KR20090103784A - Thermal conductive laminate and method for preparing the same - Google Patents

Abstract

PURPOSE: A thermal conductive laminate and a method for preparing the same are provided to be easily attached to heat-generating electronic components or heat-radiating members. CONSTITUTION: A thermal conductive laminate(1) comprises a first cured layer and a second cured layer. The both sides of the thermal conductive laminate have different adhesion force. The first cured layer is formed by molding a first silicone composition into a thin film and curing it. The second cured layer is formed by molding a second silicone composition into a thin film and curing it on the one side of the first cured layer. The first silicone composition contains: organopolysiloxane with two or more alkenyl groups bonded with silicone atom within one molecule; thermal conductive filler; organo hydrogen polysiloxane; platinum-family catalyst; reaction control agent; and silicon resin.

Description

Thermally Conductive Laminates and Methods for Manufacturing the Same {THERMAL CONDUCTIVE LAMINATE AND METHOD FOR PREPARING THE SAME}

The present invention relates in particular to a thermally conductive laminate which can be interposed on a thermal interface between a heat generating electronic component and a heat dissipating member such as a heat sink or a circuit board for cooling the heat generating electronic component and a manufacturing method thereof.

Electronic components such as CPUs, driver ICs, and memory devices used in electronic devices such as personal computers, digital video disks, and mobile phones, and light emitting devices such as LEDs, have become high-performance, high-speed, miniaturized, and highly integrated. Generates a large amount of heat The increase in temperature of these heat generating electronic components due to the heat may cause a malfunction and destruction of the heat generating electronic components themselves. Therefore, many heat dissipation methods for suppressing the temperature rise of the heat generating electronic component during operation, and the heat radiating member used for it are proposed.

Background Art Conventionally, in electronic devices and the like, heat dissipation members such as heat sinks using metal plates having high thermal conductivity such as aluminum and copper have been used in order to suppress the temperature rise of the heat generating electronic components during operation. The heat dissipation member conducts heat generated by the heat generating electronic component and emits heat from the surface due to the temperature difference from the outside air.

In order to efficiently conduct heat generated from the heat generating electronic component to the heat radiating member, it is effective to fill a small gap generated between the heat generating electronic component and the heat radiating member with the heat conductive material. As the thermally conductive material, a thermally conductive sheet incorporating a thermally conductive filler, a thermally conductive grease, or the like is used, and these thermally conductive materials are interposed between the heat generating electronic component and the heat radiating member, and the heat generating electrons through these heat conductive materials. Heat conduction from the component to the heat dissipation member is realized.

Sheets have better handling properties than greases, and thermally conductive sheets formed of thermally conductive silicone rubber or the like have been used in various fields.

A thermally conductive sheet can be largely classified into a general product which made much of handleability, and the low hardness product which made much of adhesiveness.

In general, the general product is made of a hard rubber having a hardness of 60 or more measured in a type A durometer specified in JIS K6253 in the form of a sheet, and handling in a single product is possible even in a thin film of about 0.1 mm. Do. However, since this general article has no adhesiveness on the surface, it is difficult to fix it to a heat generating electronic component and a heat dissipation member. In order to solve this, the tackifying type which apply | coated the adhesive to one side or both sides of a thin-film thermally conductive sheet, and was able to fix easily is proposed. However, since the applied adhesive has insufficient thermal conductivity, there has been a problem that the thermal resistance of the pressure-sensitive adhesive coated article is greatly increased as compared with not applied. In addition, the application of the pressure-sensitive adhesive functions disadvantageously in thermal resistance in that the thickness of the sheet itself increases.

On the other hand, the low-hardness product is formed by molding a low-hardness heat conductive material having an Asker C hardness of 60 or less in a sheet form, and maintains an adhesive force that can fix itself without applying an adhesive or the like. However, in order to realize the low hardness, since a large amount of plasticizer is mixed in the sheet or the crosslinking density is made very low, there is a difficulty in the strength and handleability when forming a thin film. The above thickness was needed. Therefore, it was difficult to reduce the thermal resistance of the low hardness article. In addition, such a low-hardness product has the drawback that oil bleeding occurs and it is easy to contaminate nearby heat generating electronic components.

As a solution to this drawback, a thermally conductive adhesive tape having a single layer thin film, which can be handled and which can be easily fixed to a heat generating electronic component and a heat radiating member, has been developed (Patent Document 1). . However, these thermally conductive adhesive tapes are uniform in their adhesive strength and could not meet finer characteristic requirements such as strong adhesion on one side and non-adhesion on one side. For example, in the case of fixing and dissipating a low-strength electronic device and a high-strength radiator with an adhesive tape, when adhesion fails once, peeling (rework) is very difficult. do. In order to solve this problem, there is a method of controlling the adhesive force by performing a chip treatment or the like on one side of the adhesive tape, but in this case, the adhesion between the thermally conductive adhesive tape and the adherend becomes poor and the thermal conductivity is significantly reduced. A problem arises.

In addition, patent documents 2-5 are mentioned as disclosing the prior art which concerns on this invention.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-030212

[Patent Document 2] Japanese Patent Application Laid-Open No. 2005-035264

[Patent Document 3] Japanese Unexamined Patent Publication No. 2005-206733

[Patent Document 4] Japanese Patent Application Laid-Open No. 2006-182888

[Patent Document 5] Japanese Patent Application Laid-Open No. 2006-188610

Therefore, the problem of the present invention is a thin film, good handleability, and having proper adhesiveness, so that it can be easily fixed to a heat generating electronic component or a heat dissipation member by itself, and the reworkability is good because the adhesive strength of both surfaces is different. And a thermally conductive laminate having excellent thermal conductivity and a method for producing the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, the present inventors consisted of the layer which consists of the hardened | cured material of the specific addition reaction hardening type silicone composition, and the hardened | cured material of the addition reaction hardening type silicone composition which has another composition as a result. It discovered that the said subject could be solved by comprised as a laminated body with a layer.

