KR20150008140A - Stretchable heat-radiation sheet, and article having same attached thereto - Google Patents

Abstract

The present invention relates to a heat radiation layer having a tensile elongation percentage of 100% or more obtained by the resin composition I containing the resin (A) having a tensile elongation percentage of 200% or more, the crosslinking agent (B) and the infrared absorbing inorganic particles (C) (EN) A stretchable heat - dissipating sheet having a two - layer structure having a tensile elongation percentage of 100% or more and a pressure - sensitive adhesive layer having a tensile elongation percentage of 200% or more obtained by the resin composition II containing the pressure - sensitive adhesive resin (D). The present invention also provides an article to which the stretchable heat-radiating sheet of the above-described two-layer structure is attached.

Description

STRATCHABLE HEAT-RADIATION SHEET, AND ARTICLE HAVING SAME ATTACHED THERETO BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a stretchable heat-

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

BACKGROUND ART [0002] Recently, as the performances of electronic components, optical components such as semiconductors, LED elements, and electronic boards, and electronic products, electric products, and optical products, which are cases including these components, have been improved, Accordingly, when these parts and products can not be cooled properly, problems such as breakage and short life span arise. Therefore, various heat-radiating sheets are used as a means for releasing heat generated from these parts and products to the outside.

For example, in Patent Document 1, a flexible heat-radiating film having an infrared radiation effect is formed on the surface of a flexible heat-absorbing layer having thermal conductivity to form a pressure-sensitive adhesive layer of a thermally conductive adhesive on the back surface of the heat- A heat radiation sheet having a three-layer structure is proposed. Fig. 1 shows a schematic view of the conventional heat radiation sheet. 1, reference numeral 1 denotes a heat radiation sheet, 2 denotes a heat radiation film, 3 denotes an heat absorbing layer such as an aluminum plate, and 4 denotes an adhesive layer. However, the heat-radiating sheet has flexibility because it uses a thin metal plate such as aluminum as the heat-absorbing layer, but has insufficient flexibility and stretchability when it is adhered to a component having a complicated shape. Since the heat radiation sheet of Patent Document 1 has a three-layer structure of a heat radiation film, an endothermic layer and an adhesive layer, thermal resistance is generated between the respective layers from the heat source to the heat radiation film as the outermost layer, .

To this end, Patent Document 2 discloses a heat-radiating sheet having a two-layer structure in which a total thickness of 2 to 14 占 퐉 and a total infrared absorptivity of 0.85 or more and a heat conductivity in the thickness direction of 1 W / mK, As shown in Fig. By incorporating boron nitride, carbon fiber or the like into the polyimide film, safety heat radiation efficiency is secured. However, since the polyimide film used as the heat-radiating layer is a resin which is originally lacking in flexibility and stretchability, the flexibility and stretchability required for attaching to a component having a complicated shape are also insufficient.

Accordingly, there is a demand for a heat-radiating sheet excellent in flexibility and stretchability, which can easily adhere to various parts such as electronic parts and optical parts and various parts such as a case including these parts or all of them.

Publication 2004-200199 Publication No. 2011-32430

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

The present inventors have studied hard to solve the above problems. As a result, it has been found that a two-layer stretchable heat-radiating sheet having a specific tensile elongation percentage composed of a heat-radiating layer containing a specific component and having a specific tensile elongation percentage and an adhesive layer having a specific tensile elongation percentage can solve the above problems Thus, the present invention has been completed.

That is, the present invention provides the following elastic heat-radiating sheet and the article to which the elastic heat-

1. A heat dissipation layer having a tensile elongation percentage of 100% or more obtained by the resin composition I containing a resin (A) having a tensile elongation of 200% or more, a crosslinking agent (B) and an infrared absorbing inorganic particle (C)

A stretchable heat-radiating sheet having a two-layer structure having a tensile elongation percentage of 100% or more and a pressure-sensitive adhesive layer having a tensile elongation percentage of 200% or more obtained by the resin composition II containing the pressure-sensitive adhesive resin (D).

2. The resin composition 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 Heat-shielding sheet.

3. The method of claim 1,

Wherein 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 mg KOH / g or less.

4. The stretchable heat-dissipating sheet according to claim 1, wherein the cross-linking agent (B) is an amino resin-based cross-linking agent.

5. The infrared absorbing inorganic particle (C) according to claim 1, wherein the infrared absorbing inorganic particles (C) are selected from the group consisting of nonporous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, silicide, Wherein the elastic sheet is at least one member selected from the group consisting of mica and cordierite.

6. The stretchable heat-radiating sheet according to claim 1, wherein the infrared-absorbing inorganic particles (C) absorb infrared rays in a wavelength range of 6.3 to 10.5 m.

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

8. The stretchable 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-radiating layer.

9. The resin composition according to claim 1, wherein the content of the crosslinking agent (B) in the resin composition I is 1 to 40 parts by weight (in terms of solid content) and 100 parts by weight (in terms of solid content) Wherein the content of the infrared absorbing inorganic particles (C) is 20 to 200 parts by weight.

10. The heat-radiating sheet according to claim 1, wherein the heat radiation layer has a thermal emissivity of 0.95 or more at 70 占 폚.

11. The stretchable heat-radiating sheet according to claim 1, wherein the viscous 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.

12. The stretchable heat-dissipating sheet according to claim 1, wherein the pressure-sensitive adhesive layer contains 10 to 80% by weight of inorganic particles (E) having a thermal conductivity of 10 to 300 W / m · K.

13. The heat-radiating sheet according to claim 1, wherein the thickness of the heat-radiating layer is 10 to 100 占 퐉.

14. The stretchable heat-radiating sheet according to claim 1, wherein the thickness of the adhesive layer is 10 to 150 占 퐉.

15. An article to which the flexible heat-radiating sheet of claim 1 is attached.

According to the present invention, the following effects are obtained.

(1) The stretchable heat-radiating sheet of the present invention has a two-layer structure of a heat-radiating layer having a specific tensile elongation percentage and a pressure-sensitive adhesive layer having a specific tensile elongation percentage without inserting a metal layer such as aluminum or copper. Not only excellent but also excellent in elasticity. Further, the heat-radiating sheet according to the present invention efficiently emits heat transmitted to the heat-radiating layer to the outside world while passing through the pressure-sensitive adhesive layer of the heat-radiating sheet in a heating element such as an electronic component as a skin complex to cool the heating element. Accordingly, the heat-radiating sheet of the present invention has sufficient flexibility, followability, adhesion, and excellent heat radiation property to adhere to various components, particularly, components having a complicated shape.

