阅读说明：本技术 导热性薄膜状固化物及其制造方法以及导热性构件 (Heat-conductive film-like cured product, method for producing same, and heat-conductive member ) 是由 伊藤崇则 远藤晃洋 田中优树 于 2019-01-08 设计创作，主要内容包括：提供导热性薄膜状固化物,其为可处理的有机硅组合物的固化物,向构件的转印性、剥离后的处理性良好,即使在高温下也显示与发热性元件良好的粘接强度。使有机硅组合物固化而成的导热性薄膜状固化物,该有机硅组合物含有：(a)在1分子具有2个以上的烯基的有机聚硅氧烷：100质量份；(b)导热性填充剂：200～2000质量份；(c)在1分子中具有2个以上的与硅原子直接结合的氢原子的有机氢聚硅氧烷：其量使得Si-H/烯基成为0.5～50.0；(d)铂族金属系化合物：以铂族金属系元素量计,相对于(a)成分,为0.1～1000ppm(质量)；(e)反应控制剂：必要量；(f)有机硅树脂：50～300质量份；(g)选自下述(g-1)和(g-2)中的粘接成分：0.1～20质量份。(Disclosed is a heat-conductive film-like cured product of a processable silicone composition which has good transferability to a member and good handleability after peeling, and which exhibits good adhesion strength to a heat-generating element even at high temperatures. A heat-conductive film-like cured product obtained by curing a silicone composition, the silicone composition comprising: (a) an organopolysiloxane having 2 or more alkenyl groups in 1 molecule: 100 parts by mass; (b) thermally conductive filler: 200-2000 parts by mass; (c) an organohydrogenpolysiloxane having 2 or more hydrogen atoms directly bonded to silicon atoms in 1 molecule: in an amount such that the Si-H/alkenyl group is 0.5 to 50.0; (d) platinum group metal-based compound: 0.1 to 1000ppm (by mass) based on the amount of the platinum group metal element relative to the component (a); (e) reaction control agent: a necessary amount; (f) silicone resin: 50-300 parts by mass; (g) a bonding component selected from the following (g-1) and (g-2): 0.1 to 20 parts by mass.)

1. A thermally conductive film-like cured product obtained by curing a silicone composition containing:

(a) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass of a water-soluble polymer,

(b) thermally conductive filler: 200 to 2000 parts by mass of a water-soluble polymer,

(c) an organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to silicon atoms in 1 molecule: the amount of the (C) component is such that the number of hydrogen atoms directly bonded to silicon atoms/the number of alkenyl groups (a) component is 0.5 to 50.0,

(d) platinum group metal-based compound: 0.1 to 1000ppm (by mass) based on the amount of the platinum group metal-based element relative to the component (a),

(e) reaction control agent: the necessary amount of the water-soluble polymer,

(f) silicone resin: 50 to 300 parts by mass, and

(g) a bonding component selected from the following (g-1) and (g-2): 0.1 to 20 parts by mass

(g-1) Compound represented by the following general formula (1)

[ solution 1]

n is an integer of 1 to 15,

(g-2) an organosilicon compound having 1 to 100 silicon atoms, which has at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom bonded to a silicon atom.

2. The thermally conductive cured product in the form of a film according to claim 1, wherein the component (f) contains R¹ ₃SiO_1/2Unit and SiO_4/2Unit, use (R)¹ ₃SiO_1/2Unit)/(SiO_4/2Unit) of a silicone resin in a molar ratio of 0.1 to 3.0, R¹Represents an unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond.

3. The thermally conductive cured product in the form of a film according to claim 1 or 2, wherein the silicone composition further contains 1 or more surface-treating agents selected from the following (h-1) and (h-2): 0.1 to 40 parts by mass of a stabilizer,

(h-1): an alkoxysilane compound represented by the following general formula (2)

R² _aR³ _bSi(OR⁴)_4-a-b(2)

In the formula, R²Independently an alkyl group having 6 to 15 carbon atoms, R³Independently an unsubstituted or substituted C1-8 alkyl group, R⁴Independently an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, however, a + b is an integer of 1 to 3,

(h-2): dimethylpolysiloxane having one end of the molecular chain blocked with a trialkoxy group, represented by the following general formula (3)

[ solution 2]

In the formula, R⁵Independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100.

4. A thermally conductive cured product in the form of a film according to any one of claims 1 to 3, wherein the component (b) is a thermally conductive filler selected from the group consisting of metals, oxides and nitrides.