That is, the present invention firstly,

(a) an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule: 100 parts by volume,

(b) thermally conductive filler: 50 to 1,000 parts by volume,

(c) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule: an amount such that the molar ratio of the alkenyl group in the hydrogen atom / (a) component bonded to the silicon atom of the present component is 0.5 to 5.0,

(d) platinum group metal catalysts: an effective amount,

(e) reaction control agents: effective amounts and

(f) Silicone resin: 50 to 500 parts by volume

And a first cured product layer formed by molding and curing a silicone composition 1 comprising a thin film, and the components (a) to (f) as essential components, and the silicone composition 2 having a composition different from the silicone composition 1 above. A second cured product layer formed by molding and curing a thin film on one side of the first cured product layer, and providing a thermally conductive laminate having different adhesive strengths on both sides thereof.

In addition, the "dose" when the compounding quantity of the component of the composition used for this invention is represented by "capacity part" means the value obtained by dividing the mass of the said component by the specific gravity.

The following are mentioned as preferable embodiment of the thermally conductive laminated body of this invention.

At room temperature, one side of the 25 mm wide sample of the laminate was brought into contact with an aluminum plate, pressed with a rubber roller of 2 kg in mass, cured for 10 minutes after adhesion, and then unbonded with the aluminum plate of the laminate. After adhering to the reinforcing material on one side of the other side, one end of the laminate is gripped together with the reinforcing material to which it is bonded and peeled from the aluminum plate in the 180 ° direction at a tensile speed of 300 mm / min, and the force required for peeling (adhesive force) When measuring)) is performed on both surfaces of the said laminated body, it is preferable that the adhesive force of both surfaces is 0.3 N / cm or more, and the difference in adhesive force of both surfaces is 2 N / cm or more. As said reinforcing material, a silicone tape, aluminum foil, etc. are mentioned, for example.

The silicone resin of component (f) comprises R ¹ ₃ SiO _1/2 units (R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds) and SiO _4/2 units, that the R _{¹ 3} SiO _^1/2 units _/ SiO _4/2 unit molar ratio is 0.5 to 1.5 is preferred.

Said silicone composition 1 and / or silicone composition 2 are further (g) component,

(g-1) at least one selected from the group consisting of an alkoxysilane compound represented by the following formula (1) and (g-2) dimethylpolysiloxane in which one end of the molecular chain represented by the following formula (2) is sealed with a trialkoxysilyl group: 0.01 It is preferred to contain from 50 to 50 parts by volume.

R ² _a R ³ _b Si (OR ⁴ ) _4-ab

(Wherein R ² is independently an alkyl group having 6 to 15 carbon atoms, R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ independently is carbon number Is an alkyl group of 1 to 6, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is an integer of 1 to 3)

(Wherein R ⁵ is independently an alkyl group having 1 to 6 carbon atoms, c is an integer of 5 to 100)

The silicone composition 1 and / or silicone composition 2 further preferably contain an organopolysiloxane having a kinematic viscosity of 10 to 100,000 mm 2 / s at 23 ° C. represented by the following general formula (3). .

R ^6- (SiR ⁶ ₂ O) _d SiR ⁶ ₂ -R ⁶

(R ⁶ is independently a monovalent hydrocarbon group containing no aliphatic unsaturated bonds of 1 to 18 carbon atoms, d is an integer from 5 to 2,000)

It is preferable that the said heat conductive laminated body is 20-1,000 micrometers in thickness.

-It is preferable that the said heat conductive laminated body is 10 cm <2> * K / W or less in heat resistance in 25 degreeC measured by the laser flash method.

Secondly, the present invention

(a) an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule: 100 parts by volume,

(b) thermally conductive filler: 50 to 1,000 parts by volume,

(c) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule: an amount such that the molar ratio of the alkenyl group in the hydrogen atom / (a) component bonded to the silicon atom of the present component is 0.5 to 5.0,

(d) platinum group metal catalysts: an effective amount,

(e) reaction control agents: effective amounts and

(f) Silicone resin: 50 to 500 parts by volume

Applying the silicone composition 1 comprising a thin film on the surface of the substrate subjected to the surface release treatment for a silicone pressure-sensitive adhesive and cured to form a first cured product layer, and then containing the components (a) to (f) And a silicone composition 2 having a composition different from that of the silicone composition 1 in a thin film form on the surface of the first cured product layer and cured to form a second cured product layer. Provided are methods of making different thermally conductive laminates.

As one of the preferable embodiment of the said manufacturing method of this invention, the manufacturing method in which the mold release process for the silicone adhesive which is given to the said base material is the process by modified silicone which contains a fluorine substituent in a main chain is mentioned.

The thermally conductive laminate of the present invention is excellent in reworkability because the surface adhesiveness of both surfaces is different, and the desired adhesive force different from one surface can be provided. Since the adhesiveness of each surface of the said heat conductive laminated body is appropriate, it can adhere to a heat generating electronic component or a heat radiating member, and can fix it easily, and also it is easy to peel off from a to-be-adhered body as needed, and handling property is favorable. . In addition, when interposed between the heat generating electronic component and the heat dissipation member, both can be satisfactorily brought into contact with each other, and exhibit very good thermal conductivity. In addition, bleeding of the oil is suppressed and does not become a problem. Therefore, the laminate of the present invention is useful as a thermally conductive sheet.

BRIEF DESCRIPTION OF THE DRAWINGS It is a conceptual diagram which shows the longitudinal cross section of the heat-generating / heat radiating apparatus to which the thermally conductive laminated body of this invention was applied in an Example.

<Brief description of symbols for the main parts of the drawings>

1. Thermally Conductive Laminates

2. Pseudo CPU

3. Printed wiring board

4. Heat dissipation member

5. Clamp

Hereinafter, the present invention will be described in detail.

Although the heat conductive laminated body of this invention consists of a 1st hardened | cured material layer and a 2nd hardened | cured material layer, these are all formed from the composition which contains said (a)-(f) component as an essential component, but each has a different composition. Hereinafter, the said composition is demonstrated.

[(A) organopolysiloxane having alkenyl group]

The component (a) of the composition of the present invention is an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule, and is one of the main agents (base polymer) in the addition reaction curable composition of the present invention.

If this organopolysiloxane is liquid, the molecular structure is not limited, For example, although it is linear, branched, the linear which has some branch is mentioned, Especially preferably, it is linear.

Here, an alkenyl group contains not only a linear alkenyl group but a cycloalkenyl group. Specifically, as said alkenyl group, things, such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, etc. are usually 2-8 carbon atoms, for example. Among these, a lower alkenyl group having 2 to 3 carbon atoms such as a vinyl group and an allyl group is preferable, and a vinyl group is particularly preferable. Although this alkenyl group may couple | bond with either the silicon atom of the molecular chain terminal, or the silicon atom in the middle of a molecular chain, in order to make the softness of the hardened | cured material obtained favorable, it exists only by binding to the silicon atom of the molecular chain terminal. desirable.

