TW201004798A - Heat-conductive laminated material and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a heat-conductive laminated material and a manufacturing method thereof. The heat-conductive laminated material which comprises a first solidified product layer that is obtained through solidifying a silicone composition 1 and a second solidified product layer that is obtained through solidifying a silicone composition 2 and is formed on the first solidified product layer. The silicone composition 1 comprises the following components: (a) organopolysiloxane with alkenyl, (b) heat-conductive filler, (c) organic hydrogen polysiloxane, (d) platinum group metal base catalyst, (e) reaction retarder and (f) organosilicon resin. The silicone composition 2 comprises the components (a) to (f) but has a formula different from that of the silicone composition 1. The heat-conductive sheet of the invention has satisfactory viscosity and can be fixed to a heat-generating electronic component or heat-dissipating component by means of the self viscosity. The heat-conductive laminated material represents advantageous reprocessing property.

Description

201004798 VI. Description of the Invention: [Technical Field] The present invention relates to a thermal boundary between a heat-generating electronic component and a heat dissipating member such as a heat sink or a circuit board, particularly for cooling of a heat-generating electronic component. Thermal conductive laminate of the surface and a method for producing the same. [Prior Art] Electronic components such as CPUs for driving electronic devices such as personal computers, digital video discs, and mobile phones, semiconductor components such as 1C and memory, and light-emitting components such as LEDs High-speed, small-sized, and high-integration, a large amount of heat is generated by itself, and this heat causes the temperature of such heat-generating electronic components to rise, which may cause malfunction and destruction of the heat-generating electronic components themselves. Therefore, a heat dissipating method for suppressing a large temperature rise of a heat generating electronic component in operation and a heat dissipating member used therefor are proposed. In the prior art, in order to suppress the temperature rise of the heat generating electronic component during operation, a heat dissipating member such as a heat sink of a metal plate having a high thermal conductivity such as aluminum or copper is used. The heat dissipating member conducts heat generated by the heat generating electronic component, and heat is released from the surface by a temperature difference from the outside air. In order to efficiently conduct heat generated by the heat-generating electronic component to the heat radiating member, it is effective to embed the small gap generated between the heat-generating electronic component and the heat radiating member with a heat conductive material. The thermally conductive material is formed by using a thermally conductive sheet or a thermally conductive lubricant -5 - 201004798 grease blended with a thermally conductive chelating material, and the thermally conductive material is interposed between the heat generating electronic component and the heat dissipating member. The heat conduction of the heat conductive material from the heat generating electronic component to the heat dissipating member. The sheet is excellent in workability in comparison with grease. The heat conductive sheet formed of a thermally conductive polyoxyalkylene rubber or the like is used in various fields. The thermally conductive sheet can be roughly classified into a general product that emphasizes workability and a low hardness product that emphasizes adhesion. In the case of a general product, most of the cases are made of a hard rubber having a hardness of 60 or more as measured by a type A durometer specified in JIS K6253, even if it is a thin film state of about 0.1 mm. The operation of a single item is also possible. However, this general product is difficult to fix to heat-generating electronic components and heat-dissipating members because the surface does not have a sticky feeling. In order to solve this problem, it is proposed to apply an adhesive to one side or both sides of a film-like thermally conductive sheet so that it can be easily fixed to impart an adhesive type. However, since the applied adhesive is not sufficiently thermally conductive, there is a problem that the thermal resistance of the adhesive coated article is greatly increased as compared with the uncoated one. In addition, the application of the adhesive also has an adverse effect on the thermal resistance in terms of the increase in the thickness of the sheet itself. On the other hand, in the low-hardness product, a low-hardness heat-conductive material having an Asker C hardness of 60 or less is formed into a sheet shape, and the adhesive strength can be fixed to itself without applying an adhesive or the like. However, in order to achieve this low hardness, a large amount of a plasticizer is blended in the sheet, so that the crosslinking density is extremely low, so that there is a difficulty in strength and workability in the case of forming a film, so that excellent workability is obtained. It is necessary to have a certain thickness or more, and therefore it is difficult to reduce the thermal impedance of the low hardness product. In addition, such a low-hardness product may have the disadvantage of oil spillage in the vicinity of -6-201004798 and contamination of nearby heat-generating electronic components. In order to solve this disadvantage, a heat-conductive adhesive tape which can be easily fixed to the heat-generating electronic component and the heat-dissipating member by the heat-resistant electronic component and the heat-dissipating member is developed (Patent Document 1). However, these thermal adhesive tapes have a uniform adhesive force and cannot meet the finer characteristics of single-sided adhesion and single-sided micro-adhesion. For example, an electronic component with low strength and a high-strength heat sink are fixed by an adhesive tape. When the heat is dissipated, it is very difficult to peel off (reworkability) once it fails, and if it is peeled off, the electronic component is destroyed. In order to solve this problem, there is a method of controlling the adhesion force by performing a powder-dusting process on one side of the adhesive tape. At this time, the adhesion between the thermally conductive adhesive tape and the adherend is deteriorated, and the thermal conductivity is remarkably lowered. The problem. Further, Patent Documents 2 to 5 which disclose the prior art related to the present invention are listed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2005- 208 264. [Problem to be Solved by the Invention] Therefore, the object of the present invention is to provide a film and to have excellent operability, and it can be easily fixed by itself because of moderate adhesion. A heat-conductive laminate which is excellent in reworkability and excellent in thermal conductivity because of heat-sensitive electronic components or 201004798 heat-dissipating members, and a method of manufacturing the same. [Means for Solving the Problem] The inventors of the present invention have conducted intensive studies to achieve the above-mentioned problems, and have found that the thermally conductive sheet is composed of a specific addition reaction-curable polyoxane composition. This problem can be solved by a laminate of a layer formed of a cured product and a layer of a cured product of a polyoxyalkylene composition having an addition reaction hardening type having a different composition. That is, the first aspect of the present invention provides a thermally conductive laminate characterized by comprising an organopolyoxane having two or more alkenyl groups bonded to a halogen atom in (a) 1 molecule: 100 parts by volume, ( b) Thermally conductive chelating material: 50 to 1,000 parts by volume, (c) an organic hydrogen polyoxyalkylene having two or more hydrogen atoms bonded to a ruthenium atom in one molecule: the bond of the component to the ruthenium atom The hydrogen atom / (a) The molar ratio of the alkenyl group in the component is 0.5 to 5.0, (d) the organometallic catalyst: an effective amount, (e) the reaction controlling agent: an effective amount, and (f) Polyoxane resin: a first cured layer formed by curing a polyoxyalkylene composition 1 having a volume of 50 to 500 00 in a film form, and containing the above components (a) to (f) The polysiloxane composition 2 having a composition different from the composition of the polyoxane composition 1 described above is formed into a film shape on one surface of the first cured layer to be hardened by -8-201004798 The two hardened layers are formed, and the adhesion on both sides is different from each other. In addition, the meaning of "capacity" when the blending amount of the component of the composition used in the present invention is expressed in parts by mass means the enthalpy obtained by dividing the mass of the component by the specific gravity. Preferred embodiments of the thermally conductive laminate of the present invention are mentioned. • At room temperature, a single Q of a 25 mm wide sample of the laminate was placed on an aluminum plate, pressed with a 2 kg rubber roller and then a rear curing bell, and then the other side of the laminate not adjacent to the aluminum plate After the single-sided reinforcing material, one end of the laminate is placed together with the above-mentioned reinforcing material, and is peeled from the aluminum plate at a stretching speed of 300 mm/min in a 180° direction, and the required force (adhesion) for peeling off is measured. When the measurement is performed on the laminated surface, the adhesion on both sides is 0.3 N/cm or more, and the difference in adhesion between the two surfaces is preferably 2 N/cm or more. The reinforcing material is exemplified by, for example, a polydecane tape, an aluminum foil, or the like.