5. A method for producing a thermally conductive cured product in the form of a film according to any one of claims 1 to 4, which comprises a step of forming a surface-release-treated substrate of a silicone composition into a film and curing the film, wherein the silicone composition comprises:

(a) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass of a water-soluble polymer,

(b) thermally conductive filler: 200 to 2000 parts by mass of a water-soluble polymer,

(c) an organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to silicon atoms in 1 molecule: the amount of the (C) component is such that the number of hydrogen atoms directly bonded to silicon atoms/the number of alkenyl groups (a) component is 0.5 to 50.0,

(d) platinum group metal-based compound: 0.1 to 1000ppm (by mass) based on the amount of the platinum group metal-based element relative to the component (a),

(e) reaction control agent: the necessary amount of the water-soluble polymer,

(f) silicone resin: 50 to 300 parts by mass, and

(g) a bonding component selected from the following (g-1) and (g-2): 0.1 to 20 parts by mass

(g-1) Compound represented by the following general formula (1)

[ solution 3]

n is an integer of 1 to 15,

(g-2) an organosilicon compound having 1 to 100 silicon atoms, which has at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom bonded to a silicon atom.

6. The production method according to claim 5, wherein the treatment component used in the surface mold release treatment is a modified silicone having a fluorine substituent in the main chain.

7. A heat-conductive member obtained by molding a silicone composition into a film form on a surface-treated substrate for a silicone adhesive, and curing the molded product, the heat-conductive member comprising the substrate and a heat-conductive film-form cured product, the silicone composition comprising:

(a) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass of a water-soluble polymer,

(b) thermally conductive filler: 200 to 2000 parts by mass of a water-soluble polymer,

(c) an organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to silicon atoms in 1 molecule: the amount of the (C) component is such that the number of hydrogen atoms directly bonded to silicon atoms/the number of alkenyl groups (a) component is 0.5 to 50.0,

(d) platinum group metal-based compound: 0.1 to 1000ppm (by mass) based on the amount of the platinum group metal-based element relative to the component (a),

(e) reaction control agent: the necessary amount of the water-soluble polymer,

(f) silicone resin: 50 to 300 parts by mass, and

(g) a bonding component selected from the following (g-1) and (g-2): 0.1 to 20 parts by mass

(g-1) Compound represented by the following general formula (1)

[ solution 4]

n is an integer of 1 to 15,

(g-2) an organosilicon compound having 1 to 100 silicon atoms, which has at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom bonded to a silicon atom.

8. The thermally conductive member according to claim 7, wherein the treatment component used in the surface mold release treatment is a modified silicone containing a fluorine substituent in the main chain.

Technical Field

The present invention relates to a heat conductive cured product, and more particularly to a heat conductive film-like cured product that can be mounted between a heat boundary surface of a heat generating element and a heat dissipating member such as a heat sink or a circuit board for cooling the heat generating element, a method for producing the same, and a heat conductive member.

Background

Semiconductors such as transistors and diodes used in electronic devices such as converters and power supplies, and LED elements serving as light sources for lighting and displays generate a large amount of heat by themselves in accordance with high performance, high speed, small size, and high integration, and the temperature rise of the devices due to the heat causes operational failure and destruction. Therefore, a large number of heat dissipation methods for suppressing a temperature rise of a semiconductor in operation and a heat dissipation member used therein have been proposed.

Conventionally, in electronic devices and the like, in order to suppress a temperature rise of a semiconductor during operation, heat generated from the semiconductor is conducted to a cooling member such as a heat sink or a case using a metal plate having high thermal conductivity such as aluminum or copper via a thermal conductive material, and the heat is radiated to the outside by a temperature difference from the atmosphere. As the heat conductive material, a heat conductive sheet having insulation properties is used in a large amount. When the cooling member and the semiconductor are fixed, screws, clips, and the like are used. Further, the thermal conductive sheet interposed therebetween is also fixed by pressing with a screw or a clip. However, the fixing method using screws and clips requires the preparation of screws and clips; holes for fixing screws are formed in the housing, the semiconductor element, the substrate, and the like; the number of parts and the number of steps increase in the fixing step, which is very disadvantageous in view of manufacturing efficiency. Further, the components such as screws and clips hinder the miniaturization and thinning of the electronic device itself, and are also very disadvantageous in product design. Therefore, a method of fixing the case and the semiconductor element by giving adhesion to the thermal conductive sheet interposed between the cooling member and the semiconductor is considered.