Groups bonded to silicon atoms other than alkenyl groups in the component (a) are, for example, unsubstituted or substituted monovalent hydrocarbon groups, for example, methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups. cycloalkyl groups such as alkyl groups such as tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group, Of aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group and hydrogen atoms bonded to carbon atoms of these groups Some or all of which are substituted with halogen atoms such as fluorine, chlorine, bromine, cyano groups, etc., for example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl Group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5 And carbon atoms such as 5,6,6,6-nonnafluorohexyl groups having from 1 to 10 carbon atoms, in particular from 1 to 6 carbon atoms, and among these, methyl, ethyl, propyl and chloro Unsubstituted or substituted unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as methyl group, bromoethyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, or phenyl group, chlorophenyl group, fluorophenyl group, or Substituted phenyl group. Moreover, all the groups couple | bonded with the silicon atom other than an alkenyl group may be same or different. Unless special properties such as solvent resistance are required, all methyl groups are often selected for reasons of cost, ease of acquisition, chemical stability, and environmental load.

Moreover, the kinematic viscosity at 25 degrees C of this organopolysiloxane is 10-100,000 mm <2> / s normally, Especially preferably, it is the range of 500-50,000 mm <2> / s. When the said viscosity is too low, the storage stability of the composition obtained will worsen, and when too high, the extension of the composition obtained may deteriorate.

As a specific example of such organopolysiloxane, molecular chain both terminal dimethylvinyl siloxy group blocking polydimethylsiloxane, molecular chain both terminal methyldivinyl siloxy group blocking polydimethylsiloxane, molecular chain both terminal dimethylvinyl siloxy blocking dimethylsiloxane Methylphenylsiloxane copolymer etc. are mentioned.

The organopolysiloxane of this (a) component can be used individually by 1 type or in combination of 2 or more types from which a viscosity differs, for example.

((B) Thermally Conductive Filler]

As the thermally conductive filler as the component (b), for example, metal powder, metal oxide powder, ceramic powder are usually used, and specifically, aluminum powder, copper powder, silver powder, nickel powder, gold powder, aluminum oxide powder, Zinc oxide powder, magnesium oxide powder, iron oxide powder, titanium oxide powder, zirconium oxide powder, aluminum nitride powder, boron nitride powder, silicon nitride powder, diamond powder, carbon powder, fullerene powder, carbon graphite powder, and the like. However, it is not limited to these, Any filler may be sufficient as it is a well-known substance used conventionally as a thermally conductive filler, These may be single 1 type or it may mix 2 or more types.

As these thermally conductive fillers, the average particle diameter is 0.1-100 micrometers normally, Preferably the thing of 0.5-50 micrometers can be used. These fillers may be used individually by 1 type, and may mix and use multiple types. Moreover, it is also possible to use 2 or more types of particle | grains from which an average particle diameter differs. In addition, in this invention, an average particle diameter is a volume average particle diameter, and is a measured value by micro track particle size distribution measuring apparatus MT3300EX (Nikiso Corporation).

The compounding quantity of a thermally conductive filler is 50-1,000 volume parts with respect to 100 volume parts of (a) component from a viewpoint of the fluidity | liquidity of a composition, moldability, and the thermal conductivity obtained, Preferably it is 100-500 volume parts.

[(C) organohydrogenpolysiloxane]

Component (c) of the composition of the present invention is an organohydrogenpolysiloxane having usually two or more, preferably 2 to 100, hydrogen atoms (i.e., SiH groups) bonded to silicon atoms (a) It is a component which acts as a crosslinking agent of a component. That is, the hydrogen atom couple | bonded with the silicon atom in (c) component is added by the action of the platinum group metal catalyst of (d) component mentioned later by hydrosilylation reaction with the alkenyl group in (a) component, and has a crosslinking bond. The crosslinked hardened | cured material which has a three-dimensional mesh-like structure is provided.

As an organic group couple | bonded with the silicon atom among (c) component, the unsubstituted or substituted monovalent hydrocarbon group which does not have an aliphatic unsaturated bond, etc. are mentioned, For example, Alke described in the term of component (a) The same kind of unsubstituted or substituted hydrocarbon group as what was illustrated as group couple | bonded with the silicon atom other than a silyl group is mentioned. Especially, it is preferable that it is a methyl group from a synthetic viewpoint and economical viewpoint.

The structure of the organohydrogenpolysiloxane of the component (c) is not particularly limited, and may be any of linear, branched, and cyclic, but is preferably linear. Such linear organohydrogenpolysiloxane is represented by following formula (4), for example.

(Wherein R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group or hydrogen atom other than an alkenyl group, provided that at least two are hydrogen atoms and n is an integer of 1 or more)

In the general formula (4), an unsubstituted or substituted monovalent hydrocarbon group other than the alkenyl group represented by R ⁷ is the same as the monovalent hydrocarbon group in the group bonded to silicon atoms other than the alkenyl group described above in the section of component (a). will be.

In addition, n is preferably an integer of 2 to 100, more preferably 5 to 50.

As a preferable specific example of the organohydrogenpolysiloxane of (c) component, the molecular chain both terminal trimethylsiloxy group blocking methylhydrogenpolysiloxane, the molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane methylhydrogensiloxane copolymer, molecular chain Both terminal trimethylsiloxy group blocking dimethylsiloxane, methyl hydrogen siloxane, methylphenyl siloxane copolymer, molecular chain both terminal dimethyl hydrogen siloxane group blocking dimethyl polysiloxane, molecular chain both terminal dimethyl hydrogen siloxane group blocking dimethyl siloxane, methyl hydrogen siloxane public A copolymer, a molecular chain both terminal dimethyl hydrogen siloxy group blocking dimethylsiloxane, methylphenyl siloxane copolymer, a molecular chain both terminal dimethyl hydrogen siloxy group blocking methylphenyl polysiloxane, etc. are mentioned. In addition, the organohydrogenpolysiloxane of (c) component can be used individually by 1 type or in combination of 2 or more types.

