TW202031798A - Addition-curable silicone composition - Google Patents

Abstract

In the present invention, by blending specific quantities of an aliphatic unsaturated hydrocarbon group-containing organopolysiloxane, a thermally conductive filler, an organohydrogenpolysiloxane, a hydrolyzable organosilane compound which has a specific structure and contains a sulfur atom, a platinum group metal catalyst and, if necessary, a silicone resin having an aliphatic unsaturated hydrocarbon group, it is possible to obtain an addition-curable silicone composition that is superior to conventional silicone heat-dissipating greases in terms of exhibiting good adhesion to a surface on which a noble metal such as gold has been vapor deposited.

Description

Addition hardening type polysiloxane composition

The present invention relates to an addition hardening type polysiloxy composition. In detail, it relates to an addition-curing polysiloxane composition with high thermal conductivity and an addition-curing polysiloxane composition with good adhesion to the surface of precious metals such as gold.

Electronic components such as LSI or IC chips are widely known to have heat generation in use and the resulting performance degradation. As a solution to this, various heat dissipation technologies are used. As a general heat dissipation technology, a cooling member is arranged near the heat-generating part, and after the two are brought into close contact, heat is efficiently removed from the cooling member to perform heat dissipation.

At this time, when there is a gap between the heat-generating member and the cooling member, since there is air with poor thermal conductivity therebetween, the thermal conductivity is reduced, and the temperature of the heat-generating member is not sufficiently lowered. In order to prevent the presence of such air and increase the thermal conductivity, heat dissipation materials with good thermal conductivity and followability to the surface of the component are used, such as thermal paste or fins (Patent Documents 1-11: Japanese Patent No. 2938428, Japan Patent No. 2938429, Japanese Patent No. 3580366, Japanese Patent No. 3952184, Japanese Patent No. 4572243, Japanese Patent No. 4656340, Japanese Patent No. 4913874, Japanese Patent No. 4917380, Japanese Patent No. 493094, Japanese Patent No. 5283346, Japanese Patent No. 5233325).

For example, Patent Document 9 discloses a thermally conductive polysiloxane ointment composition containing an organopolysiloxane having a specific structure, an alkoxysilane having a specific substituent, and a thermally conductive filler, and it describes the composition Good thermal conductivity, good fluidity, and excellent workability. In addition, Patent Document 10 and Patent Document 11 disclose sheets with adhesiveness and thermal conductivity, and disclose an addition-hardening type silicone rubber composition that incorporates a thermally conductive filler and a non-aliphatic unsaturated hydrocarbon group. Thermally conductive composition made of silicone resin. Patent Document 10 and Patent Document 11 disclose that a thermally conductive cured product having moderate adhesiveness and good thermal conductivity can be provided in a thin film state.

Among the thermal pastes, there are those that impart adhesive performance to the lubricating paste for the purpose of firmly bonding the semiconductor chip and the heat sink. This is because if the semiconductor chip and the heat sink are not sufficiently bonded through the lubricating paste, the heat dissipation performance is not fully utilized, resulting in a significant decrease in performance. Therefore, it is important to firmly bond the semiconductor chip and the heat sink with the lubricating paste. On the other hand, in order to increase the thermal conductivity of the thermal paste, it is also necessary to fill a large amount of thermally conductive filler. When a large amount of thermally conductive filler is filled in the lotion, the amount of organic components is relatively reduced, so there is a problem that the adhesiveness of the resulting cured product is reduced. If the adherence decreases, the cured product cannot follow the deformation of the semiconductor wafer caused by the heat history of heating and cooling, and peeling occurs. In the worst case, the semiconductor wafer may be damaged. For example, Patent Document 12 (Japanese Patent No. 6149831) discloses a thermally conductive polysiloxane paste composition containing a specific structure of organohydrogen polysiloxane that has good adhesion to metallic silicon or nickel surfaces.

On the other hand, in recent years, for the purpose of improving the reliability of the semiconductor device, a semiconductor device in which precious metals such as gold are vapor-deposited on the surface of a semiconductor wafer or heat sink has been provided. It is known that the addition-hardening type polysiloxane composition has poor hardening on the surface on which precious metals such as gold are deposited. In this case, the adhesive strength of the substance is given a significant decrease in adhesive strength is a problem.

Patent Document 13 (Japanese Patent No. 5447337) discloses a thermally conductive polysilicon that can be adhered to the gold vapor deposition surface by using peroxide with a 10-hour half-life temperature of 80°C or more and less than 130°C as a hardener Oxygen composition, but the bonding strength is weak, is not a level that can bond the semiconductor chip and the heat sink firmly.

Patent Document 14 (Japanese Patent Application Laid-Open No. 2008-106185) discloses that by treating the surface of precious metals with a primer containing platinum compounds and solvents and not containing alkoxysilanes, it is possible to adhere to the surface of gold vapor deposition. The thermally conductive silicone composition. However, as in Patent Document 13, the bonding strength is weak, and it is not a level that can firmly bond the semiconductor wafer and the heat sink. In addition, the treatment with primer is complicated and uneconomical, so it is not good.

As mentioned above, the reliability of semiconductor devices has been emphasized in recent years. In order to achieve its strategy, there are cases in which precious metals such as gold are deposited on the surface of semiconductor chips or heat sinks. However, the conventional polysilicon heat sink It is a problem that sufficient adhesion cannot be exhibited on the surface of precious metals such as gold vapor deposited. It is a polysilicone thermal grease that is required to exhibit good adhesion on such a surface. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2938428 [Patent Document 2] Japanese Patent No. 2938429 [Patent Document 3] Japanese Patent No. 3580366 [Patent Document 4] Japanese Patent No. 3952184 [Patent Document 5] Japanese Patent No. 4572243 [Patent Document 6] Japanese Patent No. 4656340 [Patent Document 7] Japanese Patent No. 4913874 [Patent Document 8] Japanese Patent No. 4917380 [Patent Document 9] Japanese Patent No. 4933094 [Patent Document 10] Japanese Patent No. 5283346 [Patent Document 11] Japanese Patent No. 5233325 [Patent Document 12] Japanese Patent No. 6149831 [Patent Document 13] Japanese Patent No. 5447337 [Patent Document 14] JP 2008-106185 A

[The problem to be solved by the invention]

Therefore, the present invention is made in view of the above-mentioned facts, and its purpose is to provide an addition-hardening type polymer with good adhesion to the surface of precious metals such as gold vapor deposited compared to the conventional silicone heat sink. Silica composition. [Means to solve the problem]

The inventors of the present invention have conducted intensive studies in order to achieve the above object and found that by blending a specific amount of an aliphatic unsaturated hydrocarbon group-containing organopolysiloxane, a thermally conductive filler, an organohydrogenpolysiloxane, it has a specific Structure and hydrolyzable organosilane compounds containing sulfur atoms, platinum group metal catalysts, and polysiloxane resins with aliphatic unsaturated hydrocarbon groups as required can be obtained on the surface of precious metals such as gold vapor deposited The addition of a curable silicone composition with good adhesion properties completes the present invention.

