TW202400725A - Thermally conductive silicone composition, semiconductor device and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide: a thermally conductive silicone composition which has good heat dissipation performance; and a semiconductor device which uses this composition, and the like. The present invention provides a thermally conductive silicone composition which contains the following components (A), (B), (C), (D) and (E). (A) an organopolysiloxane which has at least two alkenyl groups that are each bonded to a silicon atom in each molecule, while having a kinematic viscosity of 10 to 100,000 mm2/s at 25 DEG C (B) a silver powder in an amount of 500 to 3,000 parts by mass relative to 100 parts by mass of the component (A) (C) a fatty acid in an amount of 0.01 to 10.0 parts by mass relative to 100 parts by mass of the component (B) (D) a platinum-based catalyst in a catalytic amount (E) an organohydrogen polysiloxane which has at least two hydrogen atoms that are each bonded to a silicon atom in each molecule in an addition amount at which (number of Si-H groups in component (E))/(number of alkenyl groups in component (A)) is 0.8 to 6.0.

Description

Thermal conductive silicone composition, semiconductor device and manufacturing method thereof

The present invention relates to a silicone composition excellent in thermal conductivity, a semiconductor device, and a manufacturing method thereof.

Since most electronic components generate heat during use, in order to properly perform the functions of the electronic components, it is necessary to remove heat from the electronic components. In particular, integrated circuit components used in CPUs and other components of personal computers generate more heat as the operating frequency increases, so thermal countermeasures become an important issue.

As a means of removing the heat, various methods have been proposed. Especially for electronic components that generate a large amount of heat, a method of dissipating heat by interposing a thermally conductive grease or a thermally conductive material such as a thermally conductive sheet between the electronic component and a member such as a heat sink has been proposed.

Japanese Patent Application Laid-Open No. 2-153995 (Patent Document 1) discloses a silicone grease in which spherical hexagonal aluminum nitride powder in a certain particle size range is blended with a specific organopolysiloxane. Composition; Japanese Patent Application Laid-Open No. 3-14873 (Patent Document 2) discloses a thermally conductive silicone grease that combines fine-grained aluminum nitride powder and coarse-grained aluminum nitride powder; in Japanese Patent Application Laid-Open No. 10-110179 (Patent Document 3) discloses a thermally conductive silicone grease that combines aluminum nitride powder and zinc oxide powder; Japanese Patent Application Laid-Open No. 2000-63872 (Patent Document 3) Document 4) discloses a thermally conductive grease composition using aluminum nitride powder surface-treated with organosilane.

The thermal conductivity of aluminum nitride is 70 to 270 W/mK. As a material with higher thermal conductivity than aluminum nitride, it is diamond with a thermal conductivity of 900 to 2000 W/mK. Japanese Patent Application Laid-Open No. 2002-30217 (Patent Document 5) discloses a thermally conductive silicone composition using diamond, zinc oxide, and a dispersant for a silicone resin.

In addition, Japanese Patent Laid-Open No. 2000-63873 (Patent Document 6) and Japanese Patent Laid-Open No. 222776 (Patent Document 7) disclose heat conduction in which metal aluminum powder is mixed with a base oil such as silicone oil. Sexual grease composition.

Although the above-mentioned ones are silicone compositions showing high thermal conductivity, all of the above-mentioned thermally conductive materials or thermally conductive greases have problems in dissipating heat due to the amount of heat generated by integrated circuit components such as recent CPUs. Sufficient question. existing technical documents patent documents

[Patent Document 1]: Japanese Patent Application Laid-Open No. 2-153995 [Patent document 2]: Japanese Patent Application Laid-Open No. 3-14873 [Patent Document 3]: Japanese Patent Application Publication No. 10-110179 [Patent Document 4]: Japanese Patent Application Laid-Open No. 2000-63872 [Patent document 5]: Japanese Patent Application Publication No. 2002-30217 [Patent Document 6]: Japanese Patent Application Laid-Open No. 2000-63873 [Patent Document 7]: Japanese Patent Application Laid-Open No. 2008-222776

Invent the problem to be solved

Therefore, an object of the present invention is to provide a thermally conductive silicone composition that can exhibit a good heat dissipation effect and a semiconductor device using the composition. solutions to problems

As a result of careful research to achieve the above object, the present inventors discovered a method capable of achieving the above object, and completed the present invention. This method can dramatically improve thermal conductivity by mixing silver powder and a specific fatty acid into a specific organopolysiloxane. That is, the present invention provides the following thermally conductive silicone composition and the like.