The addition amount of (c) component is the amount which SiH group of (c) component becomes 0.5-5.0 mol with respect to 1 mol of alkenyl groups in (a) component, Preferably it is 0.8-4.0 mol. If the amount of the Si-H group of the component (c) is less than 0.5 mole with respect to 1 mole of the alkenyl group in the component (a), the thermally conductive composition will not be cured or the strength of the cured product will be insufficient, so that it can be treated as a molded or laminated body. Problems such as unavailability occur. If the amount is more than 5.0 moles, the adhesiveness becomes insufficient on the cured product, and a problem arises in that the self-adhesion cannot be fixed.

[(D) Platinum Group Metal Catalysts]

The platinum group metal catalyst of (d) component in this invention promotes addition reaction of the alkenyl group in (a) component, and the hydrogen atom couple | bonded with the silicon atom in (c) component, and shows the three-dimensional mesh form from the composition of this invention. It is a component mix | blended in order to provide the crosslinked hardened | cured material of a structure.

As the component (d), any known catalyst used in a normal hydrosilylation reaction can be used. Specific examples thereof include platinum group metals such as platinum (including platinum black), rhodium and palladium, H ₂ PtCl ₄ nH ₂ O, H ₂ PtCl ₆ nH ₂ O, NaHPtCl ₆ nH ₂ O , KHPtCl ₆ nH ₂ O, Na ₂ PtCl ₆ nH ₂ O, K ₂ PtCl ₄ nH ₂ O, PtCl ₄ nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ nH ₂ O (wherein n is an integer of 0 to 6, preferably 0 or 6), or a platinum group metal such as platinum chloride, chloroplatinic acid and chloroplatinic acid salt, alcohol-modified chloroplatinic acid, complex of chloroplatinic acid and olefin, platinum black, palladium, etc. Supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), platinum chloride, chloroplatinic acid or a complex of chloroplatinate and vinyl group-containing siloxane, etc. Can be mentioned. In addition, the platinum group metal catalyst of (d) component can be used individually by 1 type or in combination of 2 or more type.

The compounding quantity of (d) component should just be an effective amount necessary in order to harden the composition of this invention, although it does not restrict | limit especially, Usually, it is 0.1-1,000 ppm in mass conversion of the platinum group metal element with respect to (a) component, Preferably it is 0.5- It is good to set it to 500 ppm.

[(E) Reaction Control Agent]

Reaction control agent of (e) component is for adjusting reaction rate of (a) component and (c) component which advance in presence of (d) component.

As (e) component, all the well-known addition reaction inhibitor used for a normal addition reaction curing type silicone composition can be used. Specific examples thereof include acetylene compounds such as 1-ethynyl-1-cyclohexanol and 3-butyn-1-ol, nitrogen compounds, organophosphorus compounds, sulfur compounds, oxime compounds, organic chloro compounds and the like. . In addition, the addition reaction inhibitor of (e) component can be used individually by 1 type or in combination of 2 or more types.

Although the compounding quantity of (e) component changes also with the usage-amount of (d) component, it cannot be defined uniformly, but what is necessary is just an effective amount which can adjust the progress of a hydrosilylation reaction to a desired reaction rate, and usually (a) component It may be about 10 to 50000 ppm with respect to the mass of. When the compounding quantity of (e) component is too small, sufficient pot life may not be secured, and when too large, the curability of a composition may fall.

[(F) Silicone Resin]

The silicone resin of (f) component used for this invention has the effect | action which provides adhesiveness to the hardened | cured material of this invention.

Examples of the component (f) include a copolymer of R ¹ ₃ SiO _1/2 units (M units) and SiO _4/2 units (Q units), and the ratio (molar ratio) between the M units and the Q units is M / Q. = 0.5 to 1.5, preferably 0.6 to 1.4, more preferably 0.7 to 1.3. Desired adhesive force is obtained in the range of M / Q = 0.5-1.5.

R ¹ is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, Cycloalkyl groups such as neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group, phenyl group, tolyl group, xylyl group, Aralkyl groups such as aryl groups such as naphthyl groups and biphenylyl groups, benzyl groups, phenylethyl groups, phenylpropyl groups and methylbenzyl groups, and some or all of the hydrogen atoms bonded to carbon atoms of these groups are fluorine, chlorine and bromine Groups substituted with halogen atoms, cyano groups and the like, for example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, Cyanoethyl group, 3,3,4,4,5,5,6,6,6-nonafluorohex The number of carbon atoms, such as a group, is 1-10, especially carbon atoms are 1-6, Among these, Preferably, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, 3,3, 3- tree Unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as fluoropropyl group and cyanoethyl group, and unsubstituted or substituted phenyl groups such as phenyl group, chlorophenyl group and fluorophenyl group. In addition, all of R ¹ may be the same or different. Unless special properties such as solvent resistance are required, all of R ^{1 's} are often selected from methyl groups for reasons of cost, their availability, chemical stability, and environmental load.

The addition amount of (f) component is 50-500 volume part with respect to 100 volume part of (a) component, Preferably it is 60-350 volume part, More preferably, it is 70-200 volume part. When the addition amount of (f) component exceeds less than 50 volume parts and 500 volume parts, desired adhesiveness will not be obtained.

The component (f) itself is a solid or viscous liquid at room temperature, but can also be used in a state dissolved in a solvent. In that case, the addition amount to a composition is determined by the quantity except the solvent powder.

[Other components]

To the composition (silicon composition 1 and / or silicone composition 2) used for this invention, if necessary, components other than said (a)-(f) component can be added in the range which does not impair the objective of this invention. have. Hereinafter, such an optional component is demonstrated.

(G) surface treatment:

 In the composition of the present invention, at the time of preparation of the composition, (b) hydrophobic treatment of the thermally conductive filler to improve wettability with (a) the organopolysiloxane, and (b) the thermally conductive filler is contained in a matrix comprising the component (a). In order to disperse | distribute uniformly, a surface treating agent (wetter) can be mix | blended. Especially as said (g) component, following (g-1) and (g-2) are preferable.

(G-1) alkoxysilane compounds

An alkoxysilane compound represented by the following formula (1).

<Formula 1>

R ² _a R ³ _b Si (OR ⁴ ) _4-ab

(Wherein R ² is independently an alkyl group having 6 to 15 carbon atoms, R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ independently is carbon number Is an alkyl group of 1 to 6, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is an integer of 1 to 3)

In the formula (1), examples of the alkyl group represented by R ² include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and the like. When the carbon number of the alkyl group represented by this R <^2> satisfy | fills the range of 6-15, the wettability of (b) component will fully improve, handling workability will be favorable, and the low temperature characteristic of a composition will become favorable.