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異；R² 係分別獨立地為非取代或取代之碳數1~20之烷基、非取代或取代之碳數6~10之芳基、碳數7~10之芳烷基、非取代或取代之碳數2~10之烯基，或非取代或取代之碳數1~20之烷氧基，R³ 為非取代或取代之碳數1~10之烷基，或非取代或取代之碳數6~10之芳基，n為1~3之整數，m為1~12之整數)； (F)鉑族金屬觸媒：有效量。 [2]. 如[1]之加成硬化型聚矽氧組成物，其進一步含有相對於(A)成分與(B)成分之合計100質量份而言為0.05~5質量份之(G)反應控制劑。 [3]. 如[1]或[2]之加成硬化型聚矽氧組成物，其進一步含有相對於(A)成分與(B)成分之合計100質量份而言為0.01~10質量份之(H)由過氧縮酮、氫過氧化物、二烷基過氧化物、二醯基過氧化物、過氧酯，及過氧二碳酸酯中選出的有機過氧化物。 [4]. 如[1]~[3]中任一項之加成硬化型聚矽氧組成物，其進一步含有相對於(A)成分與(B)成分之合計100質量份而言為0.1~30質量份之(I)下述通式(2)表示之水解性有機矽烷化合物；

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異；R⁴ 為由環氧基、丙烯醯基、甲基丙烯醯基、烷氧基矽烷基中選擇之基；X為可包含雜原子之碳數1~20之伸烷基；a為0~2之整數)。 [5]. 如[1]~[4]中任一項之加成硬化型聚矽氧組成物，其進一步含有相對於(A)成分與(B)成分之合計100質量份而言為1~200質量份之(J)下述通式(3)表示之水解性有機聚矽氧烷化合物；

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異；b為5~100之整數)。 [6]. 如[1]~[5]中任一項之加成硬化型聚矽氧組成物，其進一步含有相對於(A)成分與(B)成分之合計100質量份而言為1~50質量份之(K)下述通式(4)表示之水解性有機聚矽氧烷化合物；

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異；R⁵ 為碳數2~6之烯基；p、q為滿足1≦p≦50、1≦q≦99、5≦p+q≦100之數)。 [發明之效果]Therefore, the present invention provides the following addition-curable silicone composition. [1]. An addition-hardening polysiloxane composition, which is based on the following components: (A) There are at least two aliphatic unsaturated hydrocarbon groups in one molecule, and the dynamic viscosity at 25°C is 60~ Organopolysiloxane of 100,000 mm ² /s: 100 parts by mass; (B) Polysiloxane resin with at least one aliphatic unsaturated hydrocarbon group per molecule: 0 relative to 100 parts by mass of component (A) ~100 parts by mass; (C) At least one thermally conductive filler selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon: relative For the entire composition, the amount is 10-95% by mass; (D) Organohydrogen polysiloxanes having two or more hydrogen atoms bonded to silicon atoms in one molecule: relative to (A) and ( B) The total number of aliphatic unsaturated hydrocarbon groups in the component is such that the number of SiH groups is 0.5 to 5; (E) The hydrolyzable organosilane compound represented by the following general formula (1): relative to (A) component and (B) component total 100 parts by mass, 0.1-10 parts by mass;

(In the formula, R ¹ represents a monovalent hydrocarbon group with 1 to 10 carbons that may have a substituent, and each R ¹ may be the same or different; R ² is independently unsubstituted or substituted with 1 to 20 carbons. Alkyl group, unsubstituted or substituted aryl group with 6-10 carbons, aralkyl group with 7-10 carbons, unsubstituted or substituted alkenyl group with 2-10 carbons, or unsubstituted or substituted carbon number 1~20 alkoxy, R ^{3 is an} unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons, n is an integer of 1 to 3, and m is An integer from 1 to 12); (F) Platinum group metal catalyst: effective amount. [2]. The addition curable silicone composition as in [1], which further contains (G) 0.05-5 parts by mass relative to 100 parts by mass of the (A) component and (B) component in total Reaction control agent. [3]. The addition curable silicone composition as in [1] or [2], which further contains 0.01-10 parts by mass relative to 100 parts by mass of the (A) component and (B) component in total The (H) is an organic peroxide selected from peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate. [4]. The addition curable polysiloxane composition of any one of [1] to [3], which further contains 0.1 relative to 100 parts by mass of the (A) component and (B) component in total ~30 parts by mass of (I) the hydrolyzable organosilane compound represented by the following general formula (2);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; R ^{4 is} composed of epoxy, acryloyl and methacryloyl , The selected group in alkoxysilyl group; X is an alkylene group with 1-20 carbon atoms that may contain heteroatoms; a is an integer of 0-2). [5]. The addition curable silicone composition of any one of [1] to [4], which further contains 1 per 100 parts by mass of the (A) component and (B) component in total ~200 parts by mass of (J) the hydrolyzable organopolysiloxane compound represented by the following general formula (3);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; b is an integer from 5 to 100). [6]. The addition-curing silicone composition of any one of [1] to [5], which further contains 1 relative to the total of 100 parts by weight of (A) component and (B) component ~50 parts by mass (K) of the hydrolyzable organopolysiloxane compound represented by the following general formula (4);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; R ⁵ is an alkenyl group with a carbon number of 2 to 6; p and q are satisfied 1≦p≦50, 1≦q≦99, 5≦p+q≦100). [Effects of Invention]

The addition-hardening type polysiloxane composition of the present invention has good adhesion to the surface on which precious metals such as gold are deposited. That is, it can be applied to a semiconductor device in which precious metals such as gold are vapor-deposited on the surface of a semiconductor wafer or heat sink for the purpose of improving reliability.

The present invention will be described in detail below. (A) Component (A) Component is an aliphatic unsaturated hydrocarbon group having at least 2, preferably 2 to 100, more preferably 2 to 50 in one molecule, and has a dynamic viscosity of 60 to 100,000 at 25°C mm ² /s of organopolysiloxane.

The aliphatic unsaturated hydrocarbon group is preferably a monovalent hydrocarbon group having an aliphatic unsaturated bond having 2 to 8, more preferably a carbon number of 2 to 6, and still more preferably an alkenyl group. For example, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl can be cited. Especially preferred is vinyl. The aliphatic unsaturated hydrocarbon group can be bonded to either the silicon atom at the end of the molecular chain, the silicon atom in the middle of the molecular chain, or both. Furthermore, the organopolysiloxane of the component (A) preferably has an aliphatic unsaturated hydrocarbon group of 0.00001 to 0.01 mol/g, particularly 0.0001 to 0.01 mol/g, per molecule.