(2) The flexible heat-radiating sheet of the present invention can be suitably applied to various products such as electronic parts such as semiconductors, LED devices, electronic boards and the like, and electronic appliances including these parts in accordance with excellent flexibility and stretchability thereof And thus can effectively dissipate the heat generated by these parts and products.

(3) The flexible heat-radiating sheet of the present invention can be brought into close contact with the heat-generating portion or the whole of a heat-generating component such as an electronic board and a heat- The efficiency is very high.

(4) Further, by combining the elastic heat-radiating sheet of the present invention with other physical cooling methods such as heat-dissipating fins, downsizing of the cooling method and downsizing of the product are possible.

(5) Further, the elastic heat-radiating sheet of the present invention can be easily used without problems even when the article to which the heat-dissipating heat-dissipating sheet is attached is low in heat resistance and heat resistance, unlike a solution or paste of heat dissipation paint as an organic solvent solution or paste.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of a conventional three-layered heat-radiating sheet. FIG.
2 is a schematic view of a two-layer stretchable heat-radiating sheet according to the present invention.
3 is a photograph showing a state in which a stretchable heat-radiating sheet according to the present invention is attached to a part of a printed wiring board.

The stretchable heat-radiating sheet of the present invention has a two-layer structure composed of a heat-radiating layer having a tensile elongation percentage of at least 100% and a pressure-sensitive adhesive layer having a tensile elongation of at least 200%, and a tensile elongation percentage of the sheet itself is not less than 100% (A), a crosslinking agent (B) and an infrared absorbing inorganic particle (C) having an elongation of 200% or more.

In the present invention, the tensile elongation percentage is a value measured in accordance with the method specified in JIS K 7312. Specifically, for example, in the case of the resin (A), a sheet made of the resin is processed into a rectangle of 10 mm x 123 mm x 0.1 mm, and the distance between the marks is 10 mm and the tensile speed is 5 mm / min (Elongation at break (%)) when the elongation percentage is measured. The elongation percentage can be measured, for example, using a precision universal testing machine. As a precision universal testing machine, commercially available "Autograph AGS-X" (product name, manufactured by Shimadzu Corporation) can be used. This measurement method is also applied to the measurement of the respective tensile elongation ratios of the heat-radiating layer, the pressure-sensitive adhesive layer and the heat-radiating sheet according to the present invention.

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

As the resin (A), a known resin can be used without particular limitation as long as the tensile elongation is 200% or more. The tensile elongation percentage of the resin (A) is preferably 200 to 600%. If the tensile elongation percentage of the resin (A) exceeds 600%, the stability of the heat-radiating sheet after stretching is greatly lowered, and the adhesion of the article to be adhered tends to become insufficient. From this viewpoint, the tensile elongation percentage of the resin (A) is preferably 200 to 550%.

Specific examples of the resin (A) include a polyester resin, an acrylic resin, a polyurethane resin, an epoxy resin, and a silicone resin, and these resins can be used singly or in combination of two or more. Among them, a polyester resin is preferable in that the heat-radiating sheet of the present invention is brought into close contact with 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 make the tensile elongation percentage of the heat radiation sheet of the present invention at least 100% A stretchable heat-radiating sheet can not be obtained.

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

The dicarboxylic acid to be used includes aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. 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, maleic anhydride and the like. The alicyclic dicarboxylic acid is not particularly limited, and examples thereof include hexahydrophthalic anhydride, hexahydroisophthalic acid, and hexahydroterephthalic acid. These dicarboxylic acids may be used singly or in combination of two or more. However, it is preferable to use an aromatic dicarboxylic acid in combination with an aliphatic dicarboxylic acid. These dicarboxylic acids may be used as they are, And lower alkyl esters such as diethyl ester may be used. However, considering flexibility and tensile elongation percentage of the elastic sheet of the present invention, it is preferable that the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid are used together in the weight ratio range of about 95: 5 to about 70: 30 Do. In addition to these dicarboxylic acids, polybasic acids having three or more valences such as benzoic acid, crotonic acid, pt-butylbenzoic acid, monobasic acid, anhydrous trimellitic acid, methylcyclohexene tricarboxylic acid and anhydrous pyromellitic acid Etc. may be used in combination.

Diols to be used include aliphatic diols which do not have a pulverizing structure such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butane diol and 1,6-hexane diol; Aliphatic diols having a pulverized structure such as 1,3-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methylpentanediol and 1,4-hexanediol; And alicyclic diols such as 1,4-dimethylolcyclohexane. In particular, the aliphatic diol having a pulverized structure and the aliphatic diol having no pulverized structure are preferably used together in the weight ratio range of about 90:10 to 50:50 by the former-former. These diols may be used singly or in combination of two or more, but it is preferable to use an aliphatic diol having a pulverized structure and an aliphatic diol having no branched structure. In addition to these diols, polyol components having three or more valences such as trimethylolpropane, trimethylolethane, and glycerin may be used in combination if necessary.

The polyester resin used as the resin (A) preferably has a number average molecular weight of about 10,000 to 80,000, and more preferably about 15,000 to 50,000. The hydroxyl value of the polyester resin is preferably about 1 to 20 mg / KOH, more preferably about 4 to 16 mg KOH / g. When a polyester resin having such properties is used, the hardness of the heat radiation layer of the heat radiation sheet of the present invention and the workability of the sheet itself are balanced with each other.

As the acrylic resin, an alkyl (meth) acrylate ester in which the alkyl group has 1 to 18 carbon atoms and an acrylic resin obtained by styrene are preferable. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec- (Meth) acrylate, octadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (Meth) acrylate, octyldodecenyl acrylate, octadecenyl acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate. The adhesion between the heat radiation layer and the pressure- The number of carbon atoms of the alkyl group is preferably from about 1 to about 12, and more preferably from about 1 to about 5. Examples of the styrenes include styrene,? -Methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene and chlorovinyltoluene. (Meth) acrylic acid alkyl esters and styrenes, as well as various known α-olefins, nitriles, (meth) acrylamides and the like, in addition to the (meth) acrylic acid alkyl esters and styrenes, from the viewpoint of contributing to the adhesion to the adhesive layer and the hardness of the heat- , (Meth) acrylic acid hydroxyalkyl esters, and the like.

The amount of the (meth) acrylic acid alkyl ester, styrene and other monomers having a carbon number of 1 to 18 in the alkyl group is not particularly limited, but when the total monomer is 100 mol% More preferably about 60 to about 60 mol%, about 60 to about 40 mol% and about 0 to about 10 mol%, particularly preferably about 45 to 55 mol%, about 55 to 45 mol%, and about 0 to 5 mol% .