矽• The poly(nonane oxide) resin of the above (f) composition, which contains R^SiO (R1 represents an unsubstituted or substituted β hydrocarbon group which does not contain an aliphatic unsaturated bond) and a Si04/2 unit, R^SiO^ unit/Si04 The /2 unit is preferably 0.5 to 1.5. • The above polyoxyalkylene composition 1 and/or polyoxyalkylene composition is preferably further contained as (g) component (gl) of the following general formula (1) R2aR3bSi(OR4)4.ab The two sides which are followed by 10 points and then held up are 1 /2 single] 1 valence ratio (1) -9- 201004798 (wherein R 2 is independently an alkyl group having 6 to 15 carbon atoms R3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms; R4 independently represents an alkyl group having 1 to 6 carbon atoms; & is an integer of 1 to 3, and b is 0 to 2; An integer, but a + b is an integer of 1 to 3.) The alkoxydecane compound represented, and (g-2) the following general formula (2): [Chemical 1] ch3 CH3-(SiO)c-Si (OR5)3 (2) CH3 (wherein R5 is independently an alkyl group having 1 to 6 carbon atoms; (: an integer of 5 to 100.) The molecular chain represented by one side of the terminal is a trialkoxy decane At least one selected from the group consisting of dimethyl polysiloxanes of a base chain: 0.01 to 50 parts by volume 〇 • the aforementioned polyoxy siloxane composition 1 and/or polyoxy siloxane composition 2, It is preferred to further contain the following general formula (3) of the (h) component: R6-(SiR62〇)dSiR62-R6 ... (R6 is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms and no aliphatic unsaturated bond, and 4 is an integer of 5 to 2,000.) The dynamic viscosity expressed by 201004798 at 23 ° C is 10 〜 〇〇 , 〇〇〇 mm 2 / s organic polyoxane. • The above thermal conductive laminate, preferably having a thickness of 20 to 1,000 // m. • The above thermal conductive laminate, preferably by laser flash method The thermal impedance measured at 25 ° C is 10 cm 2 · K / W or less. The second aspect of the present invention provides a method for producing a thermally conductive laminate having mutually different adhesive forces on both sides, which is characterized by containing @ (a) An organopolyoxane having two or more alkenyl groups bonded to a ruthenium atom in one molecule: 100 parts by volume, (b) a thermally conductive chelating material: 50 to 1, a volume fraction, and (c) 1 molecule An organic hydrogen polyoxyalkylene having two or more hydrogen atoms bonded to a halogen atom: the molar ratio of the alkenyl group bonded to the hydrogen atom of the halogen atom/(a) component of the component is 0.5 to 5.0 Amount, (d) platinum group lanthanum catalyst: effective amount, (e) reaction control agent: effective amount, and φ (f) polydecane resin: 50 to 500 parts by weight The alkane composition 1 is applied as a film to the surface of the substrate subjected to surface release treatment for applying the polyoxynane adhesive, and is cured to form a first cured layer, and then contains the aforementioned (a) The polyoxonane composition 2 having a composition different from the composition of the polyoxane component 1 of the component (f) is applied to the surface of the first cured layer in a film form, and is cured to form a second Hardened layer. In a preferred embodiment of the above-described production method of the present invention, a release treatment for a polyoxyalkylene adhesive applied to the substrate is carried out by using a fluorine-containing substituent in the main chain from -11 to 201004798. A method of producing a polyoxyalkylene. [Effects of the Invention] The thermally conductive laminate of the present invention is excellent in reworkability because the surface adhesiveness of both surfaces is different and each of the single faces can have different desired adhesive strengths. The adhesiveness of each surface of the thermally conductive laminate is easily adhered to the heat-generating electronic component or the heat-dissipating member because it is moderate, and if it is easily peeled off from the adherend, the workability is excellent. Further, when interposed between the heat-sensitive electronic component and the heat-dissipating member, the two can be brought into excellent contact with each other to exhibit excellent thermal conductivity. Moreover, the overflow of oil is suppressed and it is not a problem. Therefore, the laminate of the present invention is suitable as a thermally conductive sheet. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thermally conductive laminate of the present invention is formed of the first cured layer and the second cured layer, but any of the above (a) to (f) components φ are essential components, but each has a different The composition of the composition is formed. The composition is described below. [(a) Organic polyoxyalkylene having an alkenyl group] The component (a) of the composition of the present invention is an organopolyoxyalkylene having two or more alkenyl groups bonded to a halogen atom in one molecule, which is the present invention. One of the main agents (base polymers) in the addition reaction hardening composition. The organic polyoxane is not limited as long as it is in a liquid form, and -12-201004798 may, for example, be linear or branched, or have a linear shape with a part of a divergence, and is preferably a linear one. Here, the alkenyl group does not mean only a linear alkenyl group, including a cycloalkenyl group. Specifically, the alkenyl group may, for example, be a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group, and has a usual carbon number of from 2 to 8 or so. Further, a lower alkenyl group having 2 to 3 carbon atoms such as a vinyl group or an allyl group is preferred, and a vinyl group is particularly preferred. The alkenyl group may be bonded to any one of a ruthenium atom at the end of the Q-subchain or a ruthenium atom in the middle of the molecular chain, but is only bonded to the end of the molecular chain for the softness of the obtained cured product. Deuterium atoms are preferred. (a) a group other than an alkenyl group in the component bonded to a halogen atom, such as an unsubstituted or substituted monovalent hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert a cycloalkyl group such as a butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; An aryl group such as an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthoquinone group or a biphenyl group; an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group or a methylbenzyl group; A part or all of the hydrogen atom of the carbon atom of the group is substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like, and examples thereof include a chloromethyl group, a 2-bromoethyl group, and a 3-chloropropyl group. , 3,3,3·trifluoropropyl, chlorophenyl, fluorophenyl 'cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc. The number is 1 to 1 Å, especially the number of carbon atoms is 1 to 6, and among these, methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoro is preferred. An unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as a propyl group or a cyanoethyl group, and a benzene group , Chlorophenyl, fluorophenyl -13-201004798 like non-substituted or substituted phenyl. Further, the groups other than the alkenyl group bonded to the anthracene may be the same or different. In the case where special characteristics such as solvent resistance are not required, the methyl group is selected in most cases for reasons such as cost, ease of availability, chemical stability, and environmental load. Further, the dynamic viscosity of the organopolyoxane at 25 ° C is usually in the range of 10 to 100,000 mm 2 /s' particularly preferably in the range of 500 to 50,000 mm 2 /s. When the viscosity is too low, the storage stability of the obtained composition is deteriorated, and if it is too high, the stretchability of the obtained composition may be deteriorated. Specific examples of such a suitable organic polyoxyalkylene include a dimethylvinyl fluorenyl alkyl-encapsulated polydimethyl siloxane at both ends of the molecular chain, and a methyldivinyl fluorene at both ends of the molecular chain. An oxyalkyl-encapsulated polydimethyl siloxane, a molecular chain of two unterminated dimethylvinyl sulfoxyalkyl-encapsulated dimethyl methoxy oxane, a methyl phenyl fluorene copolymer, and the like. The organopolyoxane of the component (a) may be used singly or in combination of two or more kinds having different viscosities. [(b) Thermal Conductive Filler] The thermal conductive filler of the component (b) is usually a metal powder, a metal oxide powder or a ceramic powder, and specific examples thereof include aluminum powder, copper powder, and silver powder. Nickel powder, gold powder, alumina powder, zinc oxide powder, magnesium oxide powder, iron oxide powder, titanium oxide powder, chromium oxide powder, aluminum nitride powder, boron nitride powder, tantalum nitride powder, diamond powder, carbon powder Final, fullerene powder, carbon graphite powder, and the like. However, it is not limited thereto, and any of the materials of the prior art -14-201004798, which is used as a prior art thermal conductive ruthenium, may be any ruthenium material, and these may be used alone or in combination of two or more types. These thermal conductive ruthenium materials can be used in an average particle diameter of usually 0.1 to 100 μm, and it is desirable to use 〇_5 to 50 μm. These enamel fillers can be used alone or in combination. Further, two or more kinds of particles having different average particle diameters may be used. Further, in the present invention, the average particle diameter is a volume average particle diameter, which is measured by a Microtrac particle size distribution measuring device ΜΤ3300ΕΧ (日0机装股份有限公司). The blending amount of the thermally conductive enthalpy is preferably 50 to 1,000 parts by volume, based on the fluidity, formability, and thermal conductivity of the composition, from 50 to 1,000 parts by volume of the component (a). 1〇〇~500 capacity parts. [(c) Organohydrogenpolysiloxane] The component (c) of the composition of the present invention is usually a hydrogen atom having two or more bonds to a ruthenium atom in one molecule (that is, a SiH group), preferably Q A component having 2 to 100 organic hydrogen polyoxyalkylenes and acting as a crosslinking agent of the component (a). That is, the hydrogen atom bonded to the halogen atom in the component (c) is acted upon by the platinum group metal catalyst of the component (d) described later, and the alkenyl group in the component (a) is added by hydrogen peroxide. A hydrosilylating reaction is added to form a crosslinked cured product having a 3-dimensional network structure having a cross-linking bond. The organic group bonded to the halogen atom in the component (c) may, for example, be an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and the like, and specifically, it may be enumerated as the component (a). The unsubstituted or substituted hydrocarbon group bonded to the fluorene atom other than the -15-201004798 alkenyl group is illustrated. Among them, from the viewpoint of synthetic surface and economy, a methyl group is preferred. The structure of the organic hydrogen polyoxyalkylene of the component (C) is not particularly limited, and may be any of a linear chain, a branched chain, and a cyclic chain, but is preferably linear. Such a linear organohydrogenpolyoxyalkylene is, for example, the following general formula (4): [Chemical 2] R7 1 f R7 \ R7 R7—Si〇 ( -?i〇V -Si—R7 (4) R7 ', R7 乂R7

