semiconductors, LED elements, and electronic boards, and electronic products, electrical products and optical products which are casings containing these parts has improved, heat from various parts and products has been increased. The amount began to increase. And when these components and products cannot be cooled appropriately, problems such as breakage and shortening of the service life occur. For this reason, various heat dissipation sheets have been used as means for releasing heat generated from these components and products to the outside.

  For example, in Patent Document 1, a flexible heat radiation film having an infrared radiation effect is formed on the front surface of a flexible heat absorption layer having heat conductivity, and the heat conductivity is formed on the back surface of the heat absorption layer. A heat dissipation sheet having a three-layer structure in which an adhesive layer made of an adhesive is formed to have flexibility is proposed. FIG. 1 shows a schematic diagram of this conventional heat dissipation sheet. In FIG. 1, 1 shows this heat radiating sheet, 2 shows a heat radiation film, 3 shows a heat absorbing layer such as an aluminum plate, and 4 shows an adhesive layer. However, since the heat-dissipating sheet uses a thin metal plate such as aluminum as the heat-absorbing layer, the heat-dissipating sheet has flexibility, but lacks flexibility and stretchability required when affixing to a component having a complicated shape. It was enough. Moreover, since the heat dissipation sheet of Patent Document 1 has a three-layer structure of a heat radiation film, a heat absorption layer, and an adhesive layer, a thermal resistance is generated between each layer from the heat source to the heat radiation film that is the outermost layer. It is considered that heat transfer to the heat radiation film is insufficient.

  Therefore, in Patent Document 2, as a heat dissipation sheet having a two-layer structure, the infrared absorption heat having a total infrared absorption rate of 0.85 or more at a wavelength of 2 to 14 μm and a thermal conductivity in the thickness direction of 1 W / mK. The thing which provided the silicone adhesive layer in the conductive polyimide film is proposed. And the heat dissipation efficiency of the sheet | seat is ensured by including boron nitride, carbon fiber, etc. in the said polyimide film. However, since the polyimide film used as the heat dissipation layer of the sheet is a resin having poor flexibility and stretchability in the first place, the flexibility and stretchability necessary for attaching to a component having a complicated shape are still insufficient.

  Therefore, heat dissipation sheet with excellent flexibility and stretchability that can be easily applied and dissipated on various parts such as electronic parts, optical parts, and various products that are casings containing these parts. Is desired.

JP 2004-200199 A JP 2011-32430 A

  An object of the present invention is to provide a heat dissipation sheet excellent in flexibility and stretchability.

  The present inventor has intensively studied to solve the above problems. As a result, the stretchability of the two-layer structure having a specific tensile elongation rate, which is composed of a heat radiation layer containing a specific component and having a specific tensile elongation rate, and an adhesive layer having a specific tensile elongation rate. According to the heat dissipation sheet, it has been found that the problem can be solved, and based on this, the present invention has been completed.

  That is, the present invention provides the following elastic heat-dissipating sheet and an article to which it is attached.

  1. A heat-dissipating layer having a tensile elongation of 100% or more obtained from the resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B) and infrared absorbing inorganic particles (C); A stretchable heat-dissipating sheet having a two-layer structure having a tensile elongation of 100% or more, comprising an adhesive layer having a tensile elongation of 200% or more obtained from the resin composition II containing the conductive resin (D).

  2. The stretchable heat radiation sheet according to Item 1, wherein the resin (A) having a tensile elongation of 200% or more is at least one selected from the group consisting of a polyester resin, an acrylic resin, an epoxy resin, a polyurethane resin, and a silicone resin. .

  3. The resin (A) having a tensile elongation of 200% or more is a polyester resin, the number average molecular weight thereof is 10,000 to 80,000, and the hydroxyl value thereof is 1 to 20 mgKOH / g. The elastic heat-radiating sheet according to Item 1.

  4). The stretchable heat-radiating sheet according to Item 1, wherein the crosslinking agent (B) is an amino resin-based crosslinking agent.

  5. Infrared absorbing inorganic particles (C) selected from the group consisting of non-porous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, salicite, mica and cordierite The elastic heat-dissipating sheet according to Item 1, which is at least one kind.

  6). The elastic heat-radiating sheet according to Item 1, wherein the infrared-absorbing inorganic particles (C) absorb infrared rays having a wavelength range of 6.3 to 10.5 μm.

  7). The stretchable heat radiation sheet according to Item 1, wherein the infrared-absorbing inorganic particles (C) have an average primary particle diameter of 0.1 to 15.0 μm.

  8). The elastic heat-radiating sheet according to Item 1, wherein the content of the infrared-absorbing inorganic particles (C) is 10 to 60% by weight of the heat-dissipating layer.

  9. In the resin composition I, the content of the crosslinking agent (B) is 1 to 40 parts by weight (in terms of solids) and 100 parts by weight (in terms of solids) of the resin (A) having a tensile elongation of 200% or more and The elastic heat-radiating sheet according to Item 1, wherein the content of the infrared-absorbing inorganic particles (C) is 20 to 200 parts by weight.

  10. The elastic heat-radiating sheet according to Item 1, wherein the heat emissivity of the heat-dissipating layer is 0.95 or more at 70 ° C.

  11. The elastic heat-radiating sheet according to Item 8, wherein the adhesive resin (D) is at least one resin selected from the group consisting of acrylic resins, polyurethane resins, polyester resins, and silicone resins.

  12 The elastic heat-radiating sheet according to Item 1, wherein the adhesive layer contains 10 to 80% by weight of inorganic particles (E) having a thermal conductivity of less than 10 to 300 W / m · K.

  13. The elastic heat-radiating sheet according to Item 1, wherein the heat-radiating layer has a thickness of 10 to 100 μm.

  14 The elastic heat-radiating sheet according to Item 1, wherein the pressure-sensitive adhesive layer has a thickness of 10 to 150 μm.

  15. An article to which the stretchable heat dissipation sheet according to Item 1 is attached.

  According to the present invention, the following effects can be obtained.

  (1) The stretchable heat-radiating sheet of the present invention has a two-layer structure of a heat-dissipating layer having a specific tensile elongation and an adhesive layer having a specific tensile elongation without sandwiching a metal layer such as aluminum or copper. Therefore, it is excellent not only in flexibility but also in elasticity. In addition, the heat-dissipating sheet of the present invention efficiently releases heat transmitted from the heat-generating body such as an electronic component, which is an object to be pasted, to the heat-dissipating layer through the adhesive layer of the heat-dissipating sheet, and cools the heat-generating body. Therefore, the heat-radiating sheet of the present invention has sufficient flexibility, followability, adhesion, and excellent heat-dissipating properties to be attached to various parts, particularly parts having complicated shapes.