The acrylic resin production method is not particularly limited, and various known polymerization reactions can be employed. For example, the (meth) acrylic acid alkyl esters, styrenes and other monomers may be reacted at 20 to 120 ° C for 2 to 10 hours in the presence of various known radical polymerization initiators at the above-mentioned usage. In the reaction, a suitable one of the organic solvents described later can be used as a reaction solvent. Examples of the radical polymerization initiator include potassium persulfate, ammonium persulfate, 2,2'-azobis (2-amidinopropane) 2,2'-azobisisobutylnitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and the like.

Examples of commercially available acrylic resin products include parapet SA (made by Kuraray, elongation rate: 200%), almatex 748-5M (manufactured by Mitsui Chemicals) , ALMATEX 748-16AE (manufactured by Mitsui Chemicals), and the like.

Specific examples of the epoxy resin include a non-amine-modified epoxy resin, an amine-modified epoxy resin and an amine-urethane-modified epoxy resin.

As the non-amine-modified epoxy resin, various known resins can be used without particular limitation. Specifically, for example, bisphenol-type epoxy resins obtained by glycidizing various bisphenols, hydrides of the bisphenol-type epoxy resins, phenol novolak resins and cresol novolak resins can be obtained by reacting haloepoxide Novolac epoxy resins, biphenyl type epoxy resins, and the like. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, Tetrafluorobisphenol A, and the like.

As the amine-modified epoxy resin, various known ones can be used without any particular limitation. Specifically, for example, the above-mentioned non-amine-modified epoxy resin, particularly bisphenol-type epoxy resin or its hydrated product, is reacted with various known amines. Examples of the amines include aromatic amines such as toluidines, xylidines, cumidine (isopropylanilines), hexyl anilines, nonyl anilines, and dodecyl anilines; Cycloaliphatic amines such as cyclopentylamines, cyclohexylamines and norbornylamines; But are not limited to, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, stearylamine, eicosylamine, 2-ethylhexylamine, dimethylamine, diethylamine, dipropylamine, Aliphatic amines such as dibutylamine, dipentylamine and diheptylamine; There may be mentioned alkanolamines such as diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine and N-benzylethanolamine. Of these, Considering the strength and the adhesion with the base material, it is preferable to have at least one alkyl group having 3 to 30 carbon atoms in the molecule.

As the amine-urethane-modified epoxy resin, various known ones can be used without any particular limitation. Specifically, there may be mentioned, for example, those obtained by further modifying the amine-modified epoxy resin with a polyisocyanate. Examples of the polyisocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, trilenediisocyanate, butane-1,4-diisocyanate, hexadiisocyanate, 2,2,4- Aliphatic, alicyclic or aromatic diisocyanates such as trimethyl hexadienesocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. As the amine-modified epoxy resin and the amine-urethane-modified epoxy resin, those described in JP-A-2010-235918 may be used.

As the above-mentioned polyurethane resin (except for those corresponding to the amine-urethane modified epoxy resin described above), various known ones can be used without particular limitation. Specifically, there may be mentioned, for example, a polymer polyol and a polyisocyanate as a raw material. The polymer polyol includes a polyester polyol, a polyether polyol, a polycarbonate polyol, an acryl polyol and the like, and the polyisocyanate includes those described above. Further, in order to impart aqueousity to the polyurethane resin, the above-mentioned carboxyl-containing diol such as dimethylpropanic acid or dimethylobutanoic acid may be used as the diol component. The number average molecular weight thereof is not particularly limited, but is usually about 10,000 to 80,000, particularly about 15,000 to 50,000. Examples of commercially available products include elastollan C80A (elongation percentage: 500%) and Elastollan C1180A (elongation: 550%).

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. As commercial products, there were used JCR 6125 (two-component curing type silicone elastomer, elongation percentage of 230%), SE9186 (elongation percentage of 555%) and SE6186L (elongation of 320%, acrylic modified silicone elastomer) .

The crosslinking agent (B) is used for the purpose of securing its hardness by bonding the resin (A) in a cross-linked form in the heat-releasing layer, and it may be suitably selected in accordance with the type of resin (A) and its functional group.

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

As the inorganic particles (C), various known ones can be used without particular limitation. Specific examples thereof include titanium oxide, silicon carbide, nonporous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, silicide, mica ), Cordierite, and the like. These may be used singly or as a mixture of two or more kinds.

When inorganic particles (hereinafter referred to as component (c)) which absorbs infrared rays in the wavelength range of about 6.3 to 10.5 μm among the inorganic particles (C) are used, from the viewpoint of heat radiation efficiency of the heat radiation sheet of the present invention desirable. Preferable examples thereof include porous silica, boron nitride, calcium fluoride and aluminum hydroxide. These may 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 more preferably about 20 to 80% by weight from the viewpoint of heat radiation efficiency of the heat radiation sheet.

Furthermore, the curve of the inorganic particles (C) is not particularly limited as long as it is a value equal to or smaller than the thickness of the heat dissipation layer. For example, when the inorganic particles (C) have an average primary particle diameter of about 0.1 to 15.0 μm, preferably about 0.1 to 10.0 μm, the heat radiation sheet of the present invention has good stretchability, So that it can be easily brought into close contact with the surface of the substrate.

The content of the inorganic particles (C) in the heat-radiating layer of the heat-radiating sheet of the present invention is not particularly limited, but is preferably about 10 to 60% by weight in view of the heat radiation efficiency, depending on the weight of the heat-

The heat dissipation layer is formed by using the resin composition I containing the resin (A) having a tensile elongation percentage of 200% or more, the crosslinking agent (B) and the inorganic particles (C). The content of each component in the resin composition I is not particularly limited, but the content of the crosslinking agent (B) in an amount of 1 to 40 parts by weight (in terms of solid content) relative to 100 parts by weight of the resin (A) (20 to 200 parts by weight), preferably about 5 to 25 parts by weight (in terms of solid content) of the crosslinking agent (B) and about 70 to 150 parts by weight for the inorganic particles (C) The stretchability can be improved.

To the resin composition I, known additives may be used as long as the effect of the present invention is not impaired. Usable additives include thickeners such as organic bentonite, carboxymethylcellulose, and polyvinyl alcohol; And various dispersants such as polyacrylic acid and polyacrylic acid salt. When the additive is used, the amount to be used is not particularly limited, but usually it is 5% by weight or less in terms of solid content in the resin composition I.