(wherein R7 is independently an unsubstituted or substituted monovalent hydrocarbon group or a hydrogen atom other than an alkenyl group; but at least two are hydrogen atoms, and η is an integer of 1 or more.). In the above general formula (4), an unsubstituted* or substituted monovalent hydrocarbon group other than the alkenyl group represented by R7 is bonded to a group other than the above alkenyl group in the item (a). The monovalent hydrocarbon group is the same species. Further, η is preferably from 2 to 100, more preferably from 5 to 50. Specific examples of the organic hydrogen polyoxyalkylene of the component (c) include a trimethylphosphonium alkyl group-terminated methyl hydrogen polyoxyalkylene at both ends of the molecular chain, and a trimethyl oxime at both ends of the molecular chain. Alkyl-enclosed dimethyl methoxy oxane/methylhydroquinone copolymer, molecular chain two-terminal trimethyl hydroxy oxyalkyl-encapsulated dimethyl methoxy oxane, methyl hydrazine, methyl benzene Alkoxy oxane copolymer, dimethyl hydrazine oxyalkyl-terminated dimethyl polyoxyalkylene at the two ends of the molecular chain, molecular chain-16- 201004798 two-terminal dimethylhydroquinone oxyalkyl-encapsulated dimethyl group Cobaltane/methylhydroquinone copolymer, two-terminal dimethylhydroquinone oxyalkyl-encapsulated dimethyl methoxy oxane/methylphenyl decane copolymer at the two ends of the molecular chain A hydroquinone-oxyalkyl group, a methylphenyl polyoxyalkylene chain or the like. Further, the organic hydrogen polyoxyalkylene of the component (C) may be used alone or in combination of two or more. The amount of the component (c) added is such that the SiH group of the component (c) is from 0. 5 to 5.0 moles per mole of the alkenyl group 1 in the component (a), and preferably is 0.8 _ to 4.0 moles. the amount. When the amount of the Si-H group of the component (c) is less than 0.5 mol with respect to the alkenyl group 1 in the component (a), the thermally conductive composition does not harden, and the strength of the cured product is insufficient to be Problems such as operation of a molded body or a laminate. When the amount exceeds 5.0 moles, the adhesiveness of the cured product is insufficient, and the problem of fixing itself by itself cannot be fixed. [(d) Platinum Group Metal-Based Catalyst] The uranium-based metal catalyst of the component (d) in the present invention is for promoting bonding of an alkenyl group in the φ (a) component to a ruthenium atom in the component (c). The addition reaction of a hydrogen atom is supplied from the composition of the present invention to a component blended by a crosslinked hardened product of a three-dimensional network structure. The component (d) can be used as a conventional catalyst for the usual hydrogenation addition reaction. Specific examples thereof include uranium metal monomers such as platinum (including platinum rhodium), rhodium, and palladium, H2PtCl4 · nH20, H2PtCl6 · nH2〇' NaHPtCle · ηΗ20 'KHPtCl6 · ηΗ2〇' Na2PtCl6 · ηΗ20, K2PtCl4 · ηΗ20 , PtCl4 · ηΗ20, PtCl2, Na2HPtCl4 • ηΗ20 (wherein, n is an integer of 0-6, preferably 0 or 6), etc. Chlorine-17- 201004798 Uranium, lead chloride acid and chloroplatinic acid a salt, an alcohol-modified platinic acid, a complex of chloroplatinic acid and an olefin, a carrier of a platinum group metal such as uranium, palladium or the like supported on alumina, cerium oxide, carbon, etc. An olefin complex, a chlorobenzene (triphenylphosphine) ruthenium (WILKIN SON catalyst), a platinum chloride, a lead chlorate or a uranium chloride complex with a vinyl group-containing decane. Further, the platinum group metal catalyst of the component (d) may be used singly or in combination of two or more. (d) The amount of the component to be blended is not particularly limited as long as it is an effective amount required to cure the composition φ of the present invention, but is usually converted to the mass of the uranium metal element of the component (a). Is a reaction control agent of 0.1 to 1, 〇〇〇ppm, preferably 0.5 to 500 ppm 〇 [(e) reaction control agent] (e) component for adjustment in the presence of component (d) (a) The reaction rate of the component and the component (c). (e) component, usual addition reaction hardening type polyoxane composition _ Any of the conventional addition reaction inhibitors used can be used. Specific examples thereof include an acetylene compound such as 1-ethynyl-1-cyclohexanol or 3-butyn-1-ol, a nitrogen compound, an organic phosphorus compound, a sulfur compound, a hydrazine compound, and an organic chlorine compound. In addition, the addition reaction inhibitor of the component (e) may be used alone or in combination of two or more. The amount of the component (e) to be blended is different depending on the amount of the component (d) to be used. However, as long as it is an effective amount for adjusting the reaction rate of the rhodium hydrogen addition reaction to the desired reaction rate, Usually, it is about 10 to 50000 ppm with respect to the mass of the component (a -18-201004798). When the amount of the component (e) is too small, sufficient use time may not be ensured, and if the amount is too large, the hardenability of the composition may be lowered. [(f) Polyoxane resin] The polysiloxane resin of the component (f) used in the present invention has an effect of imparting adhesion to the cured product of the present invention. Examples of the @ (f) component include R^SiOm unit (M unit), and