  (2) The stretchable heat dissipation sheet of the present invention is based on its excellent flexibility and stretchability, and is an electronic component that is a variety of components such as electronic components such as semiconductors, LED elements, and electronic substrates, and a housing that includes these components. It can be suitably affixed to various products such as products, whereby heat generated from these parts and products can be effectively released.

  (3) The stretchable heat radiation sheet of the present invention is based on its excellent flexibility and stretchability, particularly when the heat-generating component such as an electronic substrate or the heat-generating article that is the housing has unevenness or steps. In addition, since the heat generating part or the whole of the heat generating part can be brought into close contact, the heat radiation efficiency is extremely high.

  (4) Further, the stretchable heat radiation sheet of the present invention can be combined with other physical cooling means such as heat radiation fins, so that the cooling means can be reduced in size and the product can be downsized.

  (5) Further, the stretchable heat radiation sheet of the present invention is different from the heat radiation paint as an organic solvent solution or paste, and even when the article to which it is attached has low solvent resistance or heat resistance, there is no problem and is easy. Can be used for

It is a schematic diagram of the conventional heat dissipation sheet of a three-layer structure. It is a schematic diagram of a stretchable heat dissipation sheet having a two-layer structure according to the present invention. It is a photograph which shows the state which affixed the elastic heat dissipation sheet which concerns on this invention to a part of printed wiring board.

  The stretchable heat dissipation sheet of the present invention has a two-layer structure composed of a heat dissipation layer having a tensile elongation of 100% or more and an adhesive layer having a tensile elongation of 200% or more. 100% or more, and the heat dissipation layer is obtained from the resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B), and infrared absorbing inorganic particles (C). Is characterized by

  In the present invention, the tensile elongation is a value measured according to the method defined in JIS K 7312. Specifically, when the measurement target is, for example, a resin (A), a sheet made of the resin is processed into a 10 mm × 123 mm × 0.1 mm strip, the distance between the marked lines is 10 mm, and the tensile speed is 5 mm / min. It is a measured value (elongation at the time of cutting (%)) when measuring the elongation percentage. The elongation rate can be measured using, for example, a precision universal testing machine. As the precision universal testing machine, for example, commercially available “Autograph AGS-X” (product name, manufactured by Shimadzu Corporation) can be used. Moreover, this measuring method is applied also to the measurement of each tensile elongation rate of the thermal radiation layer, the adhesion layer, and the thermal radiation sheet which concern on this invention.

  The heat-dissipating layer of the stretchable heat-dissipating sheet according to the present invention uses a resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B), and infrared-absorbing inorganic particles (C). It is formed.

  The resin (A) is not particularly limited as long as the tensile elongation is 200% or more, and a known resin can be used. The tensile elongation of the resin (A) is preferably 200 or more and 600% or less. If the tensile elongation rate of the resin (A) exceeds 600%, the resilience after pulling of the heat-dissipating sheet is greatly reduced, and the adhesion to the article to be stuck tends to be insufficient. From this point of view, the tensile elongation of the resin (A) is more preferably 200 or more and 550% or less.

  Specific examples of the resin (A) include polyester resins, acrylic resins, polyurethane resins, epoxy resins, and silicone resins, and these can be used alone or in combination of two or more. Among these, it is preferable to use a polyester resin in that the heat dissipation sheet of the present invention easily follows and adheres to the surface of the article to be adhered.

  On the other hand, when a resin having a tensile elongation of less than 200%, for example, a general polyimide resin is used as the resin (A), it becomes difficult to set the tensile elongation of the heat dissipation sheet of the present invention to 100% or more. The stretchable heat dissipation sheet intended by the present invention cannot be obtained.

  The polyester resin used as the resin (A) is not particularly limited as long as the tensile elongation is about 200% or more, and a known resin can be used. The tensile elongation of the polyester resin is preferably 200 or more and 600% or less, and more preferably 200 or more and 550% or less. Specific examples of the polyester resin include a reaction product of a dicarboxylic acid and a diol.

  Examples of the dicarboxylic acid used include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. The aromatic dicarboxylic acid is not particularly limited, and examples thereof include phthalic anhydride, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic dicarboxylic acid include, but are not limited to, succinic acid, fumaric acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, and maleic anhydride. The alicyclic dicarboxylic acid is not particularly limited, and examples thereof include hexahydrophthalic anhydride, hexahydroisophthalic acid, hexahydroterephthalic acid and the like. These dicarboxylic acids may be used alone or in combination of two or more, but it is preferable to use an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid in combination. These dicarboxylic acids may be used as they are, but lower alkyl esterified products such as dimethyl esters and diethyl esters may also be used. However, considering the flexibility and tensile elongation of the stretchable sheet of the present invention, the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid are in a range where the former to the latter are in a weight ratio of about 95: 5 to 70:30. It is preferable to use together. Moreover, in addition to these dicarboxylic acids, 3 basic acids such as benzoic acid, crotonic acid, pt-butylbenzoic acid, trimellitic anhydride, methylcyclohexeric carboxylic acid, pyromellitic anhydride, etc. A polybasic acid having a valency or higher may be used in combination.

  Examples of the diol used include aliphatic diols having no branched structure such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; 1,3-butanediol, neopentyl glycol, Examples include aliphatic diols having a branched structure such as 2-methyl-1,3-propanediol, 3-methylpentanediol, and 1,4-hexanediol; and alicyclic diols such as 1,4-dimethylolcyclohexane. . In particular, it is preferable to use an aliphatic diol having a branched structure and an aliphatic diol having no branched structure in such a range that the former and the latter are in a weight ratio of about 90:10 to 50:50. These diols may be used singly or in combination of two or more, but it is preferable to use an aliphatic diol having a branched structure and an aliphatic diol having no branched structure in combination. In addition to these diols, a tri- or higher valent polyol component such as trimethylolpropane, trimethylolethane, or glycerin may be used in combination as necessary.

  The polyester resin used as the resin (A) preferably has a number average molecular weight of about 10,000 to 80,000, more preferably about 15,000 to 50,000. The hydroxyl value of the polyester resin is preferably about 1 to 20 mg / KOH, and more preferably about 4 to 16 mg KOH / g. When a polyester resin having these physical properties is used, the balance between the hardness of the heat dissipation layer of the heat dissipation sheet of the present invention and the workability of the sheet itself is improved.