[1] A thermally conductive silicone composition containing the following component (A), component (B), component (C), component (D) and component (E), wherein (A) organopolysiloxane, It contains at least two alkenyl groups bonded to silicon atoms in one molecule, and has a kinematic viscosity of 10 to 100000 mm ² /s at 25°C. (B) Silver powder: relative to 100 parts by mass of component (A), It is 500 to 3000 parts by mass (C) Fatty acid: It is 0.01 to 10.0 parts by mass relative to 100 parts by mass of component (B) (D) Platinum-based catalyst: Catalyst amount (E): Organohydrogen polysiloxane: It is A compound containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule, and {the number of Si-H groups of component (E)/the number of alkenyl groups of component (A)} is 0.8 to 6.0 quantity. [2] The thermally conductive silicone composition according to [1], wherein the silver powder of component (B) is atomized silver powder with an aspect ratio of 1 to 2. [3] The thermally conductive silicone composition according to [1] or [2], wherein the component (C) is a fatty acid having 2 to 24 carbon atoms. [4] The thermally conductive silicone composition according to any one of [1] to [3], further comprising as component (F) represented by the following average composition formula (1), at 25°C For organopolysiloxane or organosilane represented by the following general formula (2), the kinematic viscosity under the conditions is 10 to 100000 mm ² /s, R ¹ _a SiO _{(4-a) /2} (1) in the average composition formula In (1), R ¹ is a hydrogen atom and/or a saturated or unsaturated monovalent hydrocarbon group with 1 to 18 carbon atoms, a is 1.8≤a≤2.2, R ² _b Si(OR ³ ) _4-b (2) In the general formula (2), R ² is one or more selected from the group consisting of saturated or unsaturated monovalent hydrocarbon groups that may have substituents, epoxy groups, and (meth)acrylic acid groups. Group, R ³ represents a monovalent hydrocarbon group, b is 1≤b≤3, and relative to 100 parts by mass of the component (A), the component (F) is 0.1 to 20 parts by mass. [5] A semiconductor device including a heat-generating electronic component and a heat sink, and the thermally conductive silicone composition according to any one of [1] to [4] is interposed between the between heat-generating electronic components and the heat sink. [6] The method for manufacturing a semiconductor device according to [5], which includes the step of: placing a heat sink between the heat-generating electronic component and the heat sink while applying a pressure of 0.1 MPa or more. The thermally conductive silicone composition described in any one of [1] to [4] is heated to 100°C or above. Effect of the invention

Since the thermally conductive silicone composition of the present invention has excellent thermal conductivity, it is useful for semiconductor devices that require good heat dissipation effects.

Hereinafter, the thermally conductive silicone composition of the present invention will be described in detail.

Ingredient(A) The organopolysiloxane used as component (A) of the thermally conductive silicone composition of the present invention is an organopolysiloxane having at least two alkenyl groups directly bonded to silicon atoms in one molecule. It may be a linear chain or a branched chain, and it may also be a mixture of two or more types of these organopolysiloxanes with different viscosities.

Examples of the component (A) include, for example, an organopolysiloxane represented by the following average composition formula and having at least two alkenyl groups bonded to a silicon atom in one molecule. R ⁴ _c R ⁵ SiO _{( 4-c -d ) /2} (In the above average composition formula, R ⁴ is independently an unsubstituted or substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, and R ⁵ independently represents is an alkenyl group, c is a positive number from 0.5 to 2.5, preferably a positive number from 0.8 to 2.2, and d is a positive number from 0.001 to 0.2, preferably a positive number from 0.0005 to 0.1. However, c+d is preferably a positive number from 0.8 to 2.7 A positive number, preferably a positive number between 0.9 and 2.2.)

As the alkenyl group, an alkenyl group having 2 to 6 carbon atoms is preferred, and an alkenyl group having 2 to 4 carbon atoms is more preferred. Specific examples include alkenyl groups such as vinyl, allyl, 1-butenyl, and 1-hexenyl. However, from the viewpoint of ease of synthesis and cost, vinyl is preferred. The alkenyl group bonded to the silicon atom may be present at the terminal or middle terminal of the organopolysiloxane molecular chain, but is preferably present at least at the terminal.