Specifically, there is a method of coating a pressure-sensitive adhesive on both sides of a thermal conductive sheet to make a thermal conductive sheet with a pressure-sensitive adhesive, and since the pressure-sensitive adhesive itself does not have thermal conductivity, the heat transfer of the thermal conductive sheet with a pressure-sensitive adhesive becomes significantly poor. Therefore, a thermally conductive pressure-sensitive adhesive tape in which a thermally conductive filler is filled in a pressure-sensitive adhesive material is known (patent document 1: Japanese patent application laid-open Nos. 2014-34652, 2: 2014-62220, and 3: 2002-121529). In particular, a heat conductive silicone pressure-sensitive adhesive tape using silicone as a polymer is known for its heat resistance, cold resistance, and durability (patent document 4: japanese patent No. 5283346). However, the pressure-sensitive adhesive tape has the following problems: the adhesive strength is inferior to that of a general adhesive material, particularly at high temperature. Further, if a heat-curable adhesive is used, the working process at the time of application becomes complicated, and there is a problem that workability is inferior to that of a pressure-sensitive adhesive sheet.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermally conductive film-like cured product of a silicone composition which can be easily handled even in a single layer or a thin film, which has good transferability to a member and good handling properties after peeling, and which exhibits good adhesion strength to a heat-generating element even at high temperatures, a method for producing the same, and a thermally conductive member using the same.

Means for solving the problems

The present inventors have intensively studied to achieve the above object, and as a result, they have found that: a heat conductive film-like cured product of a silicone composition in which a heat conductive filler is blended in an addition reaction curable silicone rubber composition and an appropriate amount of a silicone resin and a specific adhesive component are blended has good transferability to a member and good handling properties after peeling, and exhibits good adhesive strength with a heat generating element even at high temperatures, as shown in examples described later.

Accordingly, the present invention provides the following thermally conductive film-like cured product, a method for producing the same, and a thermally conductive member.

1. A thermally conductive film-like cured product obtained by curing a silicone composition containing:

(a) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass of a water-soluble polymer,

(b) thermally conductive filler: 200 to 2000 parts by mass of a water-soluble polymer,

(c) an organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to silicon atoms in 1 molecule: the amount of the (C) component is such that the number of hydrogen atoms directly bonded to silicon atoms/the number of alkenyl groups (a) component is 0.5 to 50.0,

(d) platinum group metal-based compound: 0.1 to 1000ppm (by mass) based on the amount of the platinum group metal-based element relative to the component (a),

(e) reaction control agent: the necessary amount of the water-soluble polymer,

(f) silicone resin: 50 to 300 parts by mass, and

(g) a bonding component selected from the following (g-1) and (g-2): 0.1 to 20 parts by mass (g-1) of a compound represented by the following general formula (1)

[ solution 1]

(n is an integer of 1 to 15.)

(g-2) an organosilicon compound having 1 to 100 silicon atoms, which has at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom bonded to a silicon atom.

The thermally conductive cured film of claim 2.1, wherein the component (f) contains R¹ ₃SiO_1/2Unit (R)¹Represents an unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond. ) And SiO_4/2Unit, use (R)¹ ₃SiO_1/2Unit)/(SiO_4/2Unit) is 0.1 to 3.0.

The thermally conductive cured product in the form of a film of claim 1 or 2, wherein the silicone composition further contains 1 or more surface-treating agents selected from the following (h-1) and (h-2): 0.1 to 40 parts by mass.

(h-1): an alkoxysilane compound represented by the following general formula (2)

R² _aR³ _bSi(OR⁴)_4-a-b(2)

(in the formula, R²Independently an alkyl group having 6 to 15 carbon atoms, R³Independently an unsubstituted or substituted C1-8 alkyl group, R⁴Independently an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, however, a + b is an integer of 1 to 3. )

(h-2): dimethylpolysiloxane having one end of the molecular chain blocked with a trialkoxy group, represented by the following general formula (3)

[ solution 2]

(in the formula, R⁵Independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100. )

4.1 to 3, wherein the component (b) is a thermally conductive filler selected from the group consisting of metals, oxides and nitrides.

5. A method for producing a thermally conductive cured product in the form of a film according to any one of 1 to 4, which comprises a step of forming the silicone composition into a film on a substrate whose surface has been subjected to a mold release treatment, and curing the film.

The production process according to 6.5, wherein the treatment component for the surface mold release treatment is a modified silicone having a fluorine substituent in the main chain.