  As the acrylic resin, an acrylic resin obtained from (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl group and styrenes is particularly preferable. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate. , Tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, ( Such as octadecyl (meth) acrylate, octadecenyl (meth) acrylate, icosyl (meth) acrylate, docosyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., heat dissipation layer and adhesive layer From the viewpoint of adhesion with the heat dissipation layer and the hardness of the heat dissipation layer, the alkyl group has 1 to 1 carbon atoms. Preferably of about 2, and more preferably about 1-5. Examples of the styrenes include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, chlorovinyltoluene and the like, which are easily available, and a heat dissipation layer. Styrene is preferred because it contributes to the adhesion between the adhesive layer and the adhesive layer and also contributes to the hardness of the heat dissipation layer. In addition to (meth) acrylic acid alkyl esters and styrenes, various known α olefins, nitriles, (meth) acrylamides, (meth) acrylic acid hydroxyalkyl esters, etc. may be used in combination as required. it can.

  In addition, although the usage-amount of the (meth) acrylic-acid alkylesters whose carbon number of the above-mentioned alkyl group is 1-18, styrene, and another monomer is not specifically limited, Usually, all the monomers are 100 mol%. In this case, it is preferably about 40 to 60 mol%, about 60 to 40 mol%, and about 0 to 10 mol%, in particular, about 45 to 55 mol%, especially about 55 to 45 mol%. And about 0 to 5 mol% is more preferable.

  The method for producing the acrylic resin is not particularly limited, and various known polymerization reactions can be employed. For example, the (meth) acrylic acid alkyl esters, styrenes, and other monomers are reacted in the presence of various known radical polymerization initiators at 20 to 120 ° C. for 2 to 10 hours in the amount used. Just do it. In the reaction, any suitable organic solvent described later can be used as the reaction solvent. Examples of the radical polymerization initiator include potassium persulfate, ammonium persulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobisisobutylnitrile, and 2,2′-azobis. (2,4-dimethylvaleronitrile) and the like.

  Examples of the commercially available acrylic resin include Parapet SA (manufactured by Kuraray Co., Ltd., 200% elongation), Armatex 748-5M (manufactured by Mitsui Chemicals), Armatex 748-16AE (Mitsui Chemicals, Inc.) )) And the like.

  Specific examples of the epoxy resin include non-amine-modified epoxy resins, amine-modified epoxy resins, and amine / urethane-modified epoxy resins.

  As the non-amine-modified epoxy resin, various known ones can be used without particular limitation. Specifically, for example, a bisphenol type epoxy resin obtained by glycidylating various bisphenols, a hydrogenated product of the bisphenol type epoxy resin, a phenol novolac resin, a novolac type epoxy resin obtained by reacting a cresol novolac resin with a haloepoxide. And biphenyl type epoxy resin. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol. Examples thereof include A and tetrafluorobisphenol A.

  As the amine-modified epoxy resin, various known ones can be used without particular limitation. Specifically, for example, the non-amine-modified epoxy resin, in particular, a bisphenol type epoxy resin or a hydrogenated product thereof is reacted with various known amines. Examples of the amines include aromatic amines such as toluidines, xylidines, cumidine (isopropylaniline), hexylanilines, nonylanilines, dodecylanilines; cyclopentylamines, cyclohexylamines, norbornyl Alicyclic amines such as amines; methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, stearylamine, icosylamine, 2-ethylhexylamine, dimethylamine, diethylamine, dipropylamine, Aliphatic amines such as dibutylamine, dipentylamine, diheptylamine; diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N Examples include alkanolamines such as ethylethanolamine and N-benzylethanolamine. Among these, considering the mechanical strength of the heat-dissipating coating film and adhesion to the substrate, the number of carbon atoms in the molecule is 3 to 3. Those having one or more of 30 alkyl groups are preferred.

As the amine / urethane modified epoxy resin, various known ones can be used without particular limitation. Specific examples include those obtained by further modifying the amine-modified epoxy resin with polyisocyanate. Examples of the polyisocyanate include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. And various aliphatic, alicyclic or aromatic diisocyanates such as isophorone diisocyanate and dicyclohexylmethane-4,4′-diisocyanate.
As the amine-modified epoxy resin and the amine / urethane-modified epoxy resin, for example, those described in JP 2010-235918 A can be used.

  As the polyurethane resin (excluding those corresponding to the amine / urethane-modified epoxy resin), various known ones can be used without particular limitation. Specifically, for example, those using a polymer polyol and the polyisocyanate as raw materials can be mentioned. Examples of the polymer polyol include polyester polyol, polyether polyol, polycarbonate polyol, and acrylic polyol, and examples of the polyisocyanate include those described above. Moreover, in order to provide water resistance to the polyurethane resin, the carboxyl group-containing diol such as dimethylolpropanoic acid or dimethylolbutanoic acid may be used in combination as a diol component. Further, the number average molecular weight is not particularly limited, but is usually about 10,000 to 80,000, particularly about 15,000 to 50,000. In addition, as a commercial item, Elastollan C80A (elongation rate 500%), Elastollan C1180A (elongation rate 550%), etc. are mentioned, for example (all are brand names, all manufactured by BASF).

  As the silicone resin, various known ones can be used without particular limitation. Specific examples include silicone-modified acrylic resins such as dimethylsilicone resin, methylphenylsilicone resin, diphenylsilicone resin, alkyl-modified silicone resin, aralkyl-modified silicone resin, and alkylaralkyl-modified silicone resin. Examples of commercially available products include JCR6125 (two-component curable methyl silicone elastomer, elongation rate 230%), SE9186 (elongation rate 555%) and SE6186L (elongation rate 320%, acrylic modified silicone elastomer) (both products) Name, all manufactured by Toray Dow Corning).

  The cross-linking agent (B) is used for the purpose of securing the hardness of the resin (A) by bonding in the form of a bridge inside the heat dissipation layer, and is appropriate depending on the type of the resin (A) and its functional group. You can choose the right one.

  For example, an amino resin-based crosslinking agent is preferable for the resin (A) having a hydroxyl group or a carboxyl group in the molecule. Examples of the amino resin-based crosslinking agent include melamine resins, urea resins, benzoguanamine resins, acetoguanamine resins, spiroguanamine resins, dicyandiamide, and the like, and methylolated amino resins obtained by reacting them with aldehydes. Among these, from the viewpoint of the hardness of the heat dissipation layer, a melamine resin and / or an alkylated melamine resin substituted with an alkyl group having about 1 to 5 carbon atoms is preferable.