The organic group other than the aliphatic unsaturated hydrocarbon group bonded to the silicon atom of the aforementioned organopolysiloxane has a carbon number of 1 to 18, preferably a carbon number of 1 to 10, and more preferably a carbon number of 1 to 8. An unsubstituted or substituted monovalent hydrocarbon group with an aliphatic unsaturated bond. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, etc. Alkyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc., or part or all of the hydrogen atoms of these groups are Substitutions such as fluorine, bromine, chlorine, etc., such as halogen atoms and cyano groups, such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc. Particularly preferred is methyl.

The aforementioned organopolysiloxane has a dynamic viscosity at 25°C of 60 to 100,000 mm ² /s, preferably 100 to 30,000 mm ² /s. When the dynamic viscosity of less than 60mm ² / s, the physical properties of the composition of poly-silicon oxide decreases beyond 100,000mm ² / s, the composition of poly-silicon stretching becomes oxygen deficiency. In the present invention, the dynamic viscosity is a value measured at 25° C. with a Ubbelohde type Ostwald viscometer (the same below).

The molecular structure of the aforementioned organopolysiloxane is not particularly limited as long as it has the above-mentioned properties, and examples thereof include a linear structure, a branched structure, and a linear structure partially having a branched structure or a cyclic structure. In particular, it is preferable to have a linear structure in which the main chain contains diorganosiloxane units and the two ends of the molecular chain are blocked by triorganosiloxane groups. The organopolysiloxane having a linear structure may partially have a branched structure or a cyclic structure.

The organopolysiloxane can be used alone or in combination of two or more.

(B) Ingredient (B) Component is silicone resin. (B) The silicone resin of the component has at least one aliphatic unsaturated hydrocarbon group in one molecule. The component (B) may not be blended, but when the silicone resin of the component (B) is contained, the adhesive strength of the cured product obtained from the addition-curing silicone composition of the present invention can be improved.

In the present invention, the component (B) preferably contains SiO _4/2 units, R ⁶ ₂ R ⁷ SiO _1/2 units, and R ⁶ ₃ SiO _1/2 units (where R ⁶ systems are independent of each other. A polysiloxane resin with a monovalent hydrocarbon group with aliphatic unsaturated bond, R ⁷ is a monovalent aliphatic unsaturated hydrocarbon group).

In the aforementioned formula, R ⁶ is independently of each other and has no aliphatic unsaturated bond with carbon number 1-18, preferably carbon number 1-10, more preferably carbon number 1-8 unsubstituted or substituted monovalent Hydrocarbyl. For example, R ^{6 can} include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl Alkyl groups such as phenyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc., or hydrogen atoms of these groups Part or all of it is substituted by halogen atoms such as fluorine, bromine, chlorine, etc., cyano groups, etc., such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, etc. Among these, methyl is particularly preferred.

R ⁷ is a monovalent aliphatic unsaturated hydrocarbon group, preferably a monovalent hydrocarbon group having 2 to 8 carbon atoms having an aliphatic unsaturated bond, more preferably a monovalent hydrocarbon group having 2 to 6 carbon atoms, and more preferably an alkenyl group. Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl. Especially preferred is vinyl.

(B) component of the poly-silicone, having in the molecule at least one, preferably ^{1 × 10 -5 ~ 1 × 10} -2 mol / g, more preferably ^{1 × 10 -4 ~ 2 × 10} - ³ mol/g aliphatic unsaturated hydrocarbon group.

Further, the component (B), the molar ratio of SiO _4/2 unit (Q unit) to R ⁶ ₂ R ⁷ SiO _1/2 unit, and R ⁶ ₃ SiO _1/2 unit (M unit), is preferably (M unit)/(Q unit) satisfies the number of 0.1~3, more preferably (M unit)/(Q unit) satisfies the number of 0.3~2.5, especially preferably (M unit)/(Q unit) satisfies 0.5~ Number of 2. When the molar ratio of the M unit and the Q unit is within the above range, a moisturizer with good adhesion and strength can be provided. Furthermore, the silicone resin of the present invention can be included in the molecule to a degree that does not impair the properties of the addition curable silicone composition of the present invention (for example, 1-50 in the silicone resin of component (B)) Mole%) R ₂ SiO _2/2 unit (D unit) and RSiO _3/2 unit (T unit) (where R is R ⁶ or R ⁷ ).

The silicone resin used in the present invention is solid or viscous liquid at room temperature. The average molecular weight of the silicone resin is not particularly limited, and it is preferable that the dynamic viscosity when the silicone resin is dissolved in xylene to become a 50% by mass solution is 0.5-10 mm ² /s, preferably 1~ Molecular weight of 5mm ² /s. By making the dynamic viscosity of the silicone resin within the above-mentioned range, it is preferable to prevent the physical properties of the composition from decreasing.

The amount of silicone resin of component (B) is 0-100 parts by mass relative to 100 parts by mass of component (A). When there is blending, it is preferably 1-100 parts by mass, more preferably 3-50 parts by mass. Mass parts. (B) When the amount of the component is less than the above lower limit, the adhesion may be insufficient, and when it exceeds the above upper limit, the stretchability may be insufficient.

(C) Ingredients The component (C) is one or more thermally conductive fillers selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon. For example, aluminum, silver, copper, metallic silicon, bauxite, zinc oxide, magnesium oxide, aluminum oxide, silicon dioxide, cerium oxide, iron oxide, aluminum hydroxide, cerium hydroxide, aluminum nitride, boron nitride , Silicon carbide, diamond, graphite, carbon nanotube, graphene, etc. These can be used alone or in a suitable combination of two or more, and a combination of a large particle component and a small particle component is preferred.

When the average particle size of the large particle component is less than 0.1 μm, the viscosity of the obtained composition may become too high and the stretchability may be insufficient. When it is greater than 100 μm, the obtained composition may become uneven, so it is preferably 0.1~ The range of 100μm, more preferably the range of 10-50μm, and still more preferably the range of 10~45μm. In addition, when the average particle size of the small particle component is less than 0.01 μm, the viscosity of the obtained composition may become too high and the stretchability may be insufficient. When it is 10 μm or more, the obtained composition may become uneven, so it is 0.01 The range of μm or more and less than 10 μm, preferably 0.1 to 4 μm. The ratio of the large particle component to the small particle component is not particularly limited, and is preferably in the range of 9:1 to 1:9 (mass ratio). In addition, the shape of the large particle component and the small particle component is spherical, indeterminate, needle-like, etc., and is not particularly limited. In addition, the average particle diameter can be obtained, for example, as a volume-based average value (or median diameter) in the particle size distribution measurement by the laser diffraction method.