The resin composition I may be used in the form of a liquid composition or paste 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, butylalcohol and isobutylalcohol; Polyhydric alcohols such as ethylene glycol, ester solvents such as methyl acetic acid, ethyl acetic acid and butyl acetic acid; 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 is required to have a tensile elongation percentage of 100% or more. By doing so, the heat radiation sheet of the present invention is brought into close contact with skin complexes, particularly complex parts and products. From this point of view, the tensile elongation percentage is preferably 100% or more and 300% or less, and more preferably 100% or more and 200% or less. The adjustment of the tensile elongation percentage of the heat dissipation layer is carried out by, for example, B) and the content of the inorganic particles (C).

It is preferable that the heat radiation rate of the heat radiation layer is 0.95 or more at 70 캜 from the viewpoint of heat radiation efficiency of the heat radiation sheet of the present invention.

The pressure-sensitive adhesive layer of the heat-releasing sheet of the present invention can be obtained by the resin composition II containing the tacky resin (D).

As the adhesive resin (D), a known resin may be used without particular limitation as long as it is a resin having adhesiveness. Specific examples thereof include acrylic resin, polyurethane resin, polyester resin and silicone resin. These resins may be used alone or in combination of two or more. Of these, acrylic resin is preferable. As the adhesive resin (D), for example, a sticky resin described in Japanese Patent Application Laid-Open No. 2008-195904 or a sticky resin described in Japanese Patent Laid-Open Publication No. 2012-131921 may be used.

The acrylic resin is usually obtained by polymerizing an alkyl (meth) acrylate. The alkyl (meth) acrylate to be used is not particularly limited and known ones can be used. Specific examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and isopropyl (meth) acrylate. The glass transition temperature of the acrylic resin is preferably -20 캜 or lower. The melt viscosity is preferably 50,000 mPa · s or more, more preferably 100,000 to 70,000 mPa · s.

As the polyurethane resin, the polyester resin and the silicone resin, those having adhesiveness can be selected from among those disclosed as the resin (A).

The resin composition II may contain inorganic particles (E) having a thermal conductivity of about 10 to 300 W / m · K, if necessary. For example, as will be described later, the thickness of the pressure-sensitive adhesive layer is not particularly limited, but when the value is 10 μm or more and 30 μm or less, thermal resistance relating to heat conduction of the pressure-sensitive adhesive layer can be neglected, Not required. On the other hand, when the width exceeds 30 탆, the thermal resistance of the pressure-sensitive adhesive layer becomes difficult to ignore, and therefore 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, and these may be used singly or in combination of two or more kinds. have.

The amount of the inorganic particles (E) to be used is not particularly limited, but is preferably from about 10 to about 80% by weight, depending on the weight of the pressure-sensitive adhesive layer, from the viewpoint of increasing the thermal conductivity of the pressure- .

Further, the curve of the inorganic particles (E) is not particularly limited as long as it is a value equal to or smaller than the thickness of the heat dissipation layer. For example, when the inorganic particles (E) have an average primary particle diameter of usually about 0.1 to 15.0 占 퐉, preferably about 0.1 to 10.0 占 퐉, the heat-radiating sheet of the present invention has good stretchability, So that it is easy to come into close contact with each other.

The resin composition II may contain a crosslinking monomer, a reactive diluent, and a radical polymerization initiator, if necessary.

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

The reactive diluent may be a known (mono) acrylic compound or the like. Specific examples thereof include 2-ethylhexyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloylpolyol, tricyclodecanyl acrylate, isobornyl acrylate and the like. The amount of the reactive diluent to be used is not particularly limited, but is preferably 50 parts by weight or less based on 100 parts by weight of the viscous 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 phosphineoxy-based initiator may be used. Particularly, it is preferable to use a compound having a hydroxyl group from the viewpoint of compatibility of the composition. The amount of the radical polymerization initiator to be used is not particularly limited, but is preferably 0.5 to 5 parts by weight per 100 parts by weight of the total amount of the crosslinkable monomer and the reactive diluent.

The resin composition II may further contain, as a known additive, additives which do not impair the effects of the present invention, such as tackifiers, anti-settling agents, thickening agents, thixotropy, antioxidants, plasticizers, surfactants, And the like may be included. When the additive is used, its amount to be used 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 paste composition containing an organic solvent or water, and the organic solvent is the same as that used in the resin composition I.

The adhesive layer needs to have a tensile elongation of 200% or more. When the heat-radiating sheet of the present invention is attached to various articles, the pressure-sensitive adhesive layer is located inside the heat-radiating layer and directly contacts the pressure-sensitive adhesive body. Further, since it is necessary to follow and adhere to the concavo-convex shape, it is necessary to have a larger tensile elongation percentage than the heat-radiating layer. The tensile elongation percentage is preferably 200% or more and 400% or less, and more preferably 200% or more and 300% or less, so that various skin complexes, particularly complicated shapes, It becomes easy to be made. The tensile elongation percentage of the adhesive layer can be adjusted by, for example, changing the type and amount of the adhesive resin (D) and the content of the inorganic particles (E).

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

Specifically, the resin composition I may be obtained by coating the resin composition I, which forms the heat-releasing layer, on a suitable support, then coating the resin composition II, followed by drying to peel off the support.

Further, the heat radiation sheet of the present invention can be produced by coating the resin composition II on a suitable support, then coating the resin composition I, drying it, and peeling the support.

Furthermore, the stretchable sheet of the present invention can be produced by coating the resin composition I and the resin composition II on another support, drying the laminate, pressing the heat dissipation layer and the adhesive layer, and peeling off the support.

Here, the support is not particularly limited, and for example, a plastic film or plate such as polyethylene phthalate, a glass plate, a metal plate, or the like can be used. The support may be subjected to mold release treatment as required.

In the heat-radiating sheet of the present invention, the thickness of the heat-radiating 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 mu m, preferably about 12 to 70 mu m. It is possible to maintain the strength of the heat-radiating sheet of the present invention by controlling the thicknesses of both the heat-radiating layer and the pressure-sensitive adhesive layer to 10 μm or more, suppressing breakage during expansion and contraction, By setting the thickness of the adhesive layer to 150 μm or less, heat resistance due to heat conduction can be suppressed, and heat radiation efficiency of the heat radiation sheet of the present invention can be increased.