The copolymer of the Si04/2 unit (Q unit), the ratio of the Μ unit to the Q unit (Mo ratio) is M/Q = 0.5 to 1.5, preferably 0.6 to 1.4, more preferably 〇.7 to 1.3. In the range of M/Q = 0.5 to l_5, the desired adhesion can be obtained. R1 is an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond, and may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group or a pentyl group. a cycloalkyl group such as a neopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group or the like, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group, a phenyl group, a tolyl group, An aryl group such as an aryl group such as a xylyl group, a naphthyl group or a biphenyl group; an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group or a methylbenzyl group; and a carbon atom bonded to the group One or all of a hydrogen atom, a group substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3·3 Fluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc. have 1 to 10 carbon atoms, especially The number of carbon atoms is from 1 to 6, and among these, carbons such as methyl, ethyl, propyl, chloromethyl, bromoethyl, 33,3-trifluoropropyl, cyanoethyl and the like are preferred. Unsubstituted or substituted alkyl having 1 to 3 atoms and phenyl-19- 201004798, chlorophenyl, fluorophenyl The unsubstituted or substituted phenyl. In addition, all of Rl may be the same or different. In the case where R1 is not required to have special characteristics such as solvent resistance, in many cases, a methyl group is selected for reasons such as cost, availability, chemical stability, and environmental load. The amount of the component (f) to be added is 50 to 500 parts by volume, preferably 60 to 3 50 parts by volume, and more preferably 70 to 200 parts by volume, based on 100 parts by parts of the component (a). When the amount of the component (f) added is less than 50 parts by volume and more than 500 parts by weight, the desired adhesiveness cannot be obtained. (f) The component itself is a solid or viscous liquid at room temperature, but may be used in a state of being dissolved in a solvent. At this time, the amount of addition to the composition is determined by the amount of solvent removed. [Other components] In the composition (polyoxane composition 1 and/or polyoxane composition 2) used in the present invention, if necessary, the above-mentioned (a) may be added without departing from the object of the present invention. ) Components other than the component (f). Hereinafter, any such components will be described. • ( g ) Surface treatment agent: In the composition of the present invention, when the composition is prepared, the hydrophobization treatment (b) the thermal conductive ruthenium material enhances the wettability with (a) the organopolyoxane, so that (b) The thermally conductive enthalpy is uniformly dispersed in the matrix formed of the component (a), and a surface treatment agent (wetting agent) may be blended. The (g) component is particularly preferably the following (g-ι) and (g-2). 201004798 • ( gl ) alkoxydecane compound The following general formula (1): R 2aR 3bSi(OR 4 ) 4-ab (1) (wherein R 2 is independently an alkyl group having 6 to 15 carbon atoms; R 3 independently a non-zero substituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms; R 4 independently represents an alkyl group having 1 to 6 carbon atoms; a is an integer of 1 to 3, and b is an integer of 0 to 2, but a + b is an integer of 1 to 3.) The alkoxydecane compound represented. In the above general formula (1), the alkyl group represented by R2 may, for example, be a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group or a tetradecyl group. When the number of carbon atoms of the alkyl group represented by R2 is in the range of 6 to 15, the wettability of the component (b) is sufficiently improved, and the workability is excellent, and the composition is excellent in low temperature characteristics. The unsubstituted or substituted monovalent hydrocarbon group represented by R3 may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a vinyl group or an alkene group; An alkenyl group such as a propyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a 2-phenylethyl group or a 2-methyl-2-phenylethyl group; and a 3,3,3-trifluoropropane group; A halogenated hydrocarbon group such as a 2-(nonafluorobutyl)ethyl group, a 2-(heptadecafluorooctyl)ethyl group or a P-chlorophenyl group. Among these, methyl or ethyl is particularly preferred. The alkyl group represented by R4 may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl-21 - 201004798 group, a pentyl group or a hexyl group. Among these, methyl group and ethyl group are particularly preferred. Specific examples of suitable (g-1) components include the following: C6H13Si(OCH3)3

Ci〇H2iSi(OCH3) C12H25Si(OCH3)3

C12H25Si(OC2H5)3 C10H21Si(CH3)(〇CH3)2 C10H21Si(C6H5)(OCH3)2 C10H21Si(CH3)(OC2H5)2 C10H21Si(CH=CH2)(OCH3)2 C10H21Si(CH2CH2CF3)(OCH3)2 The (g-ι) component may be used alone or in combination of two or more. Even if the blending amount of the component (g-1) exceeds a certain amount, the effect of the wetting agent does not increase, which is uneconomical. Further, since the component is volatile, the composition and the cured product after hardening are gradually hardened when placed in an open system. • · ( g-2 ) dimethyl polyoxane The following general formula (2): [Chemical 3] ch3 CH3-(SiO)c-Si(OR5)3 CH, -22- (2) 201004798 (Formula In the above, R5 is independently an alkyl group having 1 to 6 carbon atoms; c is an integer of 5 to 100.) The dimethylpolyoxane in which the one-side end of the molecular chain is blocked by a trialkoxyalkylene group . In the above general formula (2), the alkyl group represented by R5 is the same as the alkyl group represented by R4 in the above general formula (1). Specific examples of the suitable component (g-2) include the following