7. And a heat-conductive member obtained by molding the silicone composition into a film on a surface-treated substrate for silicone adhesives and curing the film, wherein the heat-conductive member comprises the substrate and a heat-conductive film-shaped cured product.

The thermally conductive member according to claim 8.7, wherein the treatment component for the surface mold release treatment is a modified silicone having a fluorine substituent in the main chain.

ADVANTAGEOUS EFFECTS OF INVENTION

The heat conductive film-like cured product of the present invention has good transferability to a member, has good handleability after peeling even in a single layer or a thin film, and can be easily fixed by adhering to a heat generating element or a heat dissipating member. Further, the adhesive exhibits excellent adhesive strength with the heat generating element even at high temperatures.

Detailed Description

The present invention will be described in detail below.

[ (a) component ]

(a) The component (b) is an organopolysiloxane having at least 2 alkenyl groups in 1 molecule, and 1 kind can be used alone or 2 or more kinds can be used in combination as appropriate. Specific examples of the component (a) include organopolysiloxanes represented by the following average structural formulae (4) to (6).

[ solution 3]

(in the formula, R⁶Independently an unsubstituted or substituted 1-valent hydrocarbon group free of aliphatic unsaturation, and X is an alkenyl group. d and e are each a positive number of 0 or 1 or more, f is a positive number of 1 or more, and g is a positive number of 2 or more. )

As R⁶Examples of the unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl and methylbenzyl, and groups obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms of these groups with halogen atoms such as fluorine, chlorine and bromine, cyano groups, and the like, for example, chloromethyl, 2-bromoethyl, 3-chloropropyl, 3, 3, 3-trichloroExamples of the alkyl group include 1-10 carbon atoms, particularly 1-6 carbon atoms, such as fluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl, and among these, an unsubstituted or substituted alkyl group having 1-3 carbon atoms such as methyl, ethyl, propyl, chloromethyl, bromoethyl, 3, 3, 3-trifluoropropyl, cyanoethyl, and an unsubstituted or substituted phenyl group such as phenyl, chlorophenyl, fluorophenyl, and the like are preferable. In addition, R⁶May be the same or different. As long as for R⁶The methyl group is preferably selected from all of the methyl groups, from the viewpoints of cost, availability, chemical stability, environmental load, and the like.

Examples of the alkenyl group of X include alkenyl groups having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group, among which a lower alkenyl group such as a vinyl group and an allyl group is preferable, and a vinyl group is more preferable.

d is a positive number of 0 or 1 or more, preferably 10. ltoreq. d.ltoreq.10000, more preferably 50. ltoreq. d.ltoreq.2000, and further preferably 100. ltoreq. d.ltoreq.1000.

e is a positive number of 0 or 1 or more, preferably 0. ltoreq. e/(d + e). ltoreq.0.5, more preferably 0. ltoreq. e/(d + e). ltoreq.0.1.

f is a positive number of 1 or more, preferably 0 < f/(d + f) ≦ 0.5, more preferably 0 < f/(d + f) ≦ 0.1.

g is a positive number of 2 or more, preferably 0 < g/(d + g) ≦ 0.5, more preferably 0 < g/(d + g) ≦ 0.1.

(A) The organopolysiloxane of component (a) may be oily or rubbery, and 1 type may be used alone or a plurality of organopolysiloxanes having different viscosities may be used in combination. The average polymerization degree is preferably 10 to 100000, more preferably 100 to 10000. The polymerization degree can be determined as a polystyrene equivalent value in Gel Permeation Chromatography (GPC) analysis using toluene as a developing solvent, and is a number average polymerization degree (the same applies below).

[ (b) component ]

The thermally conductive filler of component (b) is not particularly limited, and specific examples thereof include nonmagnetic metals such as copper and aluminum, oxides such as alumina (alumina), silica, magnesia, iron oxide, beryllium oxide, titania, and zirconia, nitrides such as aluminum nitride, silicon nitride, and boron nitride, artificial diamond, and silicon carbide. Among them, metals, oxides, and nitrides are preferable, and aluminum oxide, boron nitride, and aluminum hydroxide are more preferable.

The average particle diameter of the thermally conductive filler is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 0.5 to 30 μm. These thermally conductive fillers may be used alone in 1 kind, or may be used in combination of two or more kinds. In addition, 2 or more kinds of particles having different average particle diameters may be used. In the present invention, the average particle diameter is a volume average particle diameter (MV value) obtained by MICROTRAC (laser diffraction scattering method), and can be measured, for example, by a MICROTRAC particle size distribution measuring apparatus MT3300EX (japan ltd.).