  As the inorganic particles (C), various known particles can be used without particular limitation. Specifically, for example, titanium oxide, silicon carbide, non-porous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, salicite, mica, cordierite, etc. Can be mentioned. These may be used alone or in combination of two or more.

  Further, among the inorganic particles (C), when inorganic particles that absorb infrared rays having a wavelength range of about 6.3 to 10.5 μm (hereinafter referred to as “component (c)”) are used, the heat dissipation efficiency of the heat dissipation sheet of the present invention. From the viewpoint of Examples of such materials include porous silica, boron nitride, calcium fluoride, and aluminum hydroxide. These can be used alone or in combination of two or more. The content of the component (c) in the inorganic particles (C) is not particularly limited, but is preferably about 5 to 100% by weight, and preferably about 20 to 80% by weight from the viewpoint of heat dissipation efficiency of the heat dissipation sheet.

  The particle size of the inorganic particles (C) is not particularly limited as long as it is the same as or smaller than the thickness of the heat dissipation layer. For example, when inorganic particles (C) having an average primary particle diameter of usually about 0.1 to 15.0 μm, preferably about 0.1 to 10.0 μm, the heat dissipation sheet of the present invention has good stretchability. It is preferable because it easily follows and adheres to the surface of the object to be pasted.

  In addition, the content of the inorganic particles (C) in the heat dissipation layer of the heat dissipation sheet of the present invention is not particularly limited, but is usually about 10 to 60% by weight based on the weight of the heat dissipation layer, from the viewpoint of heat dissipation efficiency. preferable.

  The heat dissipation layer is formed using a resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B), and inorganic particles (C). Although content of each component in the resin composition I is not particularly limited, the crosslinking agent (B) is about 1 to 40 parts by weight (in terms of solids) with respect to 100 parts by weight (in terms of solids) of the resin (A), And about 20 to 200 parts by weight of inorganic particles (C), preferably about 5 to 25 parts by weight (in terms of solid content) of crosslinking agent (B), and about 70 to 150 parts by weight of inorganic particles (C). Thereby, the elasticity can be made favorable, maintaining the thermal radiation effect of the thermal radiation sheet of this invention.

  For the resin composition I, known additives can be used as long as the effects of the present invention are not impaired. Examples of additives that can be used include thickeners such as organic bentonite, carboxymethylcellulose, and polyvinyl alcohol; and various dispersants such as polyacrylic acid and polyacrylate. When the additive is used, the amount used is not particularly limited, but is usually 5% by weight or less in terms of solid content in the resin composition I.

  The resin composition I is usually used in the form of a liquid composition or a paste-like composition containing an organic solvent or water. Examples of the organic solvent include aromatic hydrocarbons such as xylene, ethylbenzene, toluene, and trimethylbenzene; aliphatic hydrocarbons such as isoparaffin, monoalcohols such as methanol, ethanol, propanol, isopropanol, butyl alcohol, and isobutyl alcohol; ethylene glycol Polyhydric alcohols such as: ester solvents such as methyl acetate, ethyl acetate and butyl acetate; acetate solvents such as propylene glycol monomethyl ether acetate; volatile ketones such as methyl ethyl ketone and cyclohexanone; naphtha and the like.

  The heat dissipation layer needs to have a tensile elongation of 100% or more. By doing so, the heat dissipation sheet of the present invention easily follows and adheres to the surface of an object to be pasted, particularly a complicated part or product. Become. From this viewpoint, the tensile elongation is preferably 100% or more and 300% or less, and more preferably 100% or more and 200% or less. In addition, adjustment of the tensile elongation rate of a thermal radiation layer is means, such as changing the kind and usage-amount of resin (A), the kind and usage-amount of a crosslinking agent (B), and content of an inorganic particle (C), for example. Is possible.

  Moreover, it is preferable from a viewpoint of the thermal radiation efficiency of the thermal radiation sheet | seat of this invention that the thermal emissivity of the said thermal radiation layer shall be 0.95 or more in 70 degreeC.

  The adhesive layer of the heat-radiating sheet of the present invention is obtained from the resin composition II containing the adhesive resin (D).

  The adhesive resin (D) is not particularly limited as long as it is an adhesive resin, and known ones can be used. Specifically, an acrylic resin, a polyurethane resin, a polyester resin, a silicone resin, etc. are mentioned, for example, These can be used individually by 1 type or in combination of 2 or more types. In these, an acrylic resin is preferable. Further, as the adhesive resin (D), for example, an adhesive resin described in Japanese Patent Application Laid-Open No. 2008-195904, or an adhesive described in Japanese Patent Application Laid-Open No. 2012-131922, for example. Resin may be used.

  The acrylic resin is usually obtained by polymerizing alkyl (meth) acrylate. The alkyl (meth) acrylate to be used is not particularly limited, and known ones can be used. Specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl It can be obtained by polymerizing (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate. The glass transition temperature of the acrylic resin is preferably −20 ° C. or lower. The melt viscosity is preferably 50,000 mPa · s or more, and more preferably about 100,000 to 70,000 mPa · s.

  As a polyurethane resin, a polyester resin, and a silicone resin, what has adhesiveness can be selected and used among what was mentioned as above-mentioned resin (A).

  In addition, the resin composition II may include inorganic particles (E) having a thermal conductivity of about 10 to 300 W / m · K as necessary. For example, as will be described later, the thickness of the pressure-sensitive adhesive layer is not particularly limited. However, when the value is 10 μm or more and 30 μm or less, the thermal resistance related to the heat conduction of the pressure-sensitive adhesive layer can be ignored. unnecessary. On the other hand, when the thickness exceeds 30 μm, it is difficult to ignore the thermal resistance of the adhesive layer, and thus there is an advantage of using the inorganic particles (E).

The inorganic particles (E) are not particularly limited as long as the thermal conductivity is about 10 to 300 W / m · K. Examples of such materials include aluminum oxide, magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silicon nitride, and silicon carbide. These are used alone or in combination of two or more. it can

The amount of the inorganic particles (E) used is not particularly limited, but is usually 10 to 80 based on the weight of the adhesive layer from the viewpoint of increasing the thermal conductivity of the adhesive layer and maintaining its adhesiveness. It is preferable that it is about weight%.

  The particle size of the inorganic particles (E) is not particularly limited as long as it is the same as or smaller than the thickness of the heat dissipation layer. For example, when an inorganic particle (E) having an average primary particle size of usually about 0.1 to 15.0 μm, preferably about 0.1 to 10.0 μm, the heat dissipation sheet of the present invention has good stretchability. It is preferable because it becomes easy to follow and adhere to the surface of the object to be pasted.