(C) The blending amount of the component is 10-95% by mass relative to the whole composition, preferably 20-90% by mass, more preferably 30-88% by mass, most preferably 50-85% by mass . When it is more than 95% by mass, the stretchability of the composition is insufficient, and when it is less than 10% by mass, the thermal conductivity is insufficient.

(D) Ingredients The component (D) is an organohydrogen polysiloxane having two or more, preferably 2 to 100, and more preferably 2 to 20 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. The organohydrogenpolysiloxane can be formed as long as the SiH group in the molecule undergoes an addition reaction in the presence of the aliphatic unsaturated hydrocarbon group of the above-mentioned components (A) and (B) and the platinum group metal catalyst The cross-linked structure is sufficient.

The molecular structure of the aforementioned organohydrogenpolysiloxane is not particularly limited as long as it has the above-mentioned properties, and examples thereof include linear structure, branched chain structure, cyclic structure, and some of which have branched or cyclic structures. Linear structure, etc. It is preferably a linear structure or a cyclic structure.

The organohydrogen polysiloxane has a dynamic viscosity at 25° C., preferably 1 to 1,000 mm ² /s, more preferably 10 to 100 mm ² /s. If the aforementioned dynamic viscosity is 1 mm ² /s or more, there is no possibility that the physical properties of the silicone composition will decrease, and if it is 1,000 mm ² /s or less, there is no possibility that the stretchability of the silicone composition will become insufficient.

Examples of the organic group bonded to the silicon atom of the aforementioned organohydrogenpolysiloxane include unsubstituted or substituted monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups. In particular, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, dodecyl, etc.; aryl groups such as phenyl; 2-phenylethyl, 2-phenylpropyl, etc. Alkyl group; part or all of these hydrogen atoms are halogen atoms such as fluorine, bromine, chlorine, cyano groups, and organic groups containing epoxy rings (alkyl groups substituted with glycidyl or glycidoxy) Substitutes such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, cyanoethyl, 2-glycidoxyethyl, 3-glycidoxypropyl, and 4- Glycidoxybutyl, etc. Among these, methyl and 3-glycidoxypropyl are particularly preferred.

This organohydrogenpolysiloxane may be used alone or in combination of two or more kinds.

The blending amount of the organohydrogen polysiloxane of component (D) is relative to the total number of aliphatic unsaturated hydrocarbon groups in component (A) and (B), and the amount of SiH group in component (D) The number becomes an amount of 0.5 to 5, preferably an amount of 0.7 to 4.5, and more preferably an amount of 1 to 4. (D) When the amount of the component does not reach the above lower limit, the addition reaction does not proceed sufficiently and the crosslinking is insufficient. In addition, when the upper limit is exceeded, the crosslinked structure may become non-uniform, or the storage properties of the composition may be significantly deteriorated.

Furthermore, in the present invention, it is more desirable that the composition (especially the (A) component, (B) component, (E) component, and the following optional components (I) component, (J) component and (K) component The total number of aliphatic unsaturated hydrocarbon groups in the middle) is that the number of SiH groups in the composition (especially in the component (D)) is 0.5 to 5, especially 1 to 4.

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異。R² 係分別獨立地為非取代或取代之碳數1~20之烷基、非取代或取代之碳數6~10之芳基、碳數7~10之芳烷基、非取代或取代之碳數2~10之烯基，或非取代或取代之碳數1~20之烷氧基，R³ 為非取代或取代之碳數1~10之烷基，或非取代或取代之碳數6~10之芳基，n為1~3之整數，m為1~12之整數)。(E) Component (E) Component is a hydrolyzable organosilane compound having both a hydrolyzable silyl group and S-Si bond in one molecule represented by the following general formula (1). It can be used alone or in combination of two or more types. It acts as an adhesive agent for improving the adhesion of the silicone composition obtained by the present invention to the surface on which noble metals such as gold are deposited.

(In the formula, R ¹ represents a monovalent hydrocarbon group with 1 to 10 carbons that may have a substituent, and each R ¹ may be the same or different. R ² is independently unsubstituted or substituted with 1 to 20 carbons. Alkyl group, unsubstituted or substituted aryl group with 6-10 carbons, aralkyl group with 7-10 carbons, unsubstituted or substituted alkenyl group with 2-10 carbons, or unsubstituted or substituted carbon number 1~20 alkoxy, R ^{3 is an} unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons, n is an integer of 1 to 3, and m is An integer from 1 to 12).

In the above formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may have a substituent, preferably a monovalent saturated aliphatic hydrocarbon group that may have a substituent, and a monovalent unsaturated hydrocarbon group that may have a substituent Aliphatic hydrocarbon group, optionally substituted monovalent aromatic hydrocarbon group (including aromatic heterocyclic ring), more preferably optionally substituted monovalent saturated aliphatic hydrocarbon group, optionally substituted monovalent aromatic hydrocarbon group; particularly preferred It is a monovalent saturated aliphatic hydrocarbon group which may have a substituent. A monovalent saturated aliphatic hydrocarbon group which may have a substituent, specifically linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.; isopropyl, isopropyl Branched chain alkyl groups such as butyl, tert-butyl, isopentyl, and neopentyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; chloromethyl, 3-chloropropyl, 3, 3,3-trifluoropropyl, bromopropyl and other halogen-substituted alkyl groups have 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Monovalent unsaturated aliphatic hydrocarbon groups that may have substituents, specifically, alkenyl groups such as vinyl, 1-methylvinyl, and 2-propenyl; alkynyl groups such as ethynyl and 2-propynyl, etc. The carbon number is 2-10, preferably the carbon number is 2-8, more preferably the carbon number is 2-6. Monovalent aromatic hydrocarbon groups that may have substituents, specifically, aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and 2-phenylethyl; α,α,α-benzotrifluoride The halogen-substituted aryl groups such as chlorobenzyl and chlorobenzyl have 6-10 carbons, preferably 6-8 carbons, more preferably 6 carbons. R ¹ in the above formula (1) is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, etc., and among these, a methyl group and an ethyl group are more preferable.