The amount of the component (b) is 200 to 2000 parts by mass, preferably 500 to 1500 parts by mass, based on 100 parts by mass of the component (a). If the amount of the thermally conductive filler blended is too large, the fluidity is lost and molding is difficult, and if it is too small, the desired thermal conductivity cannot be obtained.

[ (c) component ]

The organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to silicon atoms in 1 molecule has at least 2, preferably 3 or more hydrogen atoms directly bonded to silicon atoms (i.e., Si — H groups) in the molecular chain. The organohydrogenpolysiloxane of component (c) is not an organohydrogenpolysiloxane having a phenylene skeleton. Specific examples of such organohydrogenpolysiloxane include organohydrogenpolysiloxanes represented by the following average structural formulae (7) to (9).

[ solution 4]

(in the formula, R⁷Independently an unsubstituted or substituted 1-valent hydrocarbon group which does not contain an aliphatic unsaturated bond, h is a positive number of 0 or 1 or more, i is a positive number of 2 or more, j is a positive number of 1 or more, and k is a positive number of 0 or 1 or more. )

In the above formulae (7) to (9), R is⁷Examples of the unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl and methylbenzyl, and groups obtained by substituting part or all of hydrogen atoms bonded to carbon atoms of these groups with halogen atoms such as fluorine, chlorine and bromine, cyano groups, for example, chloromethyl, 2-bromoethyl, 3-chloropropyl, 3, 3, 3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups having 1 to 10 carbon atoms, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3, 3, 3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3, 3, 4, 4, 5, 5, 6, particularly 1-valent hydrocarbon group having 1 to 6 carbon atoms, and among these, unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group, chloromethyl group, bromoethyl group, 3, 3, 3-trifluoropropyl group, cyanoethyl group and the like, and unsubstituted or substituted phenyl group such as phenyl group, chlorophenyl group, fluorophenyl group and the like are preferable. In addition, R⁷May be the same or different, and is preferably the same as R⁶The same substituents. R⁷And R⁶Similarly, all methyl groups are preferred from the viewpoints of cost, availability, chemical stability, environmental load, and the like, as long as special characteristics such as solvent resistance are not required.

In the formula, h is a positive number of 0 or 1 or more, preferably 0 to 500, and more preferably 5 to 100. i is a positive number of 2 or more, preferably 2 to 100, more preferably 2 to 50. j is a positive number of 1 or more, preferably 1 to 100, and more preferably 1 to 50. k is a positive number of 0 or 1 or more, preferably 0 to 100, and more preferably 0 to 50. (c) The average polymerization degree of the component (A) is preferably 5 to 100, more preferably 10 to 50.

(c) The amount of component (b) is an amount such that the ratio of (the number of hydrogen atoms (Si-H groups) directly bonded to silicon atoms in component (c))/(the number of alkenyl groups in component (a)) is 0.5 to 50.0, preferably 1.0 to 30.0, and more preferably 2.0 to 20.0. If the amount of the Si-H group in the component (c) is less than 0.5 based on 1 alkenyl group in the component (a), there are problems that the curing of the molded sheet does not proceed so much, the strength of the molded sheet is insufficient, and the molded sheet cannot be handled as a molded article. If the amount exceeds 50.0, the sheet after molding may have an insufficient sticky feeling and may not be fixed by self-adhesion.

[ (d) component ]

(d) The component (b) is a platinum group metal compound, and 1 kind thereof may be used alone or 2 or more kinds thereof may be used in combination as appropriate. (d) The platinum group metal-based compound (platinum group-based curing catalyst) of the component (a) is a catalyst for promoting an addition reaction between the alkenyl group of the component (a) and the Si — H group of the component (c), and known catalysts for hydrosilylation reactions are exemplified. Specific examples thereof include platinum (including platinum black), rhodium, palladium, and other platinum group metal simple substances, and H₂PtCl₄·m’H₂O、H₂PtCl₆·m’H₂O、NaHPtCl₆·m’H₂O、KHPtCl₆·m’H₂O、Na₂PtCl₆·m’H₂O、K₂PtCl₄·m’H₂O、PtCl₄·m’H₂O、PtCl₂、Na₂HPtCl₄·m’H₂And (ii) platinum chloride such as O (wherein m' is an integer of 0 to 6, preferably 0 or 6), chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, a product obtained by supporting platinum group metal such as platinum black or palladium on a carrier such as alumina, silica or carbon, a rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (wilkinson catalyst), platinum chloride, chloroplatinic acid or a complex of chloroplatinate and vinyl group-containing siloxane, and the like.