  The resin composition II may further contain a crosslinkable monomer, a reactive diluent and a radical polymerization initiator as necessary.

  Examples of the crosslinkable monomer include 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, cyclohexane di (meth) acrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol. Bifunctional acrylates such as diacrylate and 1,9-nonanediol diacrylate; trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol tri (meth) acrylate, polyglycerol tri (meth) acrylate, Trifunctional acrylates such as polyglycerol di (meth) acrylate and pentaerythritol tri (meth) acrylate can be used. The amount of the crosslinking monomer is preferably about 0.01 to 10.0 parts by weight and about 0.03 to 5.0 parts by weight with respect to 100 parts by weight (in terms of solid content) of the pressure-sensitive adhesive resin (D). It is more preferable that

  Examples of the reactive diluent include known monofunctional (meth) acrylic compounds. Specific examples include 2-ethylhexyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloylmorpholine, tricyclodecanyl acrylate, and isobornyl acrylate. Although the usage-amount of a reactive diluent is not specifically limited, Usually, it is preferable that it is 50 weight part or less with respect to 100 weight part of adhesive resin (D).

  As the radical polymerization initiator, known ones such as an acetophenone-based initiator, a benzoin-based initiator, a benzophenone-based initiator, and a phosphine oxide-based initiator can be used. In particular, it is preferable to use a compound having a hydroxyl group from the viewpoint of the compatibility of the composition. Although the usage-amount of a radical polymerization initiator is not specifically limited, It is preferable that it is about 0.5-5 weight part with respect to 100 weight part of total amounts of the said crosslinkable monomer and the said reactive diluent.

  In the resin composition II, as long as the effects of the present invention are not impaired, further known additives include, for example, a tackifier, an anti-settling agent, a thickener, a thixotropic agent, an antioxidant, a plasticizer, and a surfactant. You may include 1 type, or 2 or more types, such as an agent, an antifoamer, and a coloring agent. When the additive is used, the amount of the additive is not particularly limited, but it is usually suitably 5% by weight or less in terms of solid content in the resin composition II.

  The resin composition II is usually used in the form of a liquid composition or a paste-like composition containing an organic solvent or water, and the organic solvent is the same as that used for the resin composition I.

  The adhesive layer needs to have a tensile elongation of 200% or more. When sticking the heat-dissipating sheet of the present invention to various articles, the pressure-sensitive adhesive layer is directly in contact with the adherend when it is located inside the heat-dissipating layer. And since it is necessary to closely adhere to the uneven shape, it is necessary that the tensile elongation is larger than that of the heat dissipation layer. Further, by making the tensile elongation rate preferably 200% or more and 400% or less, more preferably 200% or more and 300% or less, the heat-dissipating sheet has a good restorability, and various objects to be pasted, especially parts having complicated shapes. It becomes easier to follow and adhere to the surface of the product and the product. In addition, adjustment of the tensile elongation rate of an adhesion layer is possible by means, such as changing the kind and usage-amount of adhesive resin (D), and content of an inorganic particle (E), for example.

  The heat dissipation sheet of the present invention can be obtained by providing the adhesive layer on the heat dissipation layer or providing the heat dissipation layer on the adhesive layer by a known method.

  Specifically, after coating the resin composition I forming the heat dissipation layer on a suitable support, the resin composition II is further coated, then dried, and the support is peeled off. It is done.

  In addition, after coating the resin composition II on a suitable support, the resin composition I is further coated, then dried, and the support is peeled off to prepare the heat dissipation sheet of the present invention. be able to.

  Also, the resin composition I and the resin composition II can be coated on different supports and dried, and then the heat dissipation layer and the adhesive layer are pressure-bonded, and then the support is peeled off. An elastic sheet can be prepared.

  Here, although the said support body is not specifically limited, For example, plastic films or plates, such as a polyethylene phthalate, a glass plate, a metal plate, etc. can be used. Further, the support may be subjected to a mold release treatment as necessary.

  In the heat dissipation sheet of the present invention, the thickness of the heat dissipation layer is not particularly limited, but is usually about 10 to 100 μm, preferably about 12 to 70 μm. The thickness of the adhesive layer is not particularly limited, but is usually about 10 to 150 μm, preferably about 12 to 70 μm. By setting the thickness of the heat dissipation layer and the adhesive layer to 10 μm or more, the strength of the heat dissipation sheet of the present invention can be maintained, and tearing during expansion and contraction can be suppressed. Moreover, since the heat resistance by heat conduction can be suppressed by setting the thickness of the heat dissipation layer to 100 μm or less and the thickness of the adhesive layer to 150 μm or less, the heat dissipation efficiency of the heat dissipation sheet of the present invention can be enhanced.

  The heat dissipation sheet of the present invention obtained by the above method needs to have a tensile elongation of 100% or more. By making the tensile elongation rate of the stretchable sheet 100% or more, it becomes easy to follow and adhere to the surface of various articles, particularly complex shaped parts and products. From this viewpoint, the tensile elongation of the heat dissipation sheet is preferably 100% or more and 400% or less, and more preferably 100% or more and 200% or less. In addition, adjustment of the tensile elongation rate of a thermal radiation sheet | seat is possible by the combination of the thermal radiation layer and the layer which gives the said tensile elongation rate.

  In FIG. 2, the schematic diagram of an example of the elastic | stretch heat dissipation sheet which concerns on this invention was shown. In FIG. 2, 5 indicates the stretchable heat dissipation sheet of the present invention, 6 indicates the heat dissipation layer, and 7 indicates the adhesive layer.

  The heat dissipation sheet of the present invention may have a separator bonded to one side or both sides as needed for the purpose of protecting the surface. Examples of the separator include the above-described support, and a plastic film is particularly preferable from the viewpoint of maintaining the surface smoothness of the heat dissipation layer and the adhesive layer. The plastic film is not particularly limited as long as it can protect the surface of the heat dissipation sheet, and a known film can be used. Examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyvinyl chloride film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

  The heat-dissipating sheet of the present invention thus obtained is based on its excellent flexibility and stretchability, and various parts such as electronic parts such as semiconductors, LED elements, and electronic boards, and electronic products that are casings containing these parts For example, the heat generated from these parts and products can be effectively released.

  In FIG. 3, the photograph showing the state which affixed on the semiconductor chip (upper position) and center operator chip | tip (lower position) in a printed wiring board the stretchable heat-radiation sheet which concerns on this invention is shown.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Production Examples, Examples and Comparative Examples. However, the present invention is not limited to these examples.