The heat-radiating sheet of the present invention which can be obtained by the above-mentioned method needs to have a tensile elongation percentage of 100% or more. By making the tensile elongation percentage of the stretchable sheet at 100% or more, it becomes easy to closely adhere to various articles, particularly, parts of complex shapes and products. From this viewpoint, the tensile elongation percentage of the heat-radiating sheet is preferably 100% to 400%, more preferably 100% to 200%, and the adjustment of the tensile elongation percentage of the heat- It is possible by a combination of layers.

Fig. 2 shows a schematic view of an example of a stretchable heat-radiating sheet according to the present invention. In Fig. 2, 5 denotes the elastic heat-radiating sheet of the invention, 6 denotes the heat-radiating layer, and 7 denotes the adhesive layer.

The heat-radiating sheet of the present invention may have a separator attached to one or both surfaces thereof for the purpose of protecting the surface thereof, if necessary. The separator is the above-mentioned support, and a plastic film is particularly preferable from the viewpoint of maintaining the surface smoothness of the heat radiation layer and the pressure-sensitive adhesive layer. The plastic film is not particularly limited as long as it can protect the surface of the heat radiation sheet, and known plastic films can be used. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyethyleneterephthalate film, polybutylene terephthalate film, polyvinyl chloride film, polyurethane film, ethylene-vinyl acetate copolymer film And the like.

According to the excellent flexibility and stretchability of the heat-radiating sheet of the present invention, the heat-radiating sheet of the present invention can be appropriately pasted to various products such as electronic parts such as semiconductors, LED elements, and electronic boards and electronic products And thus can effectively dissipate the heat generated by these components or products.

Fig. 3 is a photograph showing a state in which a flexible heat-radiating sheet according to the present invention is stuck on a semiconductor chip (upper position) and a central operator chip (lower position) of a printed wiring board.

Example

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 by these examples.

Hereinafter, in Production Examples 1 to 14, the resin composition I is used to make a heat radiation layer (sheet-type cured product). In Production Examples 15 to 20, an adhesive layer (sheet-like cured product) is produced using Resin Composition II.

Production Example 1

65 parts by weight of a commercially available polyester resin (trade name: ARAKYD 7005N, manufactured by Arakawa Chemical Industries, Ltd., a tensile elongation of 550%), 65 parts by weight of butylated melamine resin (trade name: Uban 228, 8 parts by weight), titanium dioxide powder (trade name: TI TONE R-32, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter: 0.2 m or less) 16 parts Silicon carbide powder (trade name: Shinano Random) 2 parts by weight of boron nitride powder (trade name: Boronid S3, manufactured by ESK CERAMICS, average primary particle size of 10.0 μm or less) 2 parts by weight (GP-3000 manufactured by Shinano Electric Industries, , And 0.5 part by weight of a dinonylnaphthalenedisulfonic acid amine salt as a catalyst were mixed to prepare Resin Composition I. This resin composition I was applied to a polyethylene terephthalate film (thickness 75 mu m) subjected to release treatment so as to have a film thickness after drying of 30 mu m to 40 mu m with an applicator. After standing for about 5 minutes in the room, it was dried in a dryer at 120 DEG C for 30 minutes, and then the film was peeled off to obtain a sheet-like cured product of the heat radiation layer.

Production Examples 2 to 14

A sheet-like cured product of a heat dissipation layer was obtained in the same manner as in Production Example 1, except that the kind and amount of each component used were changed as shown in Table 1 or 2 below.

The stretchability, tensile elongation and 70 占 폚 heat emissivity of the sheets obtained in Production Examples 1 to 14 were measured by the following methods.

elasticity

A rectangular specimen of 10 mm x 123 mm x 0.03 to 0.10 mm was produced on each sheet of Production Examples 1 to 14 in accordance with the physical test method of a molding specified by JIS K 7312. The distance between marks was 10 mm, And was increased to 100% using a tester (product name: manufactured by Autograph AGS-X Shimadzu Corporation). In the case where the shape was maintained, the case was rated as?, When there was some deformation, it was evaluated as?, And when the shape was largely deformed or broken, the result was evaluated as?.

Elongation rate

A rectangular specimen of 10 mm x 123 mm x 0.03 to 0.10 mm was produced on each sheet of Production Examples 1 to 14 in accordance with the physical test method of a molding specified by JIS K 7312. The distance between the marks was 10 mm, The elongation (%) at the time of cutting was measured at a stretching speed of 5 mm / min using a tester (product name: Autograph AGS-X, Shimadzu Corporation).

70 ℃ heat emissivity

Each sheet of Production Examples 1 to 14 was laminated on the center of one side of an aluminum plate (A10.5P, size: 2.0 mm x 50 mm x 120 mm) with a thermally conductive double-sided tape (trade name: NO.5046 thermally conductive tape, (Manufactured by Maxell Sliontec Co., Ltd.). (20 mm in width × 15 mm in width × 5 mm in thickness) was fixed to the center of the back surface of the aluminum plate to which the cured product was attached with a double-sided tape as a heat source using a resistor (shunt resistor, PCN company, product number PBH1Ω D, Respectively. A constant current (2.82 A) was applied to the heat source, and after a lapse of 1.0 to 1.5 hours, the temperature of the sheet surface in equilibrium was set to about 70 캜. Thermography (product name: Thermo Gear G100, manufactured by NEC Avio Infrared Technology Co., Ltd.) was used for measurement of the thermal emissivity. The temperature of the blackbody tape adhering portion was measured by attaching a black body tape 0.5 mm x 0.5 mm having an emissivity of 0.95 to the center of the sheet surface and setting the thermal emissivity of the black body tape to the emissivity of the black body tape (0.95) The thermal emissivity setting is adjusted so that the temperature of the heat release layer side of the black body tape adhering side is the same as the temperature of the black body tape side, and the thermal emissivity is adjusted by heat dissipation Layer.