(d) The amount of the component (a) used may be a so-called catalyst amount, and is usually 0.1 to 1000ppm (by mass), preferably 0.5 to 200ppm, more preferably 1.0 to 100ppm, based on the amount of the platinum group metal-based element, relative to the component (a).

[ (e) ingredient ]

(e) The reaction control agent of component (b) is an addition reaction control agent for adjusting the reaction rate of component (a) and component (c) in the presence of component (d), and 1 kind may be used alone, or 2 or more kinds may be used in combination as appropriate. Examples of the component (e) include acetylene alcohol compounds such as ethynyl methylene methanol, amine compounds, phosphorus compounds, and sulfur compounds, and among them, acetylene alcohol compounds are preferable.

(e) The amount of the component (a) is arbitrary as long as it is an amount necessary to adjust the reaction rate to a desired level, and is preferably 0.01 to 2.0 parts by mass per 100 parts by mass of the component (a).

[ (f) ingredient ]

To impart tackiness to the cured product of the present invention, the silicone resin of component (f) used in the present invention is added. Component (f) preferably contains R¹ ₃SiO_1/2Unit (M unit) (R)¹Represents an unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond) and SiO_4/2Unit (Q unit) with (R)¹ ₃SiO_1/2Unit)/(SiO_4/2Unit) is 0.1 to 3.0, more preferably 0.6 to 1.4, and still more preferably 0.7 to 1.3. When M/Q is less than 0.1, when M/Q exceeds 3.0, desired adhesion may not be obtained.

R¹Examples of the unsubstituted or substituted 1-valent hydrocarbon group having no aliphatic unsaturated bond include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl and methylbenzyl, and groups obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms of these groups with halogen atoms such as fluorine, chlorine and bromine, cyano groups, and the like, and examples thereof includeAnd (b) a 1-valent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a 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-nonafluorohexyl group, and among these, an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, propyl group, chloromethyl group, bromoethyl group, 3, 3, 3-trifluoropropyl group, cyanoethyl group, and an unsubstituted or substituted phenyl group, such as a phenyl group, chlorophenyl group, fluorophenyl group, are preferable. In addition, R¹May be the same or different, and is preferably the same as R⁶The same substituents. R¹And R⁶Similarly, all methyl groups are preferred from the viewpoints of cost, availability, chemical stability, environmental load, and the like, as long as special characteristics such as solvent resistance are not required.

The amount of component (f) is 50 to 300 parts by mass, preferably 60 to 200 parts by mass, and more preferably 70 to 150 parts by mass, per 100 parts by mass of component (a). When the amount of the component (f) is less than 50 parts by mass and exceeds 300 parts by mass, desired tackiness is not obtained. (f) The component itself may be a solid or viscous liquid at room temperature, or may be used in a state of being dissolved in a solvent. In this case, the amount added in the composition is determined with the amount excluding the solvent part.

[ (g) ingredient ]

(g) The component (A) is a bonding component selected from the following (g-1) and (g-2), and 1 kind of the component (A) may be used alone or 2 or more kinds may be used in combination as appropriate. By blending the component (g) in the composition, a cured product thereof can have good adhesiveness even at high temperatures.

(g-1) Compound represented by the following general formula (1)

[ solution 5]

(n is an integer of 1 to 15.)

(g-2) an organosilicon compound having 1 to 100 silicon atoms and having at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom bonded to a silicon atom

The component (g-1) is a compound represented by the above general formula (1), and n is an integer of 1 to 15, preferably 2 to 10, more preferably 4 to 10, from the viewpoint of adhesiveness.

(g-2) an organosilicon compound having 1 to 100 silicon atoms and having at least 1 phenylene skeleton in 1 molecule and at least 1 hydrogen atom (Si-H group) bonded to the silicon atom. The "phenylene skeleton" in the present invention includes aromatic polycyclic skeletons having a valence of 2 to 6, particularly 2 to 4, such as a phenylene skeleton, a naphthalene skeleton, and an anthracene skeleton.

The organosilicon compound preferably has at least 1, preferably 1 to 4 phenylene-based skeletons in 1 molecule and at least 1, preferably 1 to 20, and more preferably about 2 to 10 Si — H groups (i.e., hydrogen atoms bonded to silicon atoms) in 1 molecule. Further, it may contain 1 or 2 or more kinds of functional groups such as epoxy groups such as glycidyloxy groups, alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl and methyldimethoxysilyl groups, ester groups, acryloyl groups, methacryloyl groups, carboxylic anhydride groups, isocyanate groups, amino groups, and amido groups. The number of silicon atoms is 1 to 100, preferably 2 to 30, more preferably 2 to 20, and further preferably 4 to 10. The structure is not particularly limited, and a linear or cyclic organic siloxane oligomer, an organic silicon compound such as organic silane, or the like can be preferably used.