  Among the production examples shown below, Production Examples 1 to 14 are examples in which a heat radiation layer (sheet-like cured product) is produced using the resin composition I. In addition, Production Examples 15 to 20 are examples in which an adhesive layer (sheet-like cured product) is produced using the resin composition II.

Production Example 1
Commercially available polyester resin (trade name: Arakid 7005N, manufactured by Arakawa Chemical Industries, Ltd., tensile elongation 550%) 65 parts by weight, butylated melamine resin (trade name: Uban 228, manufactured by Mitsui Chemicals, Inc.) 8 parts by weight , Titanium oxide powder (trade name: TI TONE R-32, Sakai Chemical Industry Co., Ltd., average primary particle size 0.2 μm or less) 16 parts by weight, silicon carbide powder (trade name: Shinano Random GP-3000, Shinano Electric As a catalyst, 2 parts by weight, manufactured by Smelting Co., Ltd., 2 parts by weight of an average primary particle diameter of 4.0 μm or less, boron nitride powder (trade name: Boronid S3, manufactured by ESK CERAMICS, average primary particle diameter of 10.0 μm or less) Resin composition I was prepared by mixing 0.5 parts by weight of dinonylnaphthalenedisulfonic acid amine salt. Using this resin composition I, an applicator was applied to a polyethylene terephthalate film (thickness 75 μm) subjected to a mold release treatment so that the film thickness after drying was about 30 μm to 40 μm. After leaving it indoors for about 5 minutes, it was dried in a dryer at 120 ° C. for 30 minutes, and then the film was peeled off to obtain a sheet-like cured product as a heat dissipation layer.

Production Examples 2-14
A sheet-like cured product as a heat-dissipating layer was obtained in the same manner as in Production Example 1 except that the type and amount of each component used were changed as described in Table 1 or Table 2 below.

  About the sheet | seat obtained by manufacture example 1-14, the elasticity, elongation rate, and 70 degreeC heat emissivity were measured in accordance with the following method.

Based on the physical test method of the molded article defined by JIS K 7312, a strip-shaped test piece of 10 mm × 123 mm × 0.03-0.10 mm is produced from each sheet of the stretchable production examples 1 to 14, and marked. Using a precision universal testing machine (product name: Autograph AGS-X, manufactured by Shimadzu Corporation), the distance was 10 mm. And, when the shape is maintained, ◎, when there is a partial deformation, ◯, and when greatly deformed or broken, ×.

From each sheet elongation <br/> Preparation 1-14, in compliance with the physical testing method of molding materials as specified in JIS K 7312, producing strip-shaped test piece of 10mm × 123mm × 0.03~0.10mm Then, using a precision universal testing machine (product name: Autograph AGS-X, manufactured by Shimadzu Corporation) with a distance between marked lines of 10 mm, the elongation (%) at the time of cutting was measured at a tensile speed of 5 mm / min. Went.

Heat conductive double-sided tape (product name: NO.5046) is placed on the center of one side of an aluminum plate (A10.5P, size: 2.0 mm × 50 mm × 120 mm) with each sheet of 70 ° C. thermal emissivity production examples 1-14. Affixed with a heat conductive tape, manufactured by Maxell Sliontec Co., Ltd. A resistor (shunt resistor, manufactured by PCN, model number PBH1ΩD, rated power 10 W, size: length 20 mm × width 15 mm × thickness 5 mm) is used as the heat source in the center of the back side of the aluminum plate to which the cured product is affixed. Fixed with tape. A constant current (2.82 A) was applied to the heat source, and the temperature of the sheet surface in an equilibrium state after about 1.0 to 1.5 hours was about 70 ° C. Thermography (product name: Thermogear G100, manufactured by NEC Avio Infrared Technology Co., Ltd.) was used for thermal emissivity measurement. A 0.5mm x 0.5mm blackbody tape with an emissivity of 0.95 is affixed to the center of the sheet surface, the thermal emissivity setting of the thermography is set to the emissivity of the blackbody tape (0.95), Measure temperature. After that, with analysis software (Product name: InfReC Analyzer NS9500 Standard
Ver.1.1A, manufactured by NEC Avio Infrared Technology Co., Ltd.) Adjust the thermal emissivity setting so that the temperature of the heat dissipation layer on the black tape surface is the same as the black tape surface. The thermal emissivity was taken as the measured value of the heat dissipation layer.

  In Tables 1 and 2, the composition of the resin composition I obtained in Production Examples 1 to 14 and the sheet-like cured product as the heat dissipation layer, stretchability, elongation, 70 ° C. thermal emissivity and film thickness are shown. Indicated.

  In Table 1 and Table 2, the numerical value of the blending amount of each blend is parts by weight. The details of the blend are as follows.

  Arachid 7005N: Polyester resin (manufactured by Arakawa Chemical Industries, Ltd., tensile elongation 550%, number average molecular weight 23000, hydroxyl value 6-12 mg KOH / g, nonvolatile content 35% by weight, solvent: Solvesso 100, propylene glycol monomethyl ether acetate and Cyclohexanone)

  Arachid 7021: Polyester resin (manufactured by Arakawa Chemical Industries, Ltd., tensile elongation 530%, number average molecular weight 26000, hydroxyl value 5-9 mg KOH / g, nonvolatile content 33% by weight, solvent: Solvesso 150, cyclohexanone)

  Arachid 7015N: Polyester resin (manufactured by Arakawa Chemical Industries, Ltd., number average molecular weight 15000, hydroxyl value 8-16 mg KOH / g, nonvolatile content 40% by weight, solvent: Solvesso 150, butyl glycol, tensile elongation 200%)

  Uban 228: Butylated melamine resin (manufactured by Mitsui Chemicals, solid content 60% by weight, solvent: normal butanol)

  Elitel UE-3310: Polyester resin (manufactured by Unitika Ltd., solid content 100%, number average molecular weight 34000, hydroxyl value 4, tensile elongation 590%)

  JCR 6125 (main agent / crosslinking agent): two-part curable methyl silicone elastomer (manufactured by Dow Corning Toray, solid content 100% by weight, tensile elongation 230%)

  Elastollan C80A: polyester-based thermoplastic polyurethane elastomer (manufactured by BASF, solid content: 100% by weight, tensile elongation: 500%)

  Epokey 802-30CX: urethane-modified epoxy resin (manufactured by Mitsui Chemicals, solid content 30% by weight, tensile elongation 250%, solvent: xylene, cyclohexanone, 3-methoxybutyl acetate, 2-butanol, cyclohexyl acetate)

  Parapet SA: Soft acrylic resin (manufactured by Kuraray Co., Ltd., solid content 100% by weight, tensile elongation 210%)