CH3 ch3 CH3-(SiO)5-Si(OCH3)3 CH3-('O)10-Si(OCH3)3 ch3 ch3 ch3 ch3 I i CH3-(SiO)2〇-Si(OCH3)3 CH3 - (SiO) 31-Si(OCH3)3 ch3 ch3 Further, the component (g-2) may be used alone or in combination of two or more. When the amount of the component (g-2) is too large, the heat resistance or moisture resistance of the obtained cured product tends to be lowered. The surface treatment agent of the component (g) may be used in any of the (g-Ι) component and the (g-2) component, or both. In this case, the blending amount of the component (g) is 0.01 to 50 parts by volume based on 1 part by volume of the component (a), and particularly preferably 〇 1 to 30 parts by volume. • (h) Organic polyoxyalkylene: -23- 201004798 In the composition of the present invention, the following general formula (3) is added as the component (h): R6-(SiR62〇)dSiR62-R6 (3) (R6 is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms and no aliphatic unsaturated bond, and d is an integer of 5 to 2,000.) The dynamic viscosity expressed at 23 ° C is 1 〇 to 1 〇〇 , 〇〇〇mm2/s organic polyoxane. The properties of the viscosity adjusting agent such as the thermally conductive composition are appropriately used for the purpose, but are not limited thereto. They may be used alone or in combination of two or more. The above R6 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms. R6 may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group; a cyclopentyl group; a cyclohexyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a 2-phenylethyl group or a 2-methyl-2-phenylethyl group; and a 3,3,3-trifluoropropane group; a halogenated hydrocarbon group such as 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl or p-chlorophenyl, etc., but particularly preferably a methyl group, a phenyl group, or a carbon number of 6~ 18 alkyl. The above d is preferably an integer of 5 to 2,000, particularly preferably 10 to 1, an integer of 〇〇〇 from the viewpoint of the desired viscosity. Further, the dynamic viscosity at 25 ° C is preferably 10 to 10,000,000 mm 2 / s, particularly preferably 10 〇〇 to 1 〇, 〇〇〇 mm 2 / s. When the dynamic viscosity is less than 10 mm 2 /s, the cured product of the obtained composition becomes liable to cause oil overflow. The dynamic viscosity of -24-201004798 is more than 100,000 mm2/s, and the fluidity of the obtained thermally conductive composition is insufficient. Specific examples of the component (h) include, for example, [Chemical 5] ch3 CH3-Si-Ο I ch3

CH3 Si-CH3 ch3 CH3 / 20

CH3 / CH3 \ CH3 CH3—Si—〇-r~Si—〇—Si—CH3 [Chemical 7] ch3 CH3—Si—O CH3

CH3 \ CH3 /230 CH3

Ch3 I Si-CH3 ch3

❹ When the component (h) is added to the composition of the present invention, the amount thereof is not limited as long as it is an amount at which the desired effect can be obtained, but it is preferably 〇 with respect to 100 parts by weight of the component (a). .ι~ι〇〇 capacity, more preferably 1~50 parts. When the amount of addition is within this range, the thermally conductive composition before the curing of the crucible has excellent fluidity and is easy to maintain workability, and it is easy to apply the thermally conductive filler of the component (b) to the composition. • Other optional components: -25- 201004798 Other optional components may also be added with, for example, a fluorine-modified polyoxyalkylene surfactant; carbon black, titanium dioxide, iron oxide red, etc. as a coloring agent: as a flame retardant imparting agent A platinum compound, a metal oxide such as iron oxide, titanium oxide or cerium oxide, or a metal hydroxide or the like. Further, as the precipitation preventing agent for the thermally conductive ceramium, fine powder of cerium oxide such as precipitated cerium oxide or cerium oxide, a thixotropic oxidizing agent, or the like may be added as needed. [Formation of Laminated Body] The desired components are uniformly mixed, and two or more kinds of the compositions (composition 1 and composition 2) of the present invention having different compositions are prepared. First, one of the compositions 1 is applied onto a substrate and heat-cured to form a first layer. Next, another composition (composition 2) was applied onto one surface of the first layer to be heat-cured. In this manner, the thermally conductive laminate of the present invention can be obtained. When the composition is applied to a substrate or a first layer and molded, a solvent such as toluene for adjusting the viscosity of the composition may be added. The thickness of each of the first and second hardened layers is preferably 10 to 500 μm, and more preferably 20 to 25 0 μm. The thickness of the entire laminate is preferably from 20 to 1,000 μm, more preferably from 50 to 500 μϊ. If the thickness is too thin, the operation of the laminate is poor and the adhesive feeling is lowered. On the other hand, if the thickness is too thick, the desired thermal conductivity cannot be obtained. [Characteristics] • Thermal impedance:

The thermal conductive laminate of the present invention has a thermal resistance measured by a laser flash method of from 25 ° C to -26 to 201004798, preferably 1 〇 cm 2 · Κ / W or less, particularly preferably 5 cm 2 · K / W or less. When the thermal resistance is within this range, the composition of the present invention can efficiently dissipate heat generated from the heat generating body to the heat dissipating member even when it is applied to a heat generating body having a large amount of heat. Furthermore, the measurement of the thermal impedance by the laser flash method can be carried out in accordance with ASTM E 1461. • Adhesiveness: The thermally conductive laminate of the present invention is characterized in that it has different adhesion on both sides. Prepare a 25 mm wide laminate sample, contact it with an aluminum plate at room temperature at room temperature, pressurize the laminate with a 2 kg rubber roller, and then cure for 1 minute, then The laminate was formed by a tape-like reinforcing material made of a 25 mm wide polydecane tape (manufactured by NIPPA Co., Ltd., No. 99) on the other side of the laminate which was not next to the aluminum plate. One end is peeled off from the aluminum plate together with the above-mentioned reinforcing material, and the force required for peeling off is measured when the tensile speed is 300 mm/rnin to peel Q from the aluminum plate at a 180° direction (referred to as " Adhesion"). The difference in adhesion between the two sides (strongly adhered side and weakly adhered side) is preferably 2 N/cm or more, and particularly preferably 3/cm or more. When the difference in adhesion between the two sides of the laminate is less than 3 N/cm, it is difficult to exhibit a significant difference in the adhesion on both sides, and there is a fear that the adherend is broken when it is reworked or peeled off. Further, the adhesive force measured as described above is 0.3 N/cm or more on both sides, and particularly desirably 0.5 to 20 N/cm. When the adhesion of either one is lower than 〇3 N/cm, it is difficult to fix the heat-generating electronic component or the heat-dissipating member with its own adhesive force. In addition, if the adhesion is too large, it is not easy to -27-201004798 peeling and poor reworkability. The adhesion of both surfaces of the laminate of the present invention is selected to be the polyoxyalkylene composition 1 and the polyoxyalkylene composition 2 of such a number. This selection is carried out by changing the composition of the polyoxyalkylene composition of the present invention to prepare a plurality of kinds, and applying it to a substrate to cure it to form a hardened layer. By testing the adhesion in the same manner as above, each composition can be obtained. Each adhesion. Next, the laminate of the present invention can be easily produced by combining two kinds of polyoxyalkylene compositions by setting the adhesion to the above conditions. [Method for Producing Thermal Conductive Laminate] The thermally conductive laminate of the present invention, for example, the above-described method, that is, a polyoxyalkylene composition each having a component (a) to (f) as a quantitative amount 1. Applying a film to the surface of the substrate subjected to surface release treatment for applying the polyoxynane adhesive, and hardening to form a first cured layer, and then containing the above (a) to (f) a polyoxonane composition 2 having a composition different from that of the polyoxyalkylene composition 1 described above is applied as a film to the surface of the first cured layer of the crucible 9 to be hardened to form a second hardening. Manufactured from the layer of matter. In the above method, the order of blending the components in the composition 1 or the composition 2 is not particularly limited, but a preferred method is (1) kneading the component (a) in a desired amount, and (b) a component and (d) component to prepare a base composition, and (2) a curing agent prepared by mixing the components (c) and (e), -28-201004798 (3) Next, the above-mentioned basic composition is prepared by modulating A composition which is uniformly mixed with a hardener and a polyoxyalkylene resin of the component (f). The substrate used in the method of the present invention, that is, the substrate for coating the polyoxyalkylene composition 1, is used for surface release treatment for applying a polyoxyalkylene adhesive to paper, PET film or the like. Suitable for. The surface release agent for the polyoxyalkylene adhesive may, for example, be a modified polyoxyalkylene having a fluorine substituent such as a perfluoroalkyl group or a perfluoropolyether group in its main chain. The perfluoropolyether group can be represented by the following formulas (5) to (7). F(CFCF20)pCFCF20CH2CH2CH2. (5) cf3 cf3 (p=l 〜5) f(?fcf2o)p〒fch2och2ch2ch2_ (6) cf3 cf; (P=l ～5)