Table 1 and Table 2 show the composition of the resin composition I obtained in Production Examples 1 to 14 and the sheet-like cured product of the heat-releasing layer. The stretchability, elongation, heat emissivity at 70 캜 and film thickness were shown.

ingredient Compound Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Resin (A) Arakid 7005N 65 65 Arakid 7021 69 69 Arakid 7015N 58 58 Elitel UE-3510 23 Organic solvent Butyl acetate 34 The crosslinking agent (B) YUVAN 228 8 8 8 8 8 8 8 The inorganic particles (C) TITONE R-32 16 16 16 16 16 16 16 Shinano Random GP-3000 2 2 2 2 2 2 2 Boronide S3 9 9 9 9 HO # 100 9 9 9 Physical properties of heat sink layer elasticity ◎ ◎ ◎ ◎ ◎ ◎ ○ Elongation (%) 152 178 111 148 100 108 273 70 ℃ heat emissivity 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Film thickness (㎛) 35 36 35 38 34 35 35

ingredient Compound Production Example 8 Production Example 9 Production Example 10 Production Example 11 Production Example 12 Production Example 13 Production Example 14 Resin (A) Arakid 7005N 65 65 Elitel UE-3510 23 JCR 6125 Topics 25.3 Elastollan C80A 23.0 Epoxy 802-30CX 77.0 Parapet SA 23.0 Organic solvent Butyl acetate 34 toluene 34.2 34.2 N, N-dimethylformamide 34.2 The crosslinking agent (B) JCR 6125 Crosslinking agent 2.5 YUVAN 228 8 8 8 8 8 8 The inorganic particles (C) TITONE R-32 16 16 16 16 16 16 16 Shinano Random GP-3000 2 2 2 2 2 2 2 Boronide S3 9 9 9 9 9 9 HO # 100 9 Physical properties of heat sink layer Expansion ratio ○ ◎ ◎ ◎ ◎ ◎ ◎ Elongation (%) 289 121 195 140 123 172 121 70 ℃ heat emissivity 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Film thickness (㎛) 36 36 34 36 37 15 90

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

(Manufactured by Arakawa Chemical Industries, Ltd.) having a tensile elongation percentage of 550%, a number average molecular weight of 23,000, a hydroxyl value of 6 to 12 mgKOH / g, a nonvolatile content of 35% by weight, a solvent: Solvesso 100, Propylene glycol monomethyl ether acetate and cyclohexanone)

(Manufactured by Arakawa Chemical Industries, Ltd.) having a tensile elongation percentage of 530%, a number average molecular weight of 26,000, a hydroxyl value of 5 to 9 mgKOH / g, a nonvolatile content of 33% by weight, a solvent: Solvesso 150, cyclohexanone )

(Number average molecular weight: 15,000, hydroxyl value: 8 to 16 mgKOH / g, nonvolatile content: 40% by weight, solvent: Solvesso 150, butyl glycol, tensile elongation: 200%) manufactured by Arakawa Chemical Industries,

YUBAN 228: Butylated melamine resin (manufactured by Mitsui Chemicals, Inc., solids content: 60% by weight, solvent: normal butanol)

Elitel UE-3310: polyester resin (manufactured by Unichica Corporation, solid content 100%, number average capacity 34,000, hydroxyl value 4, tensile elongation 590%)

JCR 6125 (subject / crosslinking agent): 2-L curable methyl silicone elastomer (manufactured by Dow Corning Toray, solid content: 100% by weight, tensile elongation: 230%

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

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

Parapet SA: Soft acrylic resin (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 diameter 0.2 μm)

Shinano Random GP-3000: silicon carbide powder (manufactured by Shinano Electric Industries, Ltd., average primary particle diameter 4.0 m)

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

HO # 100: Calcium fluoride powder (manufactured by Sankyo Seiyaku Co., Ltd .; average primary particle diameter of not more than 6.0 m)

Production Example 15

(Fine tec CT-6010, manufactured by DIC, nonvolatile content of 25% by weight, solvent: ethyl acetate) was used as the pressure-sensitive adhesive composition II. This composition was applied to a polyethylene terephthalate film (75 μm thick) which had been subjected to release treatment so that the film thickness after drying was 20 to 30 μm by an applicator. After standing for about 5 minutes in the room, it was dried at 100 DEG C for 3 minutes in a dryer, aged at 40 DEG C for 72 hours, and then the polyethylene terephthalate film was peeled off to obtain a sheet-like cured product of an adhesive layer.

Production Examples 16 to 20

As the pressure-sensitive adhesive composition II to be used, the sheet-like cured product of the pressure-sensitive adhesive layer was obtained in the same manner as in Production Example 15, except for the pressure-sensitive adhesive composition or composition shown in Table 2 below.

The stretchability and elongation percentage of the sheet-form cured product of the pressure-sensitive adhesive layer obtained in Production Examples 15 to 20 were measured by the following methods.

elasticity

The sheet-like cured product of the adhesive layer was processed into a rectangular shape of 10 mm × 123 mm × 0.01 to 0.15 mm in accordance with the physical test method of the molded article determined in accordance with JIS K 7312, the distance between the marked lines was increased to 200% at a distance of 10 mm, . ⊚ in the case where the shape can be maintained, ∘ in the case where some deformations are present, and x in the case where the deformations or fractures are largely deformed.

Elongation rate

The sheet-like cured product of the adhesive layer was processed into a rectangular shape having a size of 10 mm x 123 mm x 0.01 to 0.15 mm in accordance with the physical test method of a molded article defined in JIS K 7312. The obtained product was processed with a precision universal tester (%) At the time of cutting at a stretching speed of 5 mm / min using AGS-X (manufactured by Shimadzu Corporation).

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

ingredient Compound Production Example 15 Production Example 16 Production Example 17 Production Example 18 Production Example 19 Production example 20 Resin (D) Fine Tech CT-6010 100 60 100 Fine Tech CT-3080 100 Aaron Tech S-1601 100 20 The inorganic particles (E) Alumina AL-43-M 40 80 Property of adhesive layer Expansion ratio ◎ ◎ ○ ◎ ◎ ◎ Elongation (%) 271 250 352 220 284 203 Film thickness (㎛) 21 22 25 38 13 146

In Table 3, the blending amount of each blend is parts by weight of the following products. The details of the combination are as follows.

Fine-Tech CT-6010: Acryl-based polymer adhesive (manufactured by DIC, nonvolatile content 25 wt%, solvent: ethyl acetate)

Fine-Tech CT-3080: Acrylic polymer adhesive (manufactured by DIC, nonvolatile content 45 wt%, solvent: ethyl acetate, methyl ethyl ketone)

Arontec S-1601: Solvent type acrylic polymer adhesive (30% by weight, non-volatile content, manufactured by Dong-A Co., Ltd.)