  TITONE R-32: Titanium oxide powder (manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size 0.2 μm)

  Shinano Random GP-3000: Silicon carbide powder (manufactured by Shinano Denki Smelting Co., Ltd., average primary particle size 4.0 μm)

  Boronid S3: Boron nitride powder (manufactured by ESK CERAMICS, average primary particle size of 10.0 μm or less)

  HO # 100: Calcium fluoride powder (manufactured by Sankyo Flour Milling Co., Ltd., average primary particle size of 6.0 μm or less)

Production Example 15
An acrylic polymer pressure-sensitive adhesive (trade name: Finetac CT-6010, manufactured by DIC Corporation, nonvolatile content 25% by weight, solvent: ethyl acetate) was used as the pressure-sensitive adhesive composition II. This composition was applied with an applicator to a polyethylene terephthalate film (thickness 75 μm) subjected to a release treatment so that the film thickness after drying was 20 to 30 μm. After standing in a room for about 5 minutes, drying in a dryer at 100 ° C. for 3 minutes, and further aging at 40 ° C. for 72 hours, the polyethylene terephthalate film was peeled off, and the sheet was cured as an adhesive layer I got a thing.

Production Examples 16-20
As the pressure-sensitive adhesive composition II to be used, a sheet-like cured product as a pressure-sensitive adhesive layer was obtained in the same manner as in Production Example 15 except that the pressure-sensitive adhesive or component composition described in Table 2 below was used.

  About the sheet-like hardened | cured material as an adhesion layer obtained in manufacture examples 15-20, the elasticity and elongation rate were measured in accordance with the following method.

The sheet-like cured product as the stretchable adhesive layer is processed into a strip shape of 10 mm × 123 mm × 0.01 to 0.15 mm in accordance with a physical test method for a molded article defined in JIS K 7312, and the distance between marked lines is 10 mm. It was confirmed whether the shape after extending to 200% could be maintained. ◎ when the shape can be maintained, ◯ when there is some deformation, and x when greatly deformed or broken.

The sheet-like cured product as the elongation adhesive layer is processed into a strip shape of 10 mm × 123 mm × 0.01 to 0.15 mm in accordance with a physical test method of a molded article defined in JIS K 7312, and the distance between marked lines is 10 mm. The elongation (%) at the time of cutting was measured at a tensile speed of 5 mm / min using a precision universal testing machine (product name: Autograph AGS-X, manufactured by Shimadzu Corporation).

  Table 3 shows the physical properties of stretchability, elongation, and film thickness for the composition of the pressure-sensitive adhesive composition II obtained in Production Examples 15 to 20 and the pressure-sensitive adhesive layer (cured material sheet).

  In Table 3, the compounding quantity of each compound is a weight part of the following product. The details of the blend are as follows.

  Finetac CT-6010: Acrylic polymer adhesive (manufactured by DIC Corporation, nonvolatile content 25% by weight, solvent: ethyl acetate)

  Finetac CT-3080: Acrylic polymer adhesive (manufactured by DIC Corporation, non-volatile content 45% by weight, solvent: ethyl acetate, methyl ethyl ketone)

  Aron Tack S-1601: Solvent type acrylic polymer adhesive (manufactured by Toagosei Co., Ltd., nonvolatile content 30% by weight)

  Alumina AL-43-M: Alumina powder (Showa Denko K.K., average primary particle size 1.5 μm)

Examples 1-26
The cured product sheet, which is the heat dissipation layer obtained in Production Examples 1 to 14, and the sheet-like cured product as the adhesive layer obtained in Production Examples 15 to 20 were pressure-bonded to produce a heat dissipation sheet having a two-layer structure. As physical properties of the obtained heat-dissipating sheet, elongation, stretchability, adhesion, 70 ° C. thermal emissivity, and heat dissipation were measured by the following methods.

About the heat-radiation sheet of the stretchable Examples 1-26, it processed into a 10 mm x 123 mm x 0.05-0.2 mm strip shape according to the physical test method of the molding defined in JIS K 7312, and the distance between marked lines is 10 mm. It was confirmed whether the shape after extending to 100% could be maintained. ◎ when the shape can be maintained, ◯ when there is some deformation, and x when greatly deformed or broken.

Grooves with a width of 10 mm and a depth of 5 mm were formed on the surface of an adhesive aluminum plate (A10.5P, size: 10.0 mm × 50 mm × 120 mm) at intervals of 10 mm perpendicular to the length direction. Twenty-six heat dissipating sheets were attached to confirm the adhesion. After sticking, ◎ indicates that there is not much gap between the processed surface and the heat dissipation sheet, ◎ if there is a slight gap, ○ if there is a large gap and the heat dissipation sheet cannot follow the processed surface × It was.

Elongation radiating sheet, in compliance with the physical testing method of molding materials as specified in JIS K 7312, processed into a strip shape of 10mm × 123 mm × 0.05 to 0.2 mm, as the distance 10mm between marked lines, precision universal testing machine (Product name: Autograph AGS-X, manufactured by Shimadzu Corporation) was used to measure elongation (%) at the time of cutting at a tensile speed of 5 mm / min.

The 70 ° C. Thermal emissivity heat radiation sheet, an aluminum plate (A10.5P, Size: 2.0mm × 50mm × 120mm) on one side of the center of the thermally conductive double-sided tape (trade name: NO.5046 thermally conductive tape, Maxell Affixed with Sliontec Co., Ltd. A resistor (a shunt resistor, manufactured by PCN, model number PBH1ΩD, rated power 10 W, size: length 20 mm × width 15 mm × thickness 5 mm) is provided on the both sides of the center of the back side of the aluminum plate to which the sheet is attached. Fixed with tape. A constant current (2.82 A) was applied to the heat source, and after 1.0 to 1.5 hours had elapsed, the temperature of the sheet surface in an equilibrium state was set to about 70 ° C. Was about 70 ° C. Thermography (product name: Thermogear G100, manufactured by NEC Avio Infrared Technology Co., Ltd.) was used for thermal emissivity measurement. A 0.5mm x 0.5mm blackbody tape with an emissivity of 0.95 is affixed to the center of the sheet surface, the thermal emissivity setting of the thermography is set to the emissivity of the blackbody tape (0.95), Measure temperature. After that, in the analysis software (Product name: InfReC Analyzer NS9500 Standard Ver.1.1A, manufactured by NEC Avio Infrared Technology Co., Ltd.) The temperature of the heat dissipation sheet surface on the side of the black body tape is the same as that of the black body tape surface. Thus, the thermal emissivity setting was adjusted, and the thermal emissivity at that time was taken as the measured value of the heat dissipation sheet.