CqF2q+1CH2OCH2CH2CH2-(q=3 〜10) (7) Further, the modified polyoxyalkylene having the related fluorine substituent may, for example, be sold under the trade name of X-70-201 by Shin-Etsu Chemical Co., Ltd. , X-70-258 and other products. The method of coating and forming the composition on the substrate includes a bar coater, a knife coater, a comma-shaped blade coater (comma -29-201004798 CO at er ), and spin coating. The liquid material is applied to the substrate in the form of a film, but is not limited to the above-described method. Further, the heating temperature condition for heating after molding may be a temperature at which the solvent used for the addition of the solvent is volatilized, and the component (a) and the component (c) are reactable. The effect on the productivity and the substrate film is expected to be 50 to 150 ° C, and more desirably 60 to 15 〇 t:. The hardening time is usually from 0.5 to 30 minutes, preferably from 1 to 20 minutes. Even if heating is performed at the same temperature, a heating method in which the temperature is changed by step up or ramp up may be employed. ® The heat-conductive laminate after hardening is a release film which is the same as the base film, and is a protective separation film, and can be attached to the surface opposite to the substrate side of the laminate to facilitate transportation. The operation of a fixed cut or the like becomes easy. In this case, the base film changes the amount or type of the release agent, changes the material of the substrate, and imparts a light weight to the adhesion of the substrate film and the separation film from the laminate. The thermally conductive laminate obtained by the above method is adhered to the heat-generating electronic component or the heat-dissipating member after peeling off the separation film or the base film, and then, even if it is a film, it can be easily disposed by peeling off the remaining film, and Shows excellent thermal conductivity. Further, since the adhesion on both sides is different, when the red or double peeling is repeated, the strong adhesive side is maintained, and the peeling of the desired surface (weak adhesive side) can be performed. Thereby, on the weakly adhesive side, the stress applied to the adherend is lowered to prevent breakage. [Embodiment] -30 - 201004798 [Examples] Hereinafter, the present invention will be specifically described by showing examples and comparative examples of the present invention, but the present invention is not limited to the following examples. First, the components (a) to (f) used in the following examples and comparative examples are listed below. < (a) Ingredient> • (A-1) dimethylpolyoxyl group with a dynamic viscosity at 25 ° C of 60 0 mm 2 /s and a molecular chain at both ends blocked by a dimethylvinyl alkoxyalkyl group Alkane (A-2) has a dynamic viscosity of 30,000 mm 2 /s at 25 ° C and a dimethylpolyoxyalkylene chain terminated by a dimethylvinyl alkoxyalkyl group at both ends of the molecular chain < (b) > • ( B-1 ) Alumina powder with an average particle size of 10.7 M m (true specific gravity 3.98) • (8-2) Oxidized powder with an average particle diameter of 1.1 b 111 (true specific gravity 3.98) • (B-3) Zinc oxide powder having an average particle diameter of μ·6 μm (true specific gravity 5.67 < (c) component > • (C-1) the following structural formula·· -31 - 201004798 [Chemical 9]

H

Me Me μ 1 1

Me-Si—(OSi)168· Me Me

Me (〇 予 i) 6.3 —〇Si—Me

Methanohydrohalo alkane represented by Me Me <(D) component> (D-1) dimethyl-polytetramethylene oxide of uranium-divinyltetramethyldioxane complex The two ends of the chain are bound by a dimethylvinyl fluorenyl group at 25. (: a solution having a dynamic viscosity of 60 〇 1311112/3 [platinum atom content: 1% by mass] < (E) component > • ( E-1) 50% by mass toluene solution of 1-ethynyl-1-cyclohexanol <(f) component> • (F-1) substantially only by Me3SiO〇.5 unit (Μ unit) and Φ Si甲苯2 unit (Q unit) of a polyoxane resin (M/Q molar ratio ι.15) in toluene solution (nonvolatile content 60%; viscosity 30mm2 / s). (F-2) essentially A toluene solution of a polydecane resin (M/Q molar ratio 〇μ) formed only of Me3SiO〇.5 unit (Μ unit) and Si〇2 unit (Q unit) (nonvolatile content 70%; viscosity 30 mm 2 /s) < (g) component> -32- 201004798 • (Gl) Structural formula: organic decane represented by C12H25Si ( OC2H5 ) 3 • ( G-2 ) The following structural formula: [Chemical 10] ch3 ch3 I , 丨CH3—Si—Ο—(-SiO-^-Si(OCH3)3 CH3 ch3 End blocked with an alkyl trimethoxy silicon dimethylpolysiloxane silicon oxide Institute < (h) component > • (H-1) of the following structure formula: [Chemical Formula 11]

CH3 CH3—Si—Ο I ch3

Ch3 Si-CH3 I ch3 is represented by a dimethyl methacrylate with a dynamic viscosity of 600 mm 2 /s at 25 ° C <substrate > (K-1) coated with 1.0 g/m 2 of Shin-Etsu Chemical Industry ( X-70-201 thickness of ΙΟΟμπι PET film-33- 201004798 (K-2) Untreated PET film of thickness ΙΟΟμιη [Modulation Examples 1-4, Comparative Preparation Examples 1-4] < Thermal Conductivity Composition Preparation of the material> The components described in Table 1 were blended in the same manner as described in the same table, and then the compositions S1 to S7 were prepared by blending as follows. Further, the compositions S5, S6 and S7 are compositions which do not satisfy the conditions of the present invention. In a planetary mixer (specialized machine-made industrial product, trade name TK hybismix) containing 700 ml of internal volume, (a) component and (b) component are loaded with (g) component and (h) when necessary. Ingredients, let them mix for 60 minutes. Next, the component (d) and the component (e) are added to each other to form a mixture, and finally, the component (c) and the component (f) are added and uniformly mixed to prepare a composition. -34- 201004798 ❹