R ² is independently an unsubstituted or substituted alkyl group with 1 to 20 carbons, an unsubstituted or substituted aryl group with 6 to 10 carbons, an aralkyl group with 7 to 10 carbons, unsubstituted or substituted Alkenyl with 2 to 10 carbons, or unsubstituted or substituted alkoxy with 1 to 20 carbons. The alkyl group of R ^{2 can} include methyl, ethyl, tert-butyl, octyl, decyl, ten Examples of dialkyl groups include phenyl, tolyl, and xylyl groups for aryl groups, benzyl groups for aralkyl groups, vinyl groups, propenyl groups, and pentenyl groups for alkenyl groups, and methyl groups for alkoxy groups. Oxy, ethoxy, propoxy, butoxy, octoxy, dodecyloxy, etc., and the substituents in substituted alkyl, substituted aryl, substituted alkenyl, and substituted alkoxy can be Enumerate halogen atoms. As R ² , among these, methyl, ethyl, methoxy, and ethoxy are particularly preferred, and at least one of them is more preferably methoxy or ethoxy.

R ^{3 is an} unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons. The alkyl group of R ³ includes methyl, ethyl, propyl, and butyl. For the aryl group, phenyl etc. are mentioned, and the substituent in the substituted alkyl group and substituted aryl group may be a halogen atom. As R ³ , among these, methyl is particularly preferred.

Moreover, n is an integer of 1 to 3, and 3 is preferable. m is an integer of 1-12, preferably an integer of 1-8.

(式中，R¹ 、n、R² 係與上述相同，R⁸ 為非取代或取代之碳數1~20之烷基、非取代或取代之碳數6~10之芳基、碳數7~10之芳烷基，或非取代或取代之碳數2~10之烯基，Me為甲基)。The hydrolyzable organosilane compound represented by formula (1) is preferably represented by the following general formula (5).

(In the formula, R ¹ , n, R ² are the same as above, R ^{8 is an} unsubstituted or substituted alkyl group with 1 to 20 carbons, an unsubstituted or substituted aryl group with 6 to 10 carbons, and a carbon number of 7 ~10 aralkyl group, or unsubstituted or substituted alkenyl group with 2 to 10 carbon atoms, Me is methyl).

R ⁸ in the above formula (5) is an unsubstituted or substituted alkyl group with 1 to 20 carbons, an unsubstituted or substituted aryl group with 6 to 10 carbons, an aralkyl group with 7 to 10 carbons, or non- The substituted or substituted alkenyl group with 2 to 10 carbon atoms, the alkyl group of R ⁸ may include methyl, ethyl, tert-butyl, octyl, decyl, dodecyl, etc., and the aryl group may include phenyl, Examples of tolyl, xylyl, etc., aralkyl, benzyl, etc., alkenyl, vinyl, propenyl, pentenyl, etc., and substituents in substituted alkyl, substituted aryl, and substituted alkenyl, Examples include halogen atoms. As R ⁸ , among these, methyl and ethyl are particularly preferred.

(式中，R¹ 、n、Me係與上述相同，Et為乙基)。(E) The hydrolyzable organosilane compound of the component is more preferably represented by the following general formulas (6) to (11), and one or two or more of these can be used.

(In the formula, R ¹ , n, and Me are the same as above, and Et is an ethyl group).

The blending amount of (E) component is 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component. When the blending amount is less than 0.1 parts by mass, the effect of improving the adhesion of the silicone composition to the surface of precious metals vapor deposited with gold or the like is insufficient. When the amount exceeds 10 parts by mass, it may hinder the silicone composition. The addition reaction reduces the possibility of adhesion to the surface on which precious metals such as gold are deposited.

(F) Ingredients The component (F) is a platinum group metal catalyst, which functions for the purpose of promoting the addition reaction of the above-mentioned components. As the platinum group metal catalyst, conventionally known ones used in addition reactions can be used. For example, platinum-based, palladium-based, and rhodium-based catalysts can be cited, among which platinum or platinum compounds that are relatively easily available are preferred. For example, platinum simple substance, platinum black, chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, platinum coordination compound, etc. are mentioned. The platinum group metal catalyst may be used alone or in combination of two or more.

The blending amount of the component (F) may be an effective amount as a catalyst, that is, an effective amount necessary to harden the addition-curing polysiloxane composition of the present invention in order to promote the addition reaction. Preferably, the total mass of the (A) component and (B) component is 0.1 to 500 ppm, and more preferably 1 to 200 ppm based on the mass basis of platinum group metal atoms. When the amount of catalyst is less than the above lower limit, the effect as a catalyst may not be obtained. Moreover, even if it exceeds the above upper limit, the catalytic effect does not increase, which is uneconomical and therefore not preferable.

In addition to the above-mentioned components, the addition-curable silicone composition of the present invention may further add the following optional components as needed.

(G) Ingredients The component (G) is a reaction control agent that inhibits the hydrosilation reaction from proceeding at room temperature, and it can be added for the purpose of prolonging the storage life and usable time. As the reaction control agent, conventionally known reaction control agents used in addition-curable silicone compositions can be used. Among them, for example, acetylene compounds such as acetylene alcohols (for example, ethynylmethyldecylmethanol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol) and the like can be cited; Various nitrogen compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; organophosphorus compounds such as triphenylphosphine; oxime compounds, organochlorine compounds, etc.

The blending amount at the time of blending the (G) component is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 1 part by mass relative to 100 parts by mass of the total of (A) and (B) components. When the amount of the reaction control agent is less than 0.05 parts by mass, there is a risk that the desired and sufficient shelf life and usable time may not be obtained, and when it is more than 5 parts by mass, the curability of the silicone composition may decrease. Yu. In addition, in order to improve the dispersibility to the polysiloxane composition, the reaction control agent may be diluted with organic (poly)siloxane or toluene and used.

(H) Ingredient (H) Component is selected from peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate, which will decompose under specific conditions. The organic peroxide that generates free radicals can be used alone or in a suitable combination of two or more. It is used as the introduction of a silylene structure into the siloxane crosslinking structure of the polysiloxane composition obtained in the present invention The reaction initiator to function.

Specifically, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-(4,4-bis-(tert-butylperoxy)cyclohexyl)propane and the like are suitably used Peroxyketal; hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide; dicumyl peroxide, tert-butyl cumyl peroxide , 2,5-Dimethyl-2,5-bis(tert-butylperoxy) hexane and other dialkyl peroxides; Dibenzyl peroxide, disuccinic acid peroxide, etc. Diacyl peroxide; peroxy ester such as tert-butyl peroxy acetate and tert-butyl peroxy benzoate; peroxy dicarbonate such as diisopropyl peroxydicarbonate. In particular, it is preferable to use peroxyketals, hydroperoxides, dialkyl peroxides, and peroxyesters, which have a relatively high decomposition temperature, from the viewpoint of handling properties and storage properties.