A groove with a width of 10 mm and a depth of 5 mm was formed on the surface of a heat-dissipating aluminum plate (A10.5P, size: 10.0 mm × 50 mm × 120 mm) at intervals of 10 mm perpendicular to the length direction. Twenty-two heat dissipation sheets were attached. A resistor (shunt resistor, manufactured by PCN, model number PBH1ΩD, rated power 10 W, size: length 20 mm × width 15 mm × thickness 5 mm) is used as a heat source in the center of the back surface, and a thermally conductive double-sided tape (trade name: NO) 5046 was fixed with a heat conductive tape, manufactured by Maxell Sliontec Co., Ltd. A constant current (3.2 A) was applied to the heat source, and after 1.0 to 1.5 hours had passed, the temperature of the heat source that had reached an equilibrium state was about 100 ° C. A K thermocouple was used to measure the temperature of the heat source. Compared with the case where the heat-dissipation sheet was not attached, when the temperature decreased by 10 ° C. or more, “◎”, “less than 7-10 ° C.”, and “less than 7 ° C.” as x.

  Tables 4 to 9 show the sheet configuration and physical properties of the heat dissipation sheet.

Comparative production examples 1-2
Except having changed the kind and amount of each component to be used as described in Table 10 below, a cured sheet as a heat radiation layer was obtained in the same manner as in Production Example 1.

  Table 10 shows the physical properties measured in the same manner as described above for the composition of the resin composition I obtained in Comparative Production Examples 1 and 2 and the heat dissipation layer (cured material sheet).

  In Table 10, the compounding quantity of each compound is a weight part of the following product. The details of the blend are as follows.

  Elitel UE-3380: Polyester resin (manufactured by Unitika Ltd., solid content 100%, number average molecular weight 8000, hydroxyl value 15, tensile elongation 155%)

  Elitel UE-3350: Polyester resin (manufactured by Unitika Ltd., solid content 100%, number average molecular weight 5000, hydroxyl value 25, tensile elongation 105%)

  From Table 10, it can be seen that in Comparative Production Examples 1 and 2, the heat dissipation layer has a tensile elongation of 100% or less.

Comparative production examples 3-4
A sheet-like cured product as an adhesive layer was obtained in the same manner as in Production Example 15 except that the type and amount of each component used were changed as described in Table 11 below.

  Table 11 shows the properties of the pressure-sensitive adhesive composition II obtained in Comparative Production Examples 3 and 4 and the physical properties measured in the same manner as described above for the pressure-sensitive adhesive layer (cured material sheet).

Comparative Examples 1-4
Heat radiation for comparison of the two-layer structure by pressure bonding the cured sheet as the heat radiation layer obtained in Comparative Production Examples 1 and 2 and the sheet-like cured material as the adhesive layer obtained in Comparative Production Examples 3 to 4 A sheet was produced. As physical properties of the obtained heat-dissipating sheet, elongation, adhesion, 70 ° C. thermal emissivity, and heat dissipation were measured by the same method as described above.

  Table 12 shows the sheet configuration and physical properties of a comparative heat dissipation sheet.

  The stretchable heat dissipation sheet of the present invention is used by attaching to various products such as electronic components such as semiconductors, LED elements, electronic substrates, etc., and electronic products that are casings containing these components. It can be suitably used when releasing heat generated from these parts and products.

DESCRIPTION OF SYMBOLS 1 Conventional heat radiation sheet 2 Heat radiation film 3 Heat absorption layer 4 Adhesive layer 5 The elastic heat radiation sheet 6 heat radiation layer 7 adhesion layer which concerns on this invention

Claims (15)

  A heat-dissipating layer having a tensile elongation of 100% or more obtained from the resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B) and infrared absorbing inorganic particles (C); A stretchable heat-dissipating sheet having a two-layer structure having a tensile elongation of 100% or more, comprising an adhesive layer having a tensile elongation of 200% or more obtained from the resin composition II containing the conductive resin (D).   The stretchable heat radiation sheet according to claim 1, wherein the resin (A) having a tensile elongation of 200% or more is at least one selected from the group consisting of a polyester resin, an acrylic resin, an epoxy resin, a polyurethane resin, and a silicone resin. .   The resin (A) having a tensile elongation of 200% or more is a polyester resin, and its number average molecular weight is 10,000 to 80,000, and its hydroxyl value is 1 to 20 mgKOH / g or less. The stretchable heat dissipation sheet according to claim 1.   The stretchable heat-radiating sheet according to claim 1, wherein the crosslinking agent (B) is an amino resin-based crosslinking agent.   Infrared absorbing inorganic particles (C) selected from the group consisting of non-porous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, salicite, mica and cordierite The elastic heat-radiating sheet according to claim 1, which is at least one kind.   The stretchable heat-radiating sheet according to claim 1, wherein the infrared-absorbing inorganic particles (C) absorb infrared rays having a wavelength range of 6.3 to 10.5 µm.   The stretchable heat radiation sheet according to claim 1, wherein the average primary particle diameter of the infrared absorbing inorganic particles (C) is 0.1 to 15.0 µm.   The elastic heat-radiating sheet according to claim 1, wherein the content of the infrared-absorbing inorganic particles (C) is 10 to 60% by weight of the heat-dissipating layer.   In the resin composition I, the content of the crosslinking agent (B) is 1 to 40 parts by weight (in terms of solids) and 100 parts by weight (in terms of solids) of the resin (A) having a tensile elongation of 200% or more and The stretchable heat radiation sheet according to claim 1, wherein the content of the infrared-absorbing inorganic particles (C) is 20 to 200 parts by weight.   The elastic heat-radiating sheet according to claim 1, wherein the heat emissivity of the heat-dissipating layer is 0.95 or more at 70 ° C.   The stretchable heat radiation sheet according to claim 1, wherein the adhesive resin (D) is at least one resin selected from the group consisting of an acrylic resin, a polyurethane resin, a polyester resin, and a silicone resin.   The stretchable heat-radiating sheet according to claim 1, wherein the adhesive layer contains 10 to 80% by weight of inorganic particles (E) having a thermal conductivity of 10 to 300 W / m · K.   The elastic heat-radiating sheet according to claim 1, wherein the heat-radiating layer has a thickness of 10 to 100 μm.   The stretchable heat-radiating sheet according to claim 1, wherein the adhesive layer has a thickness of 10 to 150 μm.   An article to which the stretchable heat radiation sheet according to claim 1 is attached.