Alumina AL-43-M: alumina powder (manufactured by Showa Denko K.K., average primary particle diameter 1.5 mu m)

Examples 1 to 26

The sheet-like cured products of the heat radiation layer obtained in Production Examples 1 to 14 and the pressure-sensitive adhesive layer obtained in Production Examples 15 to 20 were pressed to produce a heat radiation sheet having a two-layer structure. With respect to physical properties of the obtained heat-radiating sheet, elongation, stretchability, adhesion, heat emissivity at 70 占 폚 and heat-releasing property were measured by the following methods.

elasticity

The heat radiation sheets of Examples 1 to 26 were processed into a rectangular shape of 10 mm x 123 nm x 0.05 to 0.2 mm in accordance with the physical test method of a molded article defined in JIS K 7312, It was confirmed that the shape could be maintained. The case where the shape could be maintained, the case where the shape was maintained, the case where there was some deformation, the case where the deformation was broken or the case where the deformation was broken.

Adhesiveness

The heat treatment of the heat-treated sheets of Examples 1 to 26 was carried out on the processed surface with an aluminum plate (A10.5P, size: 10.0 mm x 50 mm x 120 mm, grooves 10 mm wide and 5 mm deep, When a large clearance is formed and it is judged that the heat-radiating sheet can not follow the processing surface, it is confirmed that the X- Respectively.

Elongation rate

The heat-radiating sheet was processed into a rectangle of 10 mm x 123 mm x 0.05 mm to 0.2 mm in conformity with the physical test method of the molded article specified in JIS K 7312. The sheet was placed in a precision universal testing machine (product name: (%) At the time of cutting at a stretching speed of 5 mm / min was measured using a tensile tester (manufactured by Shimadzu Corporation).

70 ℃ heat emissivity

A heat-radiating sheet was laminated on the center of one side of an aluminum plate (A10.5P, size: 2.0 mm x 50 mm x 120 mm) with a thermally conductive double-sided tape (trade name: NO.5046, thermally conductive tape, Maxwell Sliontec) ). The aluminum sheet to which the sheet was affixed was fixed with the above double-sided tape as a heat source to the backside as a heat source (shunt resistor, product of PCN, product number PBH1? D, rated power 10W, size: 20 mm x 15 mm x thickness 5 mm). A constant current (2.82 A) was applied to the heat source, and after 1.0 to 1.5 hours elapsed, the temperature of the sheet surface in equilibrium was set to about 70 캜. Thermography (product name: Thermo Gear G100, manufactured by NEC Avio Infrared Technology Co., Ltd.) was used for measurement of the thermal emissivity. The temperature of the blackbody tape attaching portion was measured by attaching a black body tape 0.5 mm x 0.5 mm having an emissivity of 0.95 to the center of the sheet surface and setting the thermal emissivity of the black body tape to 0.95 in the thermography. : InfReC Analyzer NS9500 Standard Ver.1.1A, manufactured by NEC Avio Infrared Technology Co., Ltd.) The thermal emissivity was adjusted so that the temperature of the heat release layer side of the blackbody tape attaching side was the same as that of the blackbody tape surface, Respectively.

Heat dissipation

The aluminum plate (A10.5P, size: 10.0 mm x 50 mm x 120 mm) having grooves 10 mm wide and 5 mm deep on the surface at 10 mm intervals perpendicular to the longitudinal direction, (Length: 20 mm, width: 15 mm, thickness: 5 mm) as a heat source at the center of the back surface of the printed circuit board was attached to a thermally conductive double-sided tape (product name: PBH1? D, : No. 5046 thermally conductive tape, Maxwell Sliontec Co., Ltd.). A constant current (3.2 A) was applied to the heat source and the temperature of the heat source which became equilibrium after 1.0 to 1.5 hours elapsed The temperature was set to about 100 DEG C. A K thermocouple was used to measure the temperature of the heat source. When the temperature dropped by 10 DEG C or more as compared with the case where the heat radiation sheet adhered to the end, Respectively.

Tables 4 to 9 show the sheet structure and physical properties of the heat radiation sheet.

Sheet composition Example 1 Example 2 Example 3 Example 4 Example 5 The heat- Production Example 1 Production Example 1 Production Example 1 Production Example 1 Production Example 2 Adhesive layer Production Example 15 Production Example 16 Production Example 17 Production Example 18 Production Example 15 Properties Elongation (%) 174 162 190 167 193 Expansion ratio ◎ ◎ ◎ ◎ ◎ Adhesiveness ◎ ◎ ◎ ◎ ◎ 70% thermal emissivity 0.96 0.96 0.96 0.96 0.96 Heat dissipation ◎ ◎ ◎ ◎ ◎ Film thickness (㎛) 56 57 60 73 57

Sheet composition Example 6 Example 7 Example 8 Example 9 Example 10 The heat- Production Example 2 Production Example 2 Production Example 2 Production Example 3 Production Example 4 Adhesive layer Production Example 16 Production Example 17 Production Example 18 Production Example 15 Production Example 16 Properties Elongation (%) 190 228 178 122 165 Expansion ratio ◎ ○ ◎ ◎ ◎ Adhesiveness ◎ ○ ◎ ◎ ◎ 70% thermal emissivity 0.96 0.96 0.96 0.96 0.96 Heat dissipation ◎ ○ ◎ ◎ ◎ Film thickness (㎛) 58 61 74 56 60

Sheet composition Example 11 Example 12 Example 13 Example 14 The heat- Production Example 5 Production Example 5 Production Example 6 Production Example 6 Adhesive layer Production Example 15 Production Example 18 Production Example 15 Production Example 18 Properties Elongation (%) 118 109 123 115 Expansion ratio ◎ ◎ ◎ ◎ Adhesiveness ◎ ◎ ◎ ◎ 70% thermal emissivity 0.96 0.96 0.96 0.96 Heat dissipation ◎ ◎ ◎ ◎ Film thickness (㎛) 55 72 56 73

Sheet composition Example 15 Example 16 Example 17 Example 18 The heat- Production Example 7 Production Example 7 Production Example 8 Production Example 8 Adhesive layer Production Example 17 Production Example 18 Production Example 17 Production Example 18 Properties Elongation (%) 333 250 356 271 Expansion ratio ○ ○ ○ ○ Adhesiveness ○ ○ ○ ○ 70% thermal emissivity 0.96 0.96 0.96 0.96 Heat dissipation ○ ○ ○ ○ Film thickness (㎛) 60 73 61 74

Sheet composition Example 19 Example 20 Example 21 Example 22 The heat- Production Example 9 Production Example 10 Production Example 11 Production Example 12 Adhesive layer Production Example 15 Production Example 15 Production Example 15 Production Example 15 Properties Elongation (%) 121 185 128 111 Expansion ratio ◎ ◎ ◎ ◎ Adhesiveness ◎ ◎ ◎ ◎ 70% thermal emissivity 0.96 0.96 0.96 0.96 Heat dissipation ◎ ◎ ◎ ◎ Film thickness (㎛) 57 56 57 58

Sheet composition Example 23 Example 24 Example 25 Example 26 The heat- Production Example 13 Production Example 14 Production Example 1 Production Example 1 Adhesive layer Production Example 15 Production Example 15 Production Example 19 Production example 20 Properties Elongation (%) 184 130 166 155 Expansion ratio ◎ ◎ ◎ ◎ Adhesiveness ◎ ◎ ◎ ◎ 70% thermal emissivity 0.96 0.96 0.96 0.96 Heat dissipation ◎ ◎ ◎ ◎ Film thickness (㎛) 36 111 48 181

Comparative Production Examples 1 to 2

A cured product sheet as a heat radiation layer was obtained in the same manner as in Production Example 1, except that the kind and amount of each component used were changed as shown in Table 10 below.