As an unsubstituted or substituted monovalent hydrocarbon group represented by R <^3> , For example, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups such as vinyl group and allyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; And halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 2- (nonnafluorobutyl) ethyl group, 2- (heptadecafluorooctyl) ethyl group, and p-chlorophenyl group. Especially in this, a methyl group and an ethyl group are preferable.

As an alkyl group represented by R <^4> , alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, are mentioned, for example. Especially in this, a methyl group and an ethyl group are preferable.

The following are mentioned as a preferable specific example of this (g-1) component.

In addition, (g-1) component can be used individually by 1 type or in combination of 2 or more types. The compounding amount of the component (g-1) is not economical because the wet effect does not increase any more than a certain amount. Moreover, since the said component is volatile, when left to stand in an open system, a composition and hardened | cured material after hardening may become hard gradually.

(G-2) dimethyldimethylsiloxane

One end of the molecular chain represented by the following formula (2) is dimethylpolysiloxane sealed with a trialkoxysilyl group.

<Formula 2>

(Wherein R ⁵ is independently an alkyl group having 1 to 6 carbon atoms, c is an integer of 5 to 100)

In the formula (2), the alkyl group represented by R ⁵ is the same as the alkyl group represented by R ⁴ in the formula (1).

The following are mentioned as a preferable specific example of this (g-2) component.

In addition, (g-2) component can be used individually by 1 type or in combination of 2 or more type. When there is too much compounding quantity of this (g-2) component, there exists a tendency for the heat resistance and moisture resistance of the hardened | cured material obtained to fall.

As the surface treating agent of the component (g), any one or both of these components (g-1) and (g-2) may be used in combination. In this case, it is preferable that the compounding quantity of (g) component is 0.01-50 volume parts with respect to 100 volume parts of (a) component, especially 0.1-30 volume parts.

(H) organopolysiloxanes:

To the composition of the present invention, an organopolysiloxane having a kinematic viscosity of 10 to 100,000 mm 2 / s at 23 ° C. represented by the following general formula (3) can be further added to the composition (h). Although it uses suitably for the purpose of providing the characteristics, such as a viscosity modifier of a thermally conductive composition, it is not limited to this. It may be used individually by 1 type, or may use 2 or more types together.

<Formula 3>

R ^6- (SiR ⁶ ₂ O) _d SiR ⁶ ₂ -R ⁶

(R ⁶ is independently a monovalent hydrocarbon group containing no aliphatic unsaturated bonds of 1 to 18 carbon atoms, d is an integer from 5 to 2,000)

R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms. Examples of R ⁶ include alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group; Cyclohexyl groups, such as a cyclopentyl group and a cyclohexyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; Halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, and p-chlorophenyl group; A phenyl group and the alkyl group of 6-18 carbon atoms are preferable.

From the viewpoint of the required viscosity, d is preferably an integer of 5 to 2,000, particularly preferably an integer of 10 to 1,000.

In addition, the kinematic viscosity at 25 ° C. is preferably 10 to 100,000 mm 2 / s, and particularly preferably 100 to 10,000 mm 2 / s. When the said kinematic viscosity is lower than 10 mm <2> / s, the oil bleeding of the hardened | cured material of the composition obtained will become easy to generate | occur | produce. When the kinematic viscosity is larger than 100,000 mm 2 / s, the fluidity of the thermally conductive composition obtained tends to be insufficient.

As a specific example of (h) component, it is, for example

Etc. can be mentioned.

When adding (h) component to the composition of this invention, the addition amount is not limited, What is necessary is just an quantity from which a desired effect is acquired, About 0.1 volume part of (a) component, Preferably it is 0.1-100 volume parts, More preferably Preferably from 1 to 50 parts by volume. When the addition amount is within this range, it is easy to maintain good fluidity and workability in the thermally conductive composition before curing, and it is easy to fill the composition with a thermally conductive filler of component (b).

Other optional ingredients:

As other optional components, For example, Fluorine modified silicone surfactant; As the colorant, carbon black, titanium dioxide, red iron oxide and the like; As the flame retardant imparting agent, a metal compound such as a platinum compound, iron oxide, titanium oxide, cerium oxide, or a metal hydroxide may be added. Moreover, it is also arbitrary to add fine powder silica, such as precipitated silica or calcined silica, a thixotropy improvement agent, etc. as an antisettling agent of a thermally conductive filler.

[Formation of laminated body]

Two or more kinds of compositions (composition 1 and composition 2) of the present invention having different compositions, with uniform mixing of required components, are prepared. First, one composition 1 is apply-molded on a base material, heat-hardened, and a 1st layer is formed. Next, another 1 type of composition (composition 2) is apply-molded on one side of a 1st layer, and it heat-hardens. In this way, the thermally conductive laminate of the present invention can be obtained. When apply | coating and shape | molding a composition on a base material or a 1st layer, it is also possible to add solvents, such as toluene, for viscosity adjustment of a composition.

The thickness of a 1st and 2nd hardened layer becomes like this. Preferably it is 10-500 micrometers, More preferably, it is 20-250 micrometers. Preferably the thickness of the whole laminated body is 20-1,000 micrometers, More preferably, it is 50-500 micrometers. When thickness is too thin, handling of a laminated body will be bad and a feeling of adhesiveness will fall. On the other hand, if the thickness is too thick, the desired thermal conductivity will not be obtained.

〔characteristic〕

Thermal resistance:

It is preferable that the thermal resistance in 25 degreeC measured by the laser flash method of the thermal conductive laminated body of this invention is 10 cm <2> * K / W or less, and it is especially preferable that it is 5 cm <2> * K / W or less. When the heat resistance is within this range, the composition of the present invention can efficiently dissipate heat generated from the heat generating element into the heat dissipation component even when applied to a heat generating element having a large heat generation amount. In addition, the measurement of the thermal resistance by a laser flash method can be performed based on ASTME1461.