Examples of the organic group other than the alkenyl group bonded to the silicon atom include unsubstituted or substituted monovalent hydrocarbon groups that do not have an aliphatic unsaturated bond. An organic group having 1 to 10 carbon atoms is preferred, and an organic group having 1 to 6 carbon atoms is more preferred. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and dodecyl; aryl groups such as phenyl; and aromatic groups such as 2-phenylethyl and 2-phenylpropyl. Examples of the alkyl group include substituted hydrocarbon groups such as chloromethyl and 3,3,3-trifluoropropyl. Among them, from the viewpoint of ease of synthesis and cost, methyl is preferred.

If the kinematic viscosity of the organopolysiloxane of component (A) at 25°C is lower than 10 mm ² /s, oil leakage will easily occur when forming the composition; if the kinematic viscosity is higher than 100000 mm ² /s, The viscosity when forming the composition becomes high, making the composition difficult to handle. Therefore, the kinematic viscosity at 25°C is required to be 10~100000mm ² /s, and the optimum is 100~10000mm ² /s. It should be noted that the kinematic viscosity of organopolysiloxane is a value measured using an Ostend viscometer under conditions of 25°C.

The content of component (A) in the thermally conductive organosilicon composition of the present invention is preferably 1.0 to 30 mass%, more preferably 2.0 to 25 mass%, and still more preferably 3.0 to 20 mass%.

Component (B) Component (B) used in the thermally conductive silicone composition of the present invention is silver powder. The tap density of the silver powder of component (B) is not particularly limited, but if it is less than 3.0 g/cm ³ , the filling rate of the composition of component (B) cannot be increased, resulting in an increase in the viscosity of the composition, and further The operability of the composition deteriorates, so its tap density is preferably in the range of 3.0g/cm ³ ~10.0g/cm ³ , more preferably in the range of 4.0g/cm ³ ~10.0g/cm ³ . More preferably, it is in the range of 6.0g/cm ³ ~10.0g/cm ³ . It should be noted that the tap density described in this specification is based on weighing 100 g of silver powder, gently sprinkling the silver powder into a 100 ml graduated cylinder with a funnel, and then placing the graduated cylinder on the tap density measurement scale. The value is calculated from the volume of the compressed silver powder by placing it on the instrument and falling back 600 times at a drop distance of 20mm and a speed of 60 times/minute.

The specific surface area of the silver powder of component (B) is not particularly limited. However, if it is greater than 2.0 m ² /g, the filling rate of the composition of component (B) cannot be increased, resulting in an increase in the viscosity of the composition. In some cases, the combination The workability of the material deteriorates. Therefore, the specific surface area of the silver powder of component (B) is preferably in the range of 0.08m ² /g ~ 2.0m ² /g, and more preferably 0.08m ^{2 /} g ~ 1.5m ² /g range, and more preferably, the range is 0.08m ² /g~0.5m ² /g.

After weighing 2 g of silver powder as a sample and degassing it at 60±5° C. for 10 minutes, the total surface area was measured using an automatic specific surface area measuring device (BET method). Thereafter, the sample was weighed and calculated using the following equation (1) to calculate the specific surface area. Specific surface area (m ² /g) = total surface area (m ² )/amount of sample (g) (1)

Although the particle size of the silver powder of component (B) is not particularly limited, the average particle size is preferably in the range of 0.2 to 200 μm, more preferably in the range of 0.1 to 100 μm, and particularly preferably in the range of 1.0 to 30 μm. The average particle size is calculated by weighing 0.5g of silver powder and putting it into a 100ml beaker, then adding 60ml of isopropyl alcohol, and dispersing the silver powder with an ultrasonic homogenizer for 1 minute, and then analyzing the fineness by laser diffraction. The volume mean diameter [MV] of the volume basis measured by the instrument. In addition, the measurement was performed with the measurement time being 30 seconds.