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

ingredient Compound Comparative Preparation Example 1 Comparative Production Example 2 Resin (A) Elitel UE-3380 23 Elitel UE-3350 23 Arakid 7005N Arakid 7021 Organic solvent Butyl acetate 34 34 The crosslinking agent (B) YUVAN 228 8 8 The inorganic particles (C) TITONE R-32 16 16 Shinano Random GP-3000 2 2 Boronide S3 9 9 Physical properties of heat sink layer Expansion ratio × × Elongation (%) 88 65 70 ℃ heat emissivity 0.96 0.96 Film thickness (㎛) 35 35

In Table 10, the blending amount of each blend is parts by weight of the following products. The details of the combination are as follows.

Elitel UE-3380: polyester resin (100% solids, number average molecular weight 8,000, hydroxyl value: 15, tensile elongation: 155%, manufactured by Unichica Corporation)

Elitel UE-3350: Polyester resin (100% solids, number average molecular weight: 5000, hydroxyl value: 25, tensile elongation: 105%, manufactured by Unichica Corporation)

Table 10 shows that the tensile elongation percentage of the heat dissipation layer is 100% or less in Comparative Production Examples 1 and 2.

Comparative Production Examples 3 to 4

A sheet-like cured product of a pressure-sensitive adhesive layer was obtained in the same manner as in Production Example 15, except that the kind and amount of each component used were changed as shown in Table 11 below.

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

ingredient Compound Comparative Production Example 3 Comparative Production Example 4 Resin (D) Fine Tech CT-6010 10 Fine Tech CT-3080 Aaron Tech S-1601 10 The inorganic particles (E) Alumina AL-43-M 90 90 Property of adhesive layer Expansion ratio × × Elongation (%) 71 162 Film thickness (㎛) 22 24

Comparative Examples 1 to 4

The sheet-like cured products of the heat-sensitive layer obtained in Comparative Production Examples 1 to 2 and the pressure-sensitive adhesive layer obtained in Comparative Production Examples 3 to 4 were pressed to produce a heat-radiating sheet for comparison having a two-layer structure. With respect to the physical properties of the heat-radiating sheet thus obtained, elongation percentage, tackiness, thermal emissivity at 70 占 폚 and heat radiation property were measured by the above-mentioned methods.

Table 12 shows the sheet structure and physical properties of the heat-radiating sheet for comparison.

Sheet composition Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The heat- Comparative Preparation Example 1 Comparative Production Example 2 Production Example 1 Production Example 1 Adhesive layer Production Example 15 Production Example 15 Comparative Preparation Example 5 Comparative Preparation Example 6 Properties Elongation (%) 95 80 78 153 Expansion ratio × × × ○ Adhesiveness × × × × 70% thermal emissivity 0.96 0.96 0.96 0.96 Heat dissipation ○ × × × Film thickness (㎛) 56 56 57 59

The heat-radiating sheet of the present invention can be applied to various products such as various components such as semiconductors, LED devices, and electronic components, and electronic components such as cases including these components, thereby releasing heat generated from these components and products .

1 Conventional heat-
2 thermal desert
3 Heat absorbing layer
4 adhesive layer
5 The elastic heat-radiating sheet
6 heat dissipation layer
7 Adhesive layer

Claims (15)

A heat radiation layer having a tensile elongation percentage of 100% or more, which is obtained by the resin composition I containing the resin (A), the crosslinking agent (B) and the infrared absorbing inorganic particles (C) having a tensile elongation of 200% or more;
A stretchable heat-radiating sheet having a two-layer structure having a tensile elongation percentage of 100% or more and a pressure-sensitive adhesive layer having a tensile elongation percentage of 200% or more obtained by the resin composition II containing the pressure-sensitive adhesive resin (D).
The method according to claim 1,
Wherein the resin (A) having a tensile elongation of 200% or more is at least one member selected from the group consisting of a polyester resin, an acrylic resin, an epoxy resin, a polyurethane resin, and a silicone resin.
The method according to claim 1,
Wherein 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 mg KOH / g or less.
The method according to claim 1,
Wherein the crosslinking agent (B) is an amino resin crosslinking agent.
The method according to claim 1,
The infrared absorbing inorganic particles (C) may be selected from the group consisting of nonporous silica, porous silica, boron nitride, quartz, kaolin, calcium fluoride, aluminum hydroxide, bentonite, talc, silicide, mica, and cordierite. < RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the infrared absorbing inorganic particles (C) absorb infrared rays in a wavelength range of 6.3 to 10.5 m.
The method according to claim 1,
Wherein the infrared absorbing inorganic particles (C) have an average primary particle diameter of 0.1 to 15.0 m.
The method according to claim 1,
Wherein the content of the infrared-absorbing inorganic particles (C) is 10 to 60% by weight of the heat-radiating layer.
The method according to claim 1,
The content of the crosslinking agent (B) is 1 to 40 parts by weight (in terms of solid content) and that of the infrared absorbing inorganic particles (C) is 100 parts by weight (in terms of solid content) of the resin (A) having a tensile elongation percentage of 200% Is 20 to 200 parts by weight.
The method according to claim 1,
Wherein the heat radiation layer has a thermal emissivity of 0.95 or more at 70 占 폚.
The method according to claim 1,
Wherein the viscous 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 method according to claim 1,
Wherein the adhesive layer comprises 10 to 80% by weight of inorganic particles (E) having a thermal conductivity of 10 to 300 W / m · K.
The method according to claim 1,
Wherein the heat radiation layer has a thickness of 10 to 100 占 퐉.
The method according to claim 1,
Wherein the thickness of the adhesive layer is 10 to 150 占 퐉.
An article to which the stretchable heat-radiating sheet of claim 1 is attached.

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