Adhesiveness:

The thermally conductive laminate of the present invention is characterized by having different adhesive strengths on both surfaces. A sample of a 25 mm wide laminate was prepared, one side of the laminate was brought into contact with an aluminum plate at room temperature under room temperature, the laminate was pressed with a rubber roller of 2 kg in mass, and then cured for 10 minutes. After adhering a tape-like reinforcing member made of a 25 mm wide silicone tape (Nipper Co., Ltd., No. 99) to the other side of the laminate not bonded to the aluminum plate, one end of the laminate was adhered. When peeled and hold | maintained from the said aluminum plate with the said reinforcing material, and peeled from the said aluminum plate in 180 degree direction at the tensile velocity of 300 mm / min, the force (referred to as "adhesive force") required for peeling was measured. It is preferable that the difference of adhesive force of both surfaces (strong adhesive side surface and weak adhesive side surface) is 2 N / cm or more, and it is especially preferable that it is 3 N / cm or more. When the difference of the adhesive force of both surfaces of a laminated body is less than 3 N / cm, the significant difference in adhesiveness of both surfaces is hard to be expressed, and there exists a possibility that a to-be-adhered body may be damaged at the time of rework and adhesive peeling.

Moreover, it is preferable that the adhesive force measured as mentioned above is 0.3 N / cm or more, especially 0.5-20 N / cm in both surfaces. When either adhesive force is less than 0.3 N / cm, it becomes difficult to fix a heat generating electronic component or a heat dissipation member by own adhesive force. Moreover, when adhesive force is too big | large, since it does not peel easily, rework property is inferior.

Silicone composition 1 and silicone composition 2 are selected so that the adhesive force of both surfaces of the laminated body of this invention may be such a value. This selection can manufacture the plural types of the silicone composition of this invention, changing a composition, apply | coating to a base material, and hardening | curing to form a hardened layer, and can test the adhesive force for each composition by testing adhesive force similarly to the above. Subsequently, the laminated body of this invention can be manufactured easily by selecting and combining 2 types of silicone compositions so that adhesive force may satisfy the said conditions.

[Method for producing thermally conductive laminate]

The thermally conductive laminate of the present invention includes, for example, the method described above, that is, the silicone composition 1 each containing a predetermined amount of the components of (a) to (f) on the surface of the substrate subjected to the surface release treatment for the silicone pressure sensitive adhesive. The first cured product layer was formed by applying a thin film and curing to form a first cured product layer. Then, a silicone composition 2 having a composition different from the silicone composition 1 including the components (a) to (f) was added to the first cured product layer. It can manufacture by apply | coating in a thin film form on the surface, and hardening to form a 2nd hardened | cured material layer.

In the above-described method, the compounding order of each component when producing the composition 1 or the composition 2 is not particularly limited, but as a preferable method,

(1) A necessary amount of the (a) component, the (b) component, and the (d) component is kneaded to prepare a base composition.

(2) Separately, a curing agent obtained by mixing the components (c) and (e) is prepared.

(3) Next, manufacturing the composition which mixed the said base composition, a hardening | curing agent, and the silicone resin of (f) component uniformly is mentioned.

As a base material used for the method of this invention, ie, the base material which apply | coats the silicone composition 1, what performed the surface mold release process for silicone adhesives to paper, a PET film, etc. is suitable. As a surface release agent for silicone pressure sensitive adhesives, the modified silicone which has fluorine substituents, such as a perfluoroalkyl group and a perfluoro polyether group, in a main chain is mentioned.

The perfluoropolyether group may be represented by the following Chemical Formulas 5 to 7.

Moreover, as modified silicone which has such a fluorine substituent, products, such as Shin-Etsu Chemical Co., Ltd. brand name: X-70-201, X-70-258, etc. are mentioned specifically ,.

The method of coating and molding the composition on the substrate may include coating a liquid material on a substrate using a bar coater, a knife coater, a comma coater, a spin coater, or the like in a thin film. no.

In addition, the heating temperature conditions for heating after shaping | molding should just be a temperature which the solvent used volatilizes and (a) component and (c) component can react, when a solvent is added. 50-150 degreeC is preferable and 60-150 degreeC is more preferable in consideration of the influence on productivity and a base film. Hardening time should just be 0.5-30 minutes normally, Preferably it is 1-20 minutes. Even in the case of heating at the same temperature, a heating method in which the temperature is changed by step-up or ramp-up may be adopted.

The heat conductive laminated body after hardening is easy to handle, such as transportation, a fixed cut, by bonding the mold release process film similar to a base film to the surface on the opposite side to the base material side of a laminated body as a separator film for protection. It can be done. At this time, with a base film, it is also possible to change the throughput and kind of a mold release agent, or to change the material of a base material, and to add light weight to the adhesive force from the laminated body of a base film and a separator film.

The thermally conductive laminate thus obtained can be easily disposed even if it is a thin film by peeling the separator film or the base film and then adhering to the heat generating electronic component or the heat dissipation member, and then peeling off the remaining film. It exhibits excellent thermal conductivity properties. Moreover, since adhesiveness differs on both surfaces, peeling on the desired surface (weak adhesion side) can be performed, maintaining adhesiveness on the strong adhesion side at the time of rework or adhesive peeling. As a result, on the weak adhesion side, the stress applied to the adherend is reduced, and it is possible to prevent breakage.

<Example>

Hereinafter, although an Example and a comparative example of this invention are given and this invention is demonstrated concretely, this invention is not limited to the following Example.

First, (a)-(f) component used in the following Example and the comparative example is shown below.

<(a) component>

(A-1) Dimethyl polysiloxane having a kinematic viscosity at 25 ° C. of 600 mm 2 / s and having both ends of the molecular chain sealed with a dimethylvinylsiloxy group.

(A-2) Dimethyl polysiloxane having a kinematic viscosity at 25 ° C. of 30,000 mm 2 / s and having both ends of the molecular chain sealed with a dimethylvinylsiloxy group.

<(b) component>

(B-1) Alumina powder (average specific gravity 3.98) having an average particle diameter of 10.7 µm

(B-2) Alumina powder (average specific gravity 3.98) with an average particle diameter of 1.1 mu m

(B-3) Zinc oxide powder (average specific gravity 5.67) with an average particle diameter of 0.6 micrometers

<(c) component>

(C-1) organohydrogenpolysiloxane represented by the following structural formula

<(D) component>

(D-1) Dimethylpolysiloxane of the platinum-divinyltetramethyldisiloxane complex (molecular chain blocked at both ends by a dimethylvinylsilyl group; solution having a kinematic viscosity of 600 mm 2 / s at 25 ° C. [platinum atom content: 1 mass%〕

<(E) component>

(E-1) 50 mass% toluene solution of 1-ethynyl-1-cyclohexanol

<(f) component>

· (F-1) substantially Me ₃ SiO _0.5 unit (M unit) and SiO ₂ units (Q units), silicone resin (M / Q molar ratio of 1.15) of a toluene solution (non-volatile content of 60% containing only; viscosity 30 ㎟ / s ).