Specific examples of such a compound include the following compounds.

[ solution 6]

[ solution 7]

(p is independently 1-4.)

[ solution 8]

[ in the formula, X is

Y is as follows

(R' is as follows

Of R_w，R_xIs an unsubstituted or substituted 1-valent hydrocarbon group. p is 1 to 4, q is 1 to 50, r is 0 to 100, preferably q is 1 to 20, r is 1 to 50. )

The group shown, R' is selected from

[ solution 9]

(R_w、R_xIn the same manner as above, y is 1 to 100. )

In (1), Y' is

[ solution 10]

(R_w、R_xAs above, p is 1 to 4, q is 1 to 50, r is 0 to 100, preferably q is 1 to 20, r is 1 to 50. )

z is 1 to 50. ]

Further, as the above-mentioned R_w、R_xThe unsubstituted or substituted 1-valent hydrocarbon group of (2) is preferably a 1-valent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, and examples of the substituted 1-valent hydrocarbon group include alkyl groups, aryl groups, aralkyl groups, alkenyl groups, etc., and examples thereof include alkoxy groups,and substituted 1-valent hydrocarbon groups such as an acrylic group, a methacrylic group, an acryloyl group, a methacryloyl group, an amino group, and an alkylamino group.

As the component (g-2), an organosilicon compound in which an alkoxysilyl group such as a trimethoxysilyl group, triethoxysilyl group, or methyldimethoxysilyl group, an acryloyl group, a methacryloyl group, an ester group, a carboxylic anhydride group, an isocyanate group, an amino group, or an amido group is further introduced into the above-mentioned exemplified compounds can also be used.

The content of hydrogen atoms (Si-H groups) bonded to silicon atoms in the organosilicon compound as component (g-2) is preferably 0.001 to 0.01 mol/g, more preferably 0.002 to 0.01 mol/g. From the viewpoint of sufficient adhesiveness, it is preferably 0.001 mol/g or more, and if it is more than 0.01 mol/g, the organosilicon compound of the component (g-2) may be unstable at room temperature.

The amount of component (g) is 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1.0 to 10 parts by mass, based on 100 parts by mass of component (a). When the amount of the component (g) is less than 0.1 parts by mass and exceeds 20 parts by mass, desired adhesiveness is not obtained. Furthermore, the ratio of the number of Si-H groups/the number of alkenyl groups is preferably 0.5 to 50.0, more preferably 1.0 to 30.0, and still more preferably 2.0 to 20.0, based on the whole composition.

[ (h) ingredient ]

The silicone composition of the present invention preferably contains 1 or more surface-treating agents selected from the following (h-1) and (h-2). By blending the surface treatment agent, the thermally conductive filler as the component (b) can be uniformly dispersed in the matrix composed of the component (a) in the production of the silicone composition.

(h-1): an alkoxysilane compound represented by the following general formula (2)

R² _aR³ _bSi(OR⁴)_4-a-b(2)

(in the formula, R²Independently an alkyl group having 6 to 15 carbon atoms, R³Independently unsubstituted or substituted 1 to cA 1-valent hydrocarbon group of 8, R⁴Independently an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3. )

As a group consisting of R²Examples of the alkyl group include hexyl, octyl, nonyl, decyl, dodecyl and tetradecyl. If the R is²When the number of carbon atoms of the alkyl group is in the range of 6 to 15, the wettability of the component (C) is sufficiently improved, the handleability is good, and the low-temperature characteristics of the composition are good.

As a group consisting of R³Examples of the unsubstituted or substituted 1-valent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl, xylyl, naphthyl and biphenyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl and methylbenzyl, and groups obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms in these groups with halogen atoms such as fluorine, chlorine and bromine, cyano groups, for example, chloromethyl, 2-bromoethyl, 3-chloropropyl, 3, 3, 3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, and the like, and typical groups are those having 1 to 10 carbon atoms, particularly, the representative group is a group having 1 to 6 carbon atoms, and preferable examples thereof include an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3-trifluoropropyl group, and a cyanoethyl group, and an unsubstituted or substituted phenyl group such as a phenyl group, a chlorophenyl group, and a fluorophenyl group.