In particular, as the decomposition temperature for obtaining a half-life of 1 hour, it is preferably in the range of 50 to 200°C, more preferably in the range of 80 to 170°C. When the decomposition temperature used to obtain the half-life of 1 hour is less than 50°C, it may cause explosive reaction, so it is difficult to handle. If it exceeds 200°C, the reactivity is low, so there is a silanyl structure to the structure of a polysiloxane composition. Possibility of reduced introduction efficiency in In addition, these organic peroxides may be diluted with any organic solvent, hydrocarbon, liquid paraffin, or inactive solid.

The blending amount at the time of blending the component (H) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total of the (A) component and (B) component. When the blending amount is less than 0.01 parts by mass, the introduction efficiency of the silylene structure into the structure of the polysiloxane composition is reduced, and when the amount exceeds 10 parts by mass, the preservation of the polysiloxane composition may be reduced. .

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異。R⁴ 為由環氧基、丙烯醯基、甲基丙烯醯基、烷氧基矽烷基中選擇之基。X為可包含雜原子之碳數1~20之伸烷基。a為0~2之整數)。(I) Component The component (I) represented by the following general formula (2) is a hydrolyzable organosilane compound, which can be used alone or in a suitable combination of two or more. It is used to improve the polysiloxane obtained in the present invention. It acts as an adhesive adjuvant for the composition.

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different. R ^{4 is} composed of epoxy, acryl, and methacryl , A selected group among alkoxysilyl groups. X is an alkylene group with 1-20 carbon atoms that may contain heteroatoms. a is an integer of 0-2).

The R ¹ in the above formula (2) is the same as the foregoing, among which methyl, ethyl, 3,3,3-trifluoropropyl, and phenyl are particularly preferred; more preferably, methyl, ethyl, and phenyl are ; Especially preferred is methyl.

R ^{4 is a} group selected from epoxy group, acryloyl group, methacryloyl group, and alkoxysilyl group. For the purpose of improving the adhesion to the metal substrate such as semiconductor chips or heat sinks in semiconductor devices, epoxy groups and alkoxysilyl groups are preferably selected. Here, the alkoxysilyl group includes trimethoxy, dimethoxymethyl, methoxydimethylsilyl, triethoxy, diethoxymethyl, and ethoxydimethylsilyl. Among them, trimethoxy and triethoxy are particularly preferred.

(x為1~20之整數)。X is an alkylene group with 1 to 20 carbon atoms that may contain a hetero atom, and it is a spacer that connects R ⁴ to the silicon atom. The structure of X is linear, branched, etc., and is not particularly limited, but is preferably linear. Specific examples of X include those shown below.

(x is an integer from 1 to 20).

a is an integer of 0-2, which specifies the number of alkoxy groups of the alkoxysilyl group of the hydrolyzable organosilane compound of component (I). If the number of alkoxysilyl groups in the component (I) is large, the component (I) is easily immobilized on the surface of the thermally conductive filler of the component (C), so a is preferably 0 or 1, and more preferably 0.

The blending amount at the time of blending the component (I) is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total of the (A) component and (B) component. When the blending amount is less than 0.1 parts by mass, the amount of coating on the surface of the thermally conductive filler is reduced, so that the adhesiveness may not be fully exhibited. If it exceeds 30 parts by mass, the strength of the cured product of the silicone composition may decrease, and the adhesiveness may not be fully exhibited, which is not good.

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異。b為5~100之整數)。(J) Component In the addition curable silicone composition of the present invention, a hydrolyzable organopolysiloxane compound (J) represented by the following general formula (3) can be further blended. The hydrolyzable organopolysiloxane compound of component (J) is used for the purpose of treating the surface of the thermally conductive filler, and it is responsible for the role of assisting the filling of the filler.

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different. b is an integer of 5 to 100).

R ¹ in the above formula (3) is the same as described above, and is particularly preferably a methyl group. b is an integer of 5-100, preferably an integer of 10-60. When the value of b is less than 5, oil leakage from the silicone composition may become serious, and reliability may deteriorate. In addition, when the value of b exceeds 100, the wettability with the filler may become insufficient.

The blending amount when the component (J) is blended is preferably 1 to 200 parts by mass, particularly preferably 5 to 30 parts by mass relative to 100 parts by mass of the total of the (A) component and (B) component. (J) When the amount of the component is less than 1 part by mass, sufficient wettability may not be exhibited. In addition, when the amount of the component (J) exceeds 200 parts by mass, oil bleeding from the composition may become intense.

(式中，R¹ 表示可具有取代基之碳數1~10之1價烴基，各自之R¹ 可相同亦可相異。R⁵ 為碳數2~6之烯基。p、q為滿足1≦p≦50、1≦q≦99、5≦p+q≦100之數)。(K) Component In the addition curable silicone composition of the present invention, a hydrolyzable organopolysiloxane compound (K) represented by the following general formula (4) can be further blended. The hydrolyzable organopolysiloxane compound of component (K) has the reinforcing effect of treating the surface of the thermally conductive filler and increasing the strength of the polysiloxane composition.

(In the formula, R ¹ represents a monovalent hydrocarbon group with 1 to 10 carbons that may have a substituent, and each R ¹ may be the same or different. R ⁵ is an alkenyl with 2 to 6 carbons. p and q are satisfied 1≦p≦50, 1≦q≦99, 5≦p+q≦100).

R ¹ in the above formula (4) is the same as described above, and is particularly preferably a methyl group. R ⁵ is an alkenyl group having 2 to 6 carbon atoms. Specifically, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, etc. are mentioned, and ethylene is particularly preferred. base.

p is 1~50, preferably 1~10, q is 1~99, preferably 4~50. When p is too small, it may not provide sufficient reinforcing effect to the silicone composition. When p is too large, the crosslinking may become uneven. When q is too small, oil leakage may become serious. When q is too large, thermal conductivity may occur. When the filler surface treatment becomes insufficient. In addition, p+q is 5≦p+q≦100, preferably 5≦p+q≦60. When p+q is less than 5, oil leakage of the composition may become serious and reliability may deteriorate. In addition, when p+q is greater than 100, the wettability with the filler may become insufficient.

The blending amount when blending the component (K) is 1 to 50 parts by mass, preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the total of the (A) component and the (B) component. (K) When the amount of the component is less than the above lower limit, sufficient wettability or reinforcing effect may not be exhibited. In addition, when the amount of the component (K) exceeds the above upper limit, oil bleeding from the composition may become intense.

Other ingredients The addition-curing polysiloxane composition of the present invention can also contain non-reactive organic (poly)siloxanes such as methyl polysiloxane for the purpose of adjusting the strength or viscosity of the composition. Furthermore, it is also possible to contain conventionally known antioxidants such as 2,6-di-tert-butyl-4-methylphenol for the purpose of preventing deterioration of the silicone composition as needed. Further, dyes, pigments, flame retardants, sedimentation inhibitors, or thixotropy enhancers can be blended as needed.