· (F-2) substantially Me ₃ SiO _0.5 unit (M unit) and SiO ₂ toluene solution of silicone resin (M / Q molar ratio of 0.85) composed of only units (Q units) (non-volatile content of 70%; viscosity 30 ㎟ / s ).

<(g) component>

(G-1) structural formula: organosilane represented by C ₁₂ H ₂₅ Si (OC ₂ H ₅ ) ₃

(G-2) Molecular chain single terminal trimethoxysilyl group blockade dimethylpolysiloxane represented by the following structural formula

<(h) component>

(H-1) Dimethyl polysiloxane whose kinematic viscosity at 25 degrees C is represented by the following structural formula.

<Base material>

(K-1) PET film having a thickness of 100 μm to which 1.0 g / m 2 of X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd.

(K-2) 100 μm thick untreated PET film

Production Examples 1 to 4 and Comparative Production Examples 1 to 4

<Preparation of Thermally Conductive Composition>

The component of following Table 1 was mix | blended in the compounding quantity (mass part) described in the same table as follows, and the compositions S1-S7 were manufactured. In addition, compositions S5, S6, and S7 are compositions which do not satisfy the conditions of the present invention.

(A) component, (b) component, and optionally (g) component and (h) component were put into a 700 ml planetary mixer (manufactured by Tokushu-Kigo Kagokyo Co., Ltd., trade name: TK Hibis Mix). It was added and mixed for 60 minutes. Then, the component (d) and the component (e) were added, uniformly mixed, and finally, the component (c) and the component (f) were added and uniformly mixed to prepare a composition.

<< note 1 >>: The numerical value in parentheses in a table | surface is a capacity | capacitance part of resin in (f) component with respect to 100 capacity parts of (a) component.

<< note 2 >>: The density | concentration of (d) component and (e) component in a table | surface is the density | concentration of (D-1) component and (E-1) component with respect to the mass of (a) component. The numerical value in parentheses is 1-ethynyl-1-cyclo contained in (E-1) component with respect to the density | concentration as a platinum atom of (D-1) component with respect to the mass of (a) component, and the mass of (a) component. Concentration of hexanol.

<< note 3 >>: "SiH / Vi" means the number of SiH groups (hydrogen atom couple | bonded with the silicon atom) in (B) component with respect to one vinyl group in (A) component.

[Examples 1 to 4 and Comparative Examples 1 to 5]

<Production of Laminate>

The laminated bodies of following Table 2 and Table 3 were obtained using the conditions of the same table as follows. First, in the composition obtained in Table 1, 1 type (X1) was selected, apply | coated to a base material, it hardened | cured, and the monolayer (Y1) of the thermally conductive hardened | cured material was obtained. Subsequently, in the composition obtained in Table 1, 1 type (X2) was further selected and apply | coated on the monolayer of the heat conductive hardened | cured material obtained previously, and it hardened | cured and obtained laminated body (Y2).

About the obtained laminated body, adhesiveness, rework property, selective peelability, bleeding property, the peelability from a base material, the handleability after peeling, and heat resistance were evaluated by the following method. The results are shown in Tables 2 and 3.

Peelability:

The heat conductive laminated body after hardening was evaluated by the weight at the time of peeling by hand from a base film (evaluation by a touch). It was evaluated as "good" when the texture of peeling was light and deformation | transformation did not generate | occur | produce at all in a laminated body, and it evaluated as "defect" when the texture of peeling was heavy or deformation | transformation generate | occur | produced in a laminated body.

Handling after peeling:

The handleability by the hand of the heat conductive hardened | cured material after peeling was evaluated by paying attention to the shape of a main body. When the heat conductive hardened | cured material peeled from the base film was stuck to an aluminum plate, when adhesiveness was possible without difficulty, it evaluated as "good." When the thermally conductive cured product broke or was firmly adhered and deformed to the hand, and the original shape could not be recovered, it was judged as “poor”.

Reworkability, Selective Peelability:

Both surfaces of the thermally conductive cured product after peeling were sandwiched by the same aluminum plate, and reworkability (whether peeling did not cause damage to the adhesive) and selective peelability (always peeling from the weakly adhesive side) were evaluated.

The test which peeled the two aluminum sheets adhere | attached through a thermally conductive hardened | cured material was repeated 5 times (The thermally conductive hardened | cured material and an aluminum plate were changed for every test.). When the thermally conductive cured product is peeled off from the aluminum plate adhered to the weak adhesive force without deformation or destruction of the aluminum plate adhered to both surfaces, it is evaluated as "good" and adhered to the strong adhesive face at least once. When the heat conductive hardened | cured material peeled from an aluminum plate, when an aluminum plate or a heat conductive hardened | cured material deform | transformed and destroyed, it evaluated as "defect."

Adhesiveness:

In the above-described manner, the thermally conductive laminate is bonded to an aluminum plate on one side with a 2 kg rubber roller, and then cured for 10 minutes, and the other side that is not bonded to the aluminum plate is hardened to prevent deformation of the laminate. After adhering with a strong silicone adhesive tape (manufactured by Nipper Co., Ltd.), one end was peeled off and held by hand, and peeled at 180 ° at a tensile speed of 300 mm / min at room temperature to measure the adhesive force. The measurement results are shown in Tables 2 and 3.

Bleeding:

A 0.1 mm thick sample was cut into 20 mm sides for each substrate, placed on top of the paper toward the resin layer, and then placed on a 100 g weight thereon to be in close contact with each other. Visually confirmed and evaluated.

Thermal resistance:

The thermally conductive laminate obtained above is installed on the entire surface of a disc-shaped plate made of standard aluminum (purity: 99.9%, diameter: about 12.7 mm, thickness: about 1.0 mm), and another standard aluminum plate is superimposed thereon. The pressure of about 175.5 kPa (1.80 kgf / cm <2>) was applied by clamping the obtained structure with a clip, and the three-layer structure was obtained.