The aspect ratio of the silver powder of component (B) is in the range of 1 to 2, preferably in the range of 1 to 1.5, and particularly preferably in the range of 1 to 1.2. The so-called aspect ratio refers to the ratio of the long diameter and the short diameter of the particle (long diameter/short diameter). As a method of measuring the particle, for example, an electron microscope photograph is taken of the particle, and the major axis and minor axis of the particle are measured from the photograph, so that the aspect ratio can be calculated. The size of the particles can be measured using an electron microscope photograph taken from above, and the larger diameter in the electron microscope photograph taken from the upper surface is measured as the major diameter. With respect to the major axis, the minor axis was defined as the thickness of the particle. But the thickness of the particles cannot be measured from the electron microscope photo above. In order to measure the thickness of particles, when taking electron microscope pictures, the sample stage on which the particles are placed can be tilted, and the electron microscope pictures are taken from above, and the thickness of the particles can be calculated by correcting the inclination angle of the sample stage. Specifically, after using an electron microscope to take several pictures that have been magnified several thousand times, the major and minor diameters of 100 silver particles are randomly measured, and then the ratio of the major to minor diameters (major diameter/short diameter) is calculated. Then find the average value and use it as the aspect ratio.

The raw material silver powder used in the present invention is preferably silver powder produced by a reduction method (wet or dry) or produced by an atomization method (water atomization method, gas atomization method, plasma rotating electrode method, etc.) Silver powder (atomized silver powder). The atomized silver powder is particularly preferably atomized silver powder produced by water atomization. Silver powder that has been ground to satisfy the above numerical range may be used. When pulverizing silver powder, the apparatus is not particularly limited, and examples thereof include known apparatuses such as a pounder, a ball mill, a vibrating mill, a hammer mill, a roller mill, and a mortar. Preferably, a crusher is used. Crusher, ball mill, vibration mill and hammer mill.

The compounding amount of component (B) is 500 to 3000 parts by mass relative to 100 parts by mass of component (A). If the blending amount of component (B) is less than 500 parts by mass relative to 100 parts by mass of component (A), the thermal conductivity of the resulting composition will deteriorate; relative to 100 parts by mass of component (A), the component ( If the blending amount of B) exceeds 3000 parts by mass, the fluidity of the obtained composition will deteriorate, and the operability of the composition will deteriorate. The blending amount of component (B) is preferably in the range of 600 to 2500 parts by mass, more preferably in the range of 700 to 1800 parts by mass relative to 100 parts by mass of component (A).

Ingredients(C) The component (C) used in the thermally conductive silicone composition of the present invention is fatty acid. The fatty acid has the effect of accelerating the sintering of the silver powder of component (B) and improving the thermal conductivity of the composition. Any of various fatty acids can be used in the present invention, but fatty acids having an unsubstituted or substituted monovalent hydrocarbon group having 2 to 24 carbon atoms, particularly 6 to 18 carbon atoms, are preferred. Examples of the component (C) include caprylic acid, nonanoic acid, capric acid, dodecanoic acid, myristanoic acid, pentadecanoic acid, hexadecanoic acid, oleic acid, stearic acid, and behenic acid. acid, linoleic acid, etc., among which caprylic acid, oleic acid, stearic acid, and behenic acid are preferred.

The blending amount of component (C) is 0.01 to 10.0 parts by mass relative to 100 parts by mass of component (B). If the blending amount of component (C) is less than 0.01 parts by mass relative to 100 parts by mass of component (B), the effect of promoting sintering will not be obtained. If the blending amount of component (C) is less than 100 parts by mass of component (B) If it is more than 10.0 parts by mass, the thermal conductivity may be deteriorated because the formation of a thermal conduction path is inhibited. Therefore, the blending amount of component (C) is preferably in the range of 0.05 to 5.0 parts by mass, and more preferably in the range of 0.1 to 3.0 parts by mass.

Ingredients(D) The component (D) used in the thermally conductive silicone composition of the present invention is a platinum-based catalyst. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefinic complex of platinum, an alkenylsiloxane complex of platinum, and a carbonyl complex of platinum.

In the composition of the present invention, the content of the platinum-based catalyst is the amount required for curing the composition of the present invention, that is, the so-called catalyst amount. Specifically, the platinum metal in this component is preferably in an amount in the range of 0.1 to 2000 ppm in terms of mass units relative to the component (A), and particularly preferably in an amount in the range of 0.1 to 1500 ppm.

Ingredients(E) The organohydrogenpolysiloxane of component (E) used in the thermally conductive silicone composition of the present invention has at least 2 (usually 2 to 300), preferably 2 to 100, per molecule. It is an organohydrogen polysiloxane with hydrogen atoms bonded to silicon atoms (i.e., SiH groups), and is any one of resinous materials with a linear, branched, cyclic or three-dimensional network structure. Examples of the bonding position of the hydrogen atom of component (E) include molecular chain terminals and/or molecular chain side chains.