Steps of making polysiloxane composition The manufacturing method of the polysiloxane composition of the present invention is described. The manufacturing method of the polysiloxane composition of the present invention is not particularly limited, and it has the ability to produce a polysiloxane composition containing the above-mentioned (A) ~ (F) components and further containing (G) ~ (K) components as required A step of.

Examples include the above-mentioned (A) ~ (F) components, and as needed (G) ~ (K) components, such as Trimix, Twinmix, Planetary Mixer (all registered trademarks of Inoue Manufacturing Co., Ltd.), Ultra Mixer (registered trademark of Mizuho Industrial Co., Ltd.), HIVIS DISPER MIX (registered trademark of Special Machinery Industry Co., Ltd. mixer) and other mixing methods.

In addition, the addition curable silicone composition of the present invention may be mixed while heating. The heating conditions are not particularly limited. The temperature is usually 25~220℃, preferably 40~200℃, particularly preferably 50~200℃, and the time is usually 3 minutes~24 hours, preferably 5 minutes~12 hours. It is preferably 10 minutes to 6 hours. It can also be degassed during heating. In the present invention, from the viewpoint that the silicone composition exhibits good adhesion, it is preferable to heat and mix the components (A) to (C) at 50 to 200°C before mixing the components (D) to (F) . Furthermore, when blending the (G)~(K) components of any component, it is preferable to heat and mix the (A)~(C) and (I)~(K) components in advance at 50~200℃, and then mix ( D)~(H) components.

The viscosity of the addition-curing polysiloxane composition of the present invention measured at 25°C is preferably 1 to 1,000 Pa･s, more preferably 20 to 700 Pa･s, and still more preferably 40 to 600 Pa･s. If the viscosity is less than 1Pa･s, it may be difficult to maintain the shape and workability may deteriorate. In addition, when the viscosity exceeds 1,000 Pa･s, it may be difficult to discharge or apply, and workability may deteriorate. The aforementioned viscosity can be obtained by adjusting the blending amounts of the aforementioned components. In addition, the addition-curing silicone composition of the present invention is thermally conductive, and usually has a thermal conductivity of 0.5 to 10 W/m･K. Furthermore, in the present invention, the viscosity is a value measured at 25° C. by a rotary viscometer, and the thermal conductivity is a value measured by a hot disk method.

The addition-hardening type polysiloxane composition of the present invention can be suitably used as a component that exists between electronic parts such as LSI or other heating components and cooling components to transfer heat from the heating components to the cooling components to dissipate heat. The composition can be used in the same way as the conventional polysilicone thermal paste. For example, the addition-curing silicone composition of the present invention can be cured by heat from heating components such as electronic parts, or it can be positively applied after coating the addition-curing silicone composition of the present invention. It is hardened by heating. The addition-hardening type polysiloxane composition of the present invention has particularly good adhesion to the surface on which precious metals such as gold are deposited. Therefore, for the purpose of improving reliability, it is particularly suitable for use as a heat dissipating paste used in a semiconductor device in which precious metals such as gold are vapor-deposited on the surface of a semiconductor chip or heat dissipating material. Thereby, it is possible to provide a semiconductor device in which there is a cured product of the addition-curing polysilicon oxide composition of the present invention between the heating member and the cooling member.

There are no special restrictions on the curing conditions when the addition-curing silicone composition of the present invention is heated and cured. It is usually 80~200°C, preferably 100~180°C, for 30 minutes to 4 hours, preferably It is 30 minutes to 2 hours. [Example]

Hereinafter, examples and comparative examples are shown to illustrate the present invention in more detail, but the present invention is not limited by the following examples. Furthermore, the dynamic viscosity means the value at 25°C obtained by the Uberlot Oswath Viscometer. First, the following components of the addition curable silicone composition of the present invention are prepared.

(A) Component A-1: Dimethylpolysiloxane with both ends blocked by dimethylvinylsilyl groups and a dynamic viscosity of 600mm ² /s at 25°C: SiVi group content 0.00014 mol/g

(B) Component B-1: Polysiloxane resin expressed by the following average composition formula: when it becomes a 50% by mass solution in xylene solvent, the dynamic viscosity is 3.0 mm ² /s, and the amount of SiVi group is 0.0004 mol/g

(C) Ingredients C-1: Aluminum powder obtained by pre-mixing aluminum powder with an average particle size of 20.0μm and an aluminum powder with an average particle size of 2.0μm at a mass ratio of 60:40 C-2: Zinc oxide powder with an average particle size of 1.0μm

D-2：下述式(13)表示之聚矽氧烷 (於25℃之動黏度=25mm² /s)

D-3：下述式(14)表示之聚矽氧烷 (於25℃之動黏度=11mm² /s)

(D) Component D-1: Methyl hydrogen dimethyl polysiloxane represented by the following formula (12) (Kinetic viscosity at 25°C = 12mm ² /s)

D-2: Polysiloxane represented by the following formula (13) (Kinetic viscosity at 25°C = 25mm ² /s)

D-3: Polysiloxane represented by the following formula (14) (Kinetic viscosity at 25°C = 11mm ² /s)

(式中，Me為甲基)。 E-2：下述式(16)表示之水解性有機矽烷化合物

(式中，Me為甲基、Et為乙基)。 E-3：下述式(17)表示之水解性有機矽烷化合物

(式中，Me為甲基)。(E) Component E-1: Hydrolyzable organosilane compound represented by the following formula (15)

(In the formula, Me is a methyl group). E-2: Hydrolyzable organosilane compound represented by the following formula (16)

(In the formula, Me is a methyl group and Et is an ethyl group). E-3: Hydrolyzable organosilane compound represented by the following formula (17)

(In the formula, Me is a methyl group).