The thickness of the thermally conductive laminate was calculated by measuring the thickness of the obtained test piece and subtracting the known thickness of the plate of standard aluminum. In addition, the micrometer (Mitsutoyo Corporation make, model: M820-25VA) was used for the measurement of the thickness of a test piece. The obtained results are shown in Tables 2 and 3. Using the said test piece, the thermal resistance (cm <2> * K / W) of the thermally conductive laminated body was measured by the heat resistance measuring instrument (the Nessen make, Xenon flash analyzer; LFA447 Nano Flash). The obtained thermal resistance is shown in Table 2 and Table 3.

Application to heat generating and radiating device:

 1 is a schematic cross-sectional view showing the structure of a heat generating / heat radiating device. It demonstrates based on FIG. The thermally conductive laminated body 1 obtained in the said Examples 1-3 was installed on the surface of the pseudo CPU 2 of 2 cm x 2 cm. The pseudo CPU 2 is mounted on the printed wiring board 3. The heat dissipation member 4 was superimposed on the laminated body 1, and it crimped by clamp-stopping the heat dissipation member 4 and the printed wiring board 3 with the clamp 5. In this way, the heat generating and heat radiating device 6 in which the pseudo CPU 2 and the heat dissipation member 4 are bonded to each other via the thermally conductive laminate 1 is obtained.

When power was supplied to the pseudo CPU 2, the pseudo CPU 2 generated heat and the temperature rose, but was stabilized at about 100 ° C. Stable heat conduction and heat dissipation were possible for a long time of 1000 hours, and no failure of the pseudo CPU due to overheat accumulation occurred. In addition, damage to the pseudo CPU 2 and the printed wiring board was also prevented when the heat dissipation member 4 was removed. Therefore, it was confirmed that the reliability of heat generating / heat radiating devices such as semiconductor devices is improved by adopting the thermally conductive laminate of the present invention.

Claims (9)

(a) an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule: 100 parts by volume, (b) thermally conductive filler: 50 to 1,000 parts by volume, (c) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule: an amount such that the molar ratio of the alkenyl group in the hydrogen atom / (a) component bonded to the silicon atom of the present component is 0.5 to 5.0, (d) platinum group metal catalysts: an effective amount, (e) reaction control agents: effective amounts and (f) Silicone resin: 50 to 500 parts by volume And a first cured product layer formed by molding and curing a silicone composition 1 comprising a thin film, and the components (a) to (f) as essential components, and the silicone composition 2 having a composition different from the silicone composition 1 above. The heat conductive laminated body which consists of a 2nd hardened | cured material layer formed by shape | molding and hardening in a thin film form on one side of a 1st hardened | cured material layer, and the adhesive force of both surfaces differs. The method according to claim 1, wherein at room temperature, one side of a 25 mm wide sample of the laminate is brought into contact with an aluminum plate at room temperature, and the laminate is pressed with a rubber roller of 2 kg by mass to cure for 10 minutes after adhesion. Then, the other side of the laminate, which is not bonded to the other side of the laminate, is adhered to the reinforcing material, and then one end of the laminate is gripped together with the reinforcing material bonded thereto, and the aluminum is rotated in a 180 ° direction at a tensile speed of 300 mm / min. When peeling from a plate and measuring the force (adhesive force) required for peeling on both surfaces of the said laminated body, the adhesive force of both surfaces is 0.3 N / cm or more, and the thermal conductivity whose difference of adhesive strength of both surfaces is 2 N / cm or more Laminate. The silicone resin of component (f) is composed of R ¹ ₃ SiO _1/2 units (R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond) and SiO. _A thermally conductive laminate comprising _4/2 units and having a molar ratio of R ¹ ₃ SiO _1/2 units / SiO _4/2 units between 0.5 and 1.5. The terminal of one of claims 1 or 2, wherein (g) alkoxysilane compound represented by the following general formula (1) and (g-2) one end of the molecular chain represented by the following general formula (2) is a tree. 1 or more types chosen from the group which consists of dimethylpolysiloxane sealed by the alkoxy silyl group: The heat conductive laminated body containing 0.01-50 volume parts. <Formula 1> R ² _a R ³ _b Si (OR ⁴ ) _4-ab (Wherein R ² is independently an alkyl group having 6 to 15 carbon atoms, R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ independently is carbon number Is an alkyl group of 1 to 6, a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b is an integer of 1 to 3) <Formula 2> (Wherein R ⁵ is independently an alkyl group having 1 to 6 carbon atoms, c is an integer of 5 to 100) The thermal conductivity according to claim 1 or 2, further comprising (h) an organopolysiloxane having a kinematic viscosity of 10 to 100,000 mm 2 / s at 23 ° C. represented by the following general formula (3). Laminate. <Formula 3> R ^6- (SiR ⁶ ₂ O) _d SiR ⁶ ₂ -R ⁶ (In formula, R <^6> is the monovalent hydrocarbon group which does not contain the aliphatic unsaturated bond of C1-C18 independently, d is an integer of 5-2,000.) The thermally conductive laminate according to claim 1 or 2, wherein the thermally conductive laminate has a thickness of 20 to 1,000 µm. The thermally conductive laminate according to claim 1 or 2, wherein the thermal resistance at 25 ° C. measured by the laser flash method is 10 cm 2 · K / W or less. (a) an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule: 100 parts by volume, (b) thermally conductive filler: 50 to 1,000 parts by volume, (c) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule: an amount such that the molar ratio of the alkenyl group in the hydrogen atom / (a) component bonded to the silicon atom of the present component is 0.5 to 5.0, (d) platinum group metal catalysts: an effective amount, (e) reaction control agents: effective amounts and (f) Silicone resin: 50 to 500 parts by volume Applying the silicone composition 1 comprising a thin film on the surface of the substrate subjected to the surface release treatment for a silicone pressure-sensitive adhesive and cured to form a first cured product layer, and then containing the components (a) to (f) By applying a silicone composition 2 having a composition different from the silicone composition 1 in a thin film form on the surface of the first cured product layer to form a second cured product layer. Method for producing a conductive laminate. The manufacturing method of Claim 8 whose release process for silicone adhesives performed on the base material is the process by modified silicone which contains a fluorine substituent in a main chain.