[Table i] Modulation example comparison modulation 1 column 1 2 3 4 1 2 3 SI S2 S3 S4 S5 S6 S7 Composition capacity part (8) Al 100 • 100 • 100 100 100 A-2 - 100 100 - - 0>) Bl 300 215 200 215 240 800 300 B-2 75 55 50 55 60 250 75 B-3 - - 25 - - - - (c) Cl 8.6 2.9 7.0 2.9 8.6 8.6 1.2 (f) Note 1 Fl 300 (180) 300 ( 180) 320 (192) - 50 (30) 300 (180) 300 (180) F-2 - - - 257 (180) - - (g) Gl - _ 5 - - - - G-2 15 15 5 15 15 15 15 (h) Hl - 5 - - Concentration (ppm) {Note 2> (d) Dl 7000 (70) 7000 (70) 7000 (70) 7000 (70) 7000 (70) 7000 (70) 7000 (70) (e) El 7000 (3500) 7000 (3500) 7000 (3500) 7000 (3500) 7000 (3500) 7000 (3500) 7000 (3500) SiH/Vi Note 3 2.2 3.1 1.8 3.1 2.2 2.2 0.3 "Note i" The number in the parentheses in the table is the volume fraction of the resin component in one component of 100 parts by volume of the component (8). "Note 2": the concentration of the component (d) and the component (e) in the table, and the concentration of the component (D-1) and the component (E-1) with respect to the mass of the component (a). The number 値 in the parentheses is the concentration of the platinum atom relative to the (D-1) component of the mass of the component (a) and the ethynyl group 1 contained in the component (E-1) relative to the mass of the component (8). • The concentration of cyclohexanol. "Note 3": "SiH/Vi" means the number of SiH groups (hydrogen atoms bonded to a halogen atom) in one (B) component of the vinyl group in the component (A). [Examples 1 to 4 and Comparative Examples 1 to 5] <Production of Laminated Body> The laminates described in Tables 2 and 3 were treated as described in the same section as in the section -35-201004798. get. First, among the compositions obtained in Table 1, one (XI) was applied to a substrate and cured to obtain a monolayer (Y1) of a thermally conductive cured product. Then, one of the compositions obtained in Table 1 (X2) was selected and applied to a monolayer of the previously obtained thermally conductive cured product, followed by curing to obtain a laminate (Y2). With respect to the obtained laminate, adhesion, recyclability, selective peeling property, overflow property, peelability from a substrate, workability after peeling, and thermal resistance were evaluated by the following methods. The results are shown in Tables 2 and 3. • Peelability: It was evaluated by the weight when the heat-conductive laminate after hardening was peeled off from the base film by hand (by evaluation of touch). When the peeling touch was light and the laminate was not deformed at all, it was evaluated as "good", and when the peeling touch was heavy or the laminate was deformed, it was evaluated as "poor". • Handling property after peeling: The heat-conductive cured product after peeling was evaluated by the operability of the hand, focusing on the shape of the body. When the thermally conductive cured product peeled off from the base film was adhered to the aluminum plate, it was evaluated as "good" without any difficulty. When the heat-conductive hardened material is broken and is firmly attached to the hand and deformed, it cannot be returned to the original shape, and it is judged as "poor". • Reworkability • Selectability: Select both sides of the thermally conductive cured product after peeling off with the same aluminum plate -36- 201004798 'Evaluate the reworkability (when peeling off, it will not damage the adhesive body) and choose Peelability (whether it is often peeled off by the weakly adhesive side). The test was carried out by peeling off two sheets of the aluminum sheets which were subsequently passed through the thermally conductive cured material five times (the thermally conductive cured product and the aluminum plate were replaced in each test). The aluminum sheets on both sides were not deformed or broken five times, and the thermally conductive cured material was evaluated as "good" when peeled off from the aluminum sheet which was adhered to the surface having weak adhesion. Even once, the thermally conductive cured material was adhered to the adhesive force. When the aluminum sheet of the surface is peeled off, the aluminum sheet or the thermally conductive cured product is also evaluated as "poor" when it is deformed or broken. • Adhesiveness: According to the above method, the thermal conductive laminate is adhered to the aluminum plate with a 2 kg rubber roller on each side, and then cured for 10 minutes. In order to prevent deformation of the laminate, the other side not adjacent to the aluminum plate is used. Then, after bonding with a strong polyoxyalkylene adhesive tape (manufactured by NIPPA Co., Ltd.), one end is peeled off and grasped by hand, and peeled off at a normal temperature at a tensile speed of 300 mm/min to 180°. Measure adhesion. The measurement results are shown in Table 2 and Table 3. • Spillage: A 0.1 mm thick sample was cut out 20 mm square together with the substrate, and the resin layer was placed on top of the high quality paper, and 100 g of copper was placed thereon to make it adhere. It was visually confirmed that the oil after one day was evaluated as the migration state of the upper paper. -37- 201004798 • Thermal resistance: The thermal conductive laminate obtained above was placed in a circular plate (purity: 99.9%, diameter: about 12.7 mm, thickness: about 1.0 mm) made of standard aluminum. On the other, a standard aluminum plate was superposed thereon, and the obtained structure was clamped by a clip, and a pressure of about 175.5 kPa (1.80 kgf/cm2) was applied to obtain a three-layer structure. The thickness of the obtained test piece was measured, and the thickness of the thermally conductive laminate was calculated by subtracting the known thickness of the standard aluminum plate. Further, the thickness of the test piece was measured using a micrometer (manufactured by Mitutoyo Co., Ltd., type: M820-25VA). The results obtained are shown in Tables 2 and 3. Using the above test piece, the thermal resistance (cm2 · K/W) of the thermally conductive laminate was measured by a thermal impedance measuring instrument (manufactured by NETZSCH, Xenon flash analyzer; LFA447 NanoFlash). The obtained thermal impedances are shown in Tables 2 and 3. • Suitable for heat generation and heat dissipation: Fig. 1 is a schematic cross-sectional view showing the structure of the heat generation and heat dissipation device, which will be described with reference to Fig. 1 . The thermally conductive laminate 1 obtained in the above Examples 1 to 3 was placed on the surface of the pseudo CPU 2 of 2 cm x 2 cm. The pseudo CPU 2 is mounted on the printed circuit board 3. The heat radiating member 4 is superposed on the laminated body 1, and the heat radiating member 4 is sandwiched by the printed circuit board 3 by the cleat 5 to be crimped. In this way, the heat generating/heat dissipating device 6 that couples the pseudo CPU 2 and the heat radiating member 4 via the thermally conductive laminate 1 is obtained. The result of supplying power to the CPU 2 seems to be that the CPU 2 generates heat and the temperature rises, but stabilizes at about 1 〇 〇 °C. After 1000 hours, 201004798 stable heat conduction and heat dissipation, no CPU failure caused by overheating. Further, when the heat dissipating member 4 is folded, damage to the pseudo CPU 2 and the printed circuit board can be prevented. Therefore, by using the thermally conductive laminate of the present invention, it is confirmed that the reliability of the heat generating and heat dissipating device of the semiconductor device or the like is improved. [Table 2] Example 1 2 3 4 Composition used in XI S1 S3 S1 S1 S2 Composition used S2 S2 S2 S4 substrate K-1 K-1 K-1 K-1 Hardening condition 80. . The oven was heated for 10 minutes and heated in an oven at 80 ° C for 10 minutes. Heated in an 80 °c oven for 10 minutes at 80 °C. . The oven is heated for 10 minutes. Thickness of Y1 (μπι) 189 210 98 198 Thickness of Υ2 (μιη) 299 320 156 302 Good peelability, good, good workability after peeling, good, good, good reworkability, good peeling selectivity, good, good, good Adhesion (N/cm) Strong adhesion side S2 side 5.8 S2 side 6.1 S2 side 6.6 S4 side 8_1 weakly adhesive side S1 side 0.6 S3 side 1.8 S1 side 1.2 S1 side 1.4 Overflow almost no almost no almost no thermal impedance (cm2 -K/W) 2.8 3.1 1.8 3.1 -39- 201004798 [Table 3] Comparative Example 1 2 3 4 5 XI S2 S6 S1 S2 S1 X2 S5 S2 S4 S2 S2 Substrate K-1 K-1 K-1 Κ-1 The K-2 hardening condition is 80. . Heating in an oven for 10 minutes, heating in an oven at 80 ° C for 1 minute, heating in an oven at 80 ° C for 10 minutes, heating in an oven at 80 ° C for 10 minutes, heating in an oven at 80 ° C for 10 minutes, thickness of Y1 (μιη) 206, hardening, forming 76 103 106 Thickness of Υ2 (μιη) 403 Y1 is not measured because it cannot be formed. 173 202 211 Good peelability, good, good, very heavy laminate deformation, work hardened material after peeling, brittleness, cracking, no good, no adhesion, no adhesion, strong adhesion on both sides. Deformation is not measured due to deformation of the laminate. Peeling of the selective hardened material can not be measured. Can not be followed by no peeling selectivity, no peeling, selective peeling, aluminum sheet deformation adhesive force (N/cm), strong adhesive side, S1 side, 0.4 S2 base Material side 6.9 weakly bonded side S4 side 0·1 S2 separator side 5.3 Spilled with a small amount of almost no thermal impedance (cm2-K/W) 6.8 1.6 2.3 ❹