(F) Ingredients F-1: A solution obtained by dissolving platinum-divinyltetramethyldisiloxane complex in the same dimethylpolysiloxane as A-1 above (platinum atom content: 1% by mass)

(G) Component G-1: 1-ethynyl-1-cyclohexanol represented by the following formula (18)

H-2：下述式(20)表示之1,1-二(tert-丁基過氧基)環己烷(用以得到1小時半衰期之分解溫度=111℃)

(H) Component H-1: 2,5-Dimethyl-2,5-bis(tert-butylperoxy)hexane represented by the following formula (19) (to obtain the decomposition temperature with a half-life of 1 hour =138℃)

H-2: 1,1-bis(tert-butylperoxy)cyclohexane represented by the following formula (20) (decomposition temperature to obtain a half-life of 1 hour = 111°C)

I-2：下述式(22)表示之8-環氧丙氧基辛基三甲氧基矽烷

(I) Component I-1: 3-glycidoxypropyltrimethoxysilane represented by the following formula (21)

I-2: 8-glycidoxy octyl trimethoxysilane represented by the following formula (22)

(J) Component J-1: Dimethylpolysiloxane represented by the following formula (23) with one end capped with trimethoxysilyl group

(K) Component K-1: Methyl vinyl polysiloxane with both ends blocked by trimethoxysilyl groups represented by the following formula (24)

[Examples 1 to 11, Comparative Examples 1 to 7] Preparation of polysiloxane composition The above-mentioned components (A) to (K) were blended with the blending amounts shown in the following Tables 1 to 3 by the method shown below to prepare a silicone composition. Furthermore, the mass of component (F) in the table is a solution obtained by dissolving platinum-divinyltetramethyldisiloxane complex in dimethylpolysiloxane (platinum atom content: 1% by mass ) Of the quality. In addition, SiH/SiVi is the ratio of the total number of SiH groups in the component (D) to the total number of alkenyl groups in the component (A), component (B), and component (K).

Add the ingredients (A), (B), (C), (J) and (K) to a 5 liter Planetary Mixer (manufactured by Inoue Manufacturing Co., Ltd.), and mix at 170°C for 1 hour. After cooling to 40°C or lower, component (I) was added, and mixed at 70°C for 1 hour. After cooling to 40°C or lower, the components (G), (F), (D), (H), and (E) are added, and mixed until uniform, to prepare a silicone composition.

For each silicone composition obtained by the above method, the viscosity, thermal conductivity, and adhesive strength were measured according to the following methods. The results are shown in Tables 1 to 3.

[Viscosity] A Malcom viscometer (model PC-1T) was used to determine the absolute viscosity of each silicone composition at 25°C (rotor A, 10 rpm, shear speed 6 [1/s]).

[Thermal conductivity] Each silicone composition was coated with plastic wrap, and the thermal conductivity was measured with TPS-2500S manufactured by Kyoto Electronics Co., Ltd.

[Next Strength] The polysiloxane composition is sandwiched between a 10mm×10mm silicon wafer and a 20mm×20mm silicon wafer deposited with gold (gold layer thickness=200μm), and pressurized by a 1.8kgf clamp, and Heat and harden at 150°C for 60 minutes. After that, the shear bonding strength was measured using Dage series-4000PXY (manufactured by Dage Deutchland GmbH).

From the results in Tables 1 to 3, it can be seen that the polysiloxy compositions of Examples 1 to 11 that meet the requirements of the present invention have high adhesion strength to the gold vapor-deposited surface. That is, it can be judged that the adhesiveness is excellent. On the other hand, the silicone compositions of Comparative Examples 1 to 7 had low adhesion strength to the gold vapor-deposited surface, or the adhesion strength could not be measured. That is, it can be judged that the adhesion is poor. Therefore, the addition-hardening type polysiloxane composition of the present invention has good adhesion to the surface on which precious metals such as gold are deposited. Due to such characteristics, the addition-curing polysiloxane composition of the present invention can be used for the purpose of improving reliability, and is particularly suitable for use as a semiconductor in which precious metals such as gold are deposited on the surface of semiconductor wafers or heat sinks. Thermal paste used by the device.

In addition, this invention is not limited to the said embodiment. The above-mentioned embodiments are just examples, and those having substantially the same constitution as the technical ideas described in the scope of the patent application of the present invention and exerting the same functions and effects are included in the technical scope of the present invention.

Claims (6)

An addition-hardening polysiloxane composition, which has the following components as essential components: (A) There are at least two aliphatic unsaturated hydrocarbon groups in one molecule, and the dynamic viscosity at 25°C is 60~100,000mm ² / Organopolysiloxane of s: 100 parts by mass; (B) Polysiloxane resin with at least one aliphatic unsaturated hydrocarbon group in 1 molecule: 0-100 parts by mass relative to 100 parts by mass of component (A) (C) At least one thermally conductive filler selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon: relative to the entire composition In terms of the amount of 10~95% by mass; (D) Organohydrogen polysiloxane having two or more hydrogen atoms bonded to silicon atoms in a molecule: relative to the components (A) and (B) The total number of aliphatic unsaturated hydrocarbon groups is to make the number of SiH groups 0.5-5; (E) Hydrolyzable organosilane compound represented by the following general formula (1): relative to component (A) 0.1~10 parts by mass for the total 100 parts by mass of component (B);

(In the formula, R ¹ represents a monovalent hydrocarbon group with 1 to 10 carbons that may have a substituent, and each R ¹ may be the same or different; R ² is independently unsubstituted or substituted with 1 to 20 carbons. Alkyl group, unsubstituted or substituted aryl group with 6-10 carbons, aralkyl group with 7-10 carbons, unsubstituted or substituted alkenyl group with 2-10 carbons, or unsubstituted or substituted carbon number 1~20 alkoxy, R ^{3 is an} unsubstituted or substituted alkyl group with 1 to 10 carbons, or an unsubstituted or substituted aryl group with 6 to 10 carbons, n is an integer of 1 to 3, and m is An integer from 1 to 12); (F) Platinum group metal catalyst: effective amount. The addition-curing polysiloxane composition of claim 1, which further contains (G) reaction control agent in an amount of 0.05 to 5 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component. For example, the addition-curing silicone composition of claim 1 or 2, which further contains 0.01 to 10 parts by mass of (H) by weight with respect to 100 parts by mass of the total of (A) and (B). An organic peroxide selected from oxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate. Such as the addition-curing silicone composition of claim 1 or 2, which further contains 0.1-30 parts by mass of (I) the following with respect to 100 parts by mass of the total of (A) component and (B) component Hydrolyzable organosilane compound represented by general formula (2);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; R ^{4 is} composed of epoxy, acryloyl and methacryloyl , The selected group in alkoxysilyl group; X is an alkylene group with 1-20 carbon atoms that may contain heteroatoms; a is an integer of 0-2). Such as the addition-curing polysiloxane composition of claim 1 or 2, which further contains 1 to 200 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component (J) Hydrolyzable organopolysiloxane compound represented by general formula (3);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; b is an integer from 5 to 100). Such as the addition-curing silicone composition of claim 1 or 2, which further contains 1-50 parts by mass relative to 100 parts by mass of the (A) component and (B) component in total (K) as follows Hydrolyzable organopolysiloxane compound represented by general formula (4);

(In the formula, R ¹ represents a monovalent hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, and each R ¹ may be the same or different; R ⁵ is an alkenyl group with a carbon number of 2 to 6; p and q are satisfied 1≦p≦50, 1≦q≦99, 5≦p+q≦100).