(h-2): dimethylpolysiloxane having one end of the molecular chain blocked with a trialkoxy group, represented by the following general formula (3)

[ solution 11]

(in the formula, R⁵Independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100. )

Furthermore, from R⁵Examples of the alkyl group include the same as R in the above general formula (2)⁴Alkyl groups shown are the same groups.

The surface-treating agent may be either one of the component (h-1) and the component (h-2), or a combination thereof. The amount of the component (h) is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the component (a). When the amount of the component (h) is less than 0.1 parts by mass, it may be difficult to fill the component (b) in the component (a), and when it exceeds 40 parts by mass, the adhesive strength of the cured product may be lowered.

[ other ingredients ]

In addition to the silicone composition of the present invention, a surface treatment agent for a thermally conductive filler, a pigment or dye for coloring, a flame retardancy-imparting agent, and other various additives for improving functions may be added within a range not impairing the object of the present invention.

[ Heat-conductive film-like cured product ]

The thermally conductive film-like cured product can be obtained, for example, by a production method including the steps of: the above-mentioned essential components and optional components are uniformly mixed to obtain a silicone composition, and the silicone composition is molded into a film on a substrate, preferably a surface-release-treated substrate, and cured.

Examples of the method of molding on the substrate include: a liquid material or the like is applied to the substrate using a bar coater, a blade coater, a comma coater, a spin coater, or the like, but the method is not limited to the above-described method.

The heating temperature condition for heating after molding may be a temperature at which the solvent used when the solvent is added volatilizes and the component (a) and the component (c) can react, and is preferably 60 to 150 ℃, more preferably 80 to 150 ℃ from the viewpoint of productivity and the like. If the temperature is less than 60 ℃, the curing reaction is slow, and the productivity is deteriorated, and if it exceeds 150 ℃, the film used as the substrate may be deformed. The curing time is usually 0.5 to 30 minutes, preferably 1 to 20 minutes.

The thickness of the heat-conductive film-like cured product is 20 to 1000 μm, and more preferably 30 to 500 μm. If the molding thickness is less than 20 μm, handling properties are poor and the sticky feeling may be reduced. On the other hand, if the molding thickness exceeds 1000 μm, the desired thermal conductivity may not be obtained any more. In addition, a solvent such as toluene or xylene may be added to adjust the viscosity during coating and molding.

As the substrate, a substrate obtained by subjecting paper or a polyethylene terephthalate (PET) film to surface release treatment for a silicone adhesive is preferable. The film thickness is preferably 15 to 100 μm. As a treatment method, a surface release treatment composition was applied to PET using a gravure coater or a lick coater. The surface release treatment component used for the surface release treatment is preferably a non-dimethyl silicone polymer, and more preferably a modified silicone having a fluorine substituent such as a perfluoroalkyl group or a perfluoropolyether group in the main chain. Specifically, the perfluoropolyether group can be represented by the following formulae (10) to (12).

[ solution 12]

Specific examples of the modified silicone having the fluorine substituent include X-70-201 and X-70-258 manufactured by shin-Etsu chemical industries, Ltd.

The cured thermally conductive film-like cured product can be bonded to the opposite surface of the substrate (film) by using a release treatment film similar to the substrate as a separator film, thereby facilitating handling such as transportation and cut-to-length. In this case, the peeling force between the base film and the separator film can be reduced or increased by changing the amount and type of the release agent to be treated with the base film and the material of the film. The thermally conductive cured product obtained in this way can be easily disposed even in a thin film and exhibits excellent thermal conductivity characteristics by peeling the separator film or the base material (film) and then attaching the separated film or the base material to the heat generating element or the heat radiating member, and then peeling the remaining film.

Furthermore, the thermal conductivity of the thermally conductive cured film is preferably 0.7W/mK or more, more preferably 1W/mK or more. The upper limit is not particularly limited, and may be 5W/mK or less. The method of measuring thermal conductivity is described in examples.

The shear bonding strength to aluminum at 150 ℃ is preferably 0.5MPa or more, and the upper limit is not particularly limited, and may be 15MPa or less, more preferably 1 to 5 MPa. The method for measuring the shear adhesion strength to aluminum at 150 ℃ is described in examples.

[ Heat-conductive Member ]

A heat-conductive member can be obtained which is obtained by molding the silicone composition in a film form on a base material, preferably a surface-release-treated base material, and curing the molded product, and which has the base material and a heat-conductive film-form cured product.