As component (E), it is, for example, an organohydrogen polysiloxane represented by the following average composition formula. R ⁶ _e H _f SiO _(4-ef)/2 (3) (In the above average composition formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group. e is 1.0~3.0, Preferably, it is 0.5~2.5, f is 0.05~2.0, preferably 0.01~1.0, and e+f is a positive number satisfying 0.5~3.0, preferably 0.8~2.5.)

Examples of R ⁶ include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tertiary butyl, and cyclohexyl; phenyl, tolyl, Aryl groups such as xylyl group; aralkyl groups such as benzyl and phenethyl groups; halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl, etc. In addition to aliphatic unsaturated bonds, carbon is preferred An unsubstituted or halogen-substituted monovalent hydrocarbon group having an atomic number of 1 to 10, preferably about 1 to 8, etc. Among them, methyl, ethyl, propyl, phenyl, and 3,3,3-trifluoropropyl are preferred, and methyl is more preferred.

In the organohydrogen polysiloxane of component (E), the organic group bonded to silicon atoms other than hydrogen atoms is preferably an organic group having a carbon number of 1 to 10, more preferably an organic group having a carbon number of It is an organic group of 1 to 8. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and benzyl groups. , phenethyl and other aralkyl groups; chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl and other haloalkyl groups, among which methyl and phenyl are preferred.

The kinematic viscosity of component (E) at 25°C is not particularly limited, but is preferably 1~10000mm ² /s, more preferably 3~5000mm ² /s, particularly preferably 5~3000mm ² /s, and more preferably Preferably, it is liquid at room temperature (25°C).

The compounding amount of component (E), if the number of Si-H groups in component (E) is relative to the number of alkenyl groups in component (A), that is {the number of Si-H groups in component (E)} /{The number of alkenyl groups in component (A)} is less than 0.8, and the adhesion between the composition and the base material becomes poor. If it is greater than 6, the heat dissipation property of the composition may decrease. Therefore, the ratio is 0.8 to 6. The range is suitable, preferably the range of 1.5~3.

In the present invention, any of the following components may be used as necessary.

Ingredients(F) The component (F) used in the thermally conductive silicone composition of the present invention is an organopolysiloxane represented by the following average composition formula (1) or an organosilane represented by the following general formula (2). However, the range that overlaps with component (A) is excluded.

The organopolysiloxane is an organopolysiloxane represented by R ¹ _a SiO _(4-a)/2 (1) and has a kinematic viscosity of 10 to 100000 mm ² /s at 25°C. (In the above average composition formula, R ¹ is a hydrogen atom and/or a saturated monovalent hydrocarbon group with 1 to 18 carbon atoms, and a is 1.8≤a≤2.2.)

In the above average composition formula (1), R ¹ represents a saturated monovalent hydrocarbon group with a carbon number of 1 to 18, preferably a saturated monovalent hydrocarbon group with a carbon number of 1 to 10, more preferably a carbon number of It is a saturated monovalent hydrocarbon group of 1 to 6. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. ; Aryl groups such as phenyl and tolyl; aralkyl groups such as 2-phenylethyl and 2-methyl-2-phenylethyl; 3,3,3-trifluoropropyl, 2-(perfluorobutyl) Halogenated hydrocarbon groups such as ethyl, 2-(perfluorooctyl)ethyl, p-chlorophenyl, etc., among which methyl is preferred.

When the silicone composition of the present invention is used as a grease, a may be in the range of 1.8 to 2.2, particularly preferably in the range of 1.9 to 2.1, from the viewpoint of the required consistency of the silicone grease composition. .

In addition, if the kinematic viscosity of the organopolysiloxane of component (F) at 25°C is less than 10 mm ² /s, oil leakage will easily occur when forming the composition. If the kinematic viscosity is greater than 100000 mm ² /s, oil leakage will occur due to The viscosity when forming the composition becomes high and processing may become insufficient. Therefore, the viscosity is preferably 10 to 100000 mm ² /s at 25° C., and particularly preferably 100 to 50000 mm ² /s. In addition, the kinematic viscosity of organopolysiloxane is the value measured with an Ostwald viscometer at 25°C.