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a longitudinal section of a heat generating and heat dissipating device to which a thermally conductive laminate of the present invention is applied in an embodiment. -40- 201004798 [Explanation of main component symbols] 1 : Thermally conductive laminate

2: Like CPU 3: Printed circuit board 4: Heat dissipating member 5: Plywood

Claims (1)

201004798 VII. Patent application scope: 1. A thermal conductive laminate characterized in that it comprises an organopolysiloxane having two or more alkenyl groups bonded to a halogen atom in (a) molecule: 100 parts by volume, (Μ Thermal conductivity 塡 filling material 50 to 1,000 parts by volume, (c) Organic hydrogen polyoxyalkylene having two or more hydrogen atoms bonded to a halogen atom in one molecule: the bonding of this component to a halogen atom The hydrogen atom / (a) the molar ratio of the alkenyl group in the component is 0.5 to 5.0, (d) the lead metal-based catalyst: an effective amount, (e) the reaction controlling agent: an effective amount, and (f) Polyoxynizer resin: a first cured layer formed by curing a polysiloxane composition of 50 to 500 parts by volume, and containing the above-mentioned components (a) to (f) The polyoxoxane composition 2 having a composition different from the composition of the polyoxane composition 1 is formed into a second cured layer formed by curing a film on one surface of the first cured layer. The adhesion between the two sides is different from each other. 2. The thermal conductive laminate according to claim 1 of the patent scope, which is at room temperature, One side of the fitted 25 mm wide sample was in contact with the aluminum plate, and the laminate was pressed with a rubber roller of 2 kg mass and then cured for 10 minutes, and then the one side of the other side of the laminate which was not next to the aluminum plate was followed. After reinforcing the strong material, one end of the laminate was held together with the above-mentioned reinforcing material, and peeled off from the aluminum plate at a tensile speed of 300 mm/min in a 180° direction, and the force required for peeling off was measured (adhesion force) When the measurement is performed on both sides of the laminate, the adhesion force on both sides is 〇3 N/cm or more, and the difference in adhesion between the two sides of -42-201004798 is 2 N/cm or more. The thermally conductive laminate of the first or second aspect, wherein the polyfluorene oxide resin of the component (f) contains a R^SiCh^ unit (R1 represents an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond) and The Si04/2 unit, 11138, the 〇1/2 unit/8丨〇4/2 unit has a molar ratio of 0.5 to 1.5. 4. The thermal conductive laminate according to claim 1 or 2, which is further contained As the component (g), ❹ (g-Ι) is the following general formula (1): R2aR3bSi(OR4)4-a- b (1) (wherein R2 is independently an alkyl group having 6 to 丨5 carbon atoms; R3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms; and R4 independently represents a carbon number An alkyl group of 1 to 6; a is an integer of 1 to 3 'b is an integer of 0 to 2 'but a + b is an integer of Q 1 to 3) alkoxydecane compound represented by (b-2) The following general formula (2): [Chemical 12] ch3 CH3- and c-Si(OR5)3 (2) CH3 -43- 201004798 (wherein R5 is independently an alkyl group having 1 to 6 carbon atoms; At least one selected from the group consisting of a group of dimethylpolysiloxanes having a one-side end of the molecular chain represented by an integer of 5 to 100, which is one-side end of the molecular chain, is 0.01 to 50 parts by volume. 5. The thermally conductive laminate as claimed in claim 1 or 2, which further contains the following general formula (3) as the component (h): R6-(SiR62〇)dSiR62-R6 (3) (R6 is independently a monovalent hydrocarbon group having 1 to 18 carbon atoms and containing no aliphatic unsaturated bond, and d is an integer of 5 to 2,000) Its dynamic viscosity is 1〇~1〇〇, 〇〇〇〇11112/3 organic polyoxalate. 6_ A thermally conductive laminate according to claim 1 or 2, wherein the thickness is 20 Å, ΟΟΟ μιη. 7. The thermally conductive laminate of claim 1 or 2, wherein the thermal impedance measured at 25 ° C by the Α laser flash method is 1 〇 cm 2 · K / W or less. 8. A method for producing a thermally conductive laminate having mutually different adhesive forces on both sides, characterized by comprising (a) an organopolyoxane having two or more alkenyl groups bonded to a ruthenium atom in one molecule: 100 parts by volume, (M thermal conductive sputum: 50 to 1,000 parts by volume, (c) organic hydrogen polyoxyalkylene having two or more hydrogen atoms bonded to a halogen atom in one molecule: a bond of this component Hydrogen atom bonded to a halogen atom / (a) -44- 201004798 The molar ratio of the alkenyl group in the composition is 0.5 to 5.0, (d) uranium metal catalyst: effective amount, (e) reaction control agent : an effective amount, and (f) polyoxyalkylene resin: 50 to 500 parts by volume of the polyoxyalkylene composition 1, which is applied as a film to the surface release treatment for the applied polyoxyxane adhesive The surface of the material is hardened to form a first-hardened layer, and then the polyoxoxane composition having the composition of the above-mentioned (a) to (f) components different from the composition of the first φ polyoxane composition 1 is formed. 2. Applying a film to the surface of the first cured layer to harden it to form a second cured layer. A production method of 8, wherein the release treatment applied to the substrate poly siloxane silicon adhesive used, based main chain modified by fluorine substitution of poly alumoxane treated silica. -45-