Organosilane R ² _b Si(OR ³ ) _4-b (2) [In the above general formula (2), R ² is a saturated or unsaturated monovalent hydrocarbon group that may have a substituent, an epoxy group, and a propylene group. group and one or more of methacryl groups, R ³ represents a monovalent hydrocarbon group, and b is 1≤b≤3. 〕

R ² in the above general formula (2) is a saturated or unsaturated monovalent hydrocarbon group which may have a substituent, preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, more preferably 1 carbon atom. ~14 monovalent hydrocarbon groups. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, nonyl, decyl, dodecyl, and tetradecyl; cycloalkenyl alkyl, Cycloalkyl groups such as acrylic, epoxy, cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and propenyl; aryl groups such as phenyl and tolyl; 2-phenylethyl and 2-methyl-2-phenyl Aralkyl groups such as ethyl; halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, p-chlorophenyl, etc. Among them, decyl is preferred. Examples of the substituent of the monovalent hydrocarbon group include an acryloxy group, a methacryloyloxy group, and the like. In addition, b is 1~3. R ³ is a monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include one or more alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl. Particularly preferred is methyl. and ethyl.

Specific examples of the organosilane represented by general formula (2) include the following. C ₁₀ H ₂₁ Si(OCH ₃ ) ₃ C ₁₂ H ₂₅ Si(OCH ₃ ) ₃ C ₁₂ H ₂₅ Si(OC ₂ H ₅ ) ₃ C ₁₀ H ₂₁ Si(CH ₃ )(OCH ₃ ) ₂ C ₁₀ H ₂₁ Si(C ₆ H ₆ )(OCH ₃ ) ₂ C ₁₀ H ₂₁ Si(CH ₃ )(OC ₂ H ₅ ) ₂ C ₁₀ H ₂₁ Si(CH=CH ₂ )(OCH ₃ ) ₂ C ₁₀ H ₂₁ Si( CH ₂ CH ₂ CF ₃ )(OCH ₃ ) ₂ CH ₂ =C(CH ₃ )COOC ₈ H ₁₆ Si(OCH ₃ ) ₃

When these organopolysiloxane and organosilane are added, the compounding amount of the organopolysiloxane and organosilane is preferably in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of component (A) Add it, preferably within the range of 5 to 10 parts by mass.

Ingredients(G) In order to adjust the curing speed of the composition of the present invention and improve the handling operability of the composition, 2-methyl-3-butyn-2-ol and 2-phenyl-3-butyn-2-ol can be , 1-ethynyl-1-cyclohexanol and other acetylene compounds; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne and other en-ynes Compounds; and other curing reaction inhibitors such as hydrazine compounds, phosphine compounds, and thiol compounds are added to the composition of the present invention. Although the content of the curing reaction inhibitor is not limited, it is preferably in the range of 0.0001 to 1.0 parts by mass relative to 100 parts by mass of component (A).

In addition, the thermally conductive siloxane composition of the present invention may contain inorganic compound powder and/or organic compound material in addition to component (B) within a range that does not impair the effects of the present invention. The inorganic compound powder is preferably an inorganic compound powder having high thermal conductivity. Examples thereof include aluminum powder, zinc oxide powder, titanium oxide powder, magnesium oxide powder, aluminum oxide powder, aluminum hydroxide powder, and boron nitride powder. , one or more of aluminum nitride powder, diamond powder, gold powder, copper powder, carbon powder, nickel powder, indium powder, gallium powder, metallic silicon powder, and silicon dioxide powder. The organic compound material is preferably an organic compound material having high thermal conductivity, and examples thereof include one or more selected from the group consisting of carbon fiber powder, graphene, graphite, carbon nanotubes, and carbon materials. If necessary, the surfaces of these inorganic compound powders and organic compound materials can also be hydrophobicized using organosilane, organazane, organopolysiloxane, organofluorine compound, or the like. Since the average particle diameter of the inorganic compound powder and the organic compound material is less than 0.5 μm or greater than 100 μm, sometimes the filling rate of the obtained grease composition cannot be increased. Therefore, the average particle diameter of the inorganic compound powder and the organic compound material is better. The range is 0.5~100μm, particularly preferably the range is 1~50μm. In addition, since the fiber length of the carbon fiber is less than 10 μm or greater than 500 μm, sometimes the filling rate of the obtained grease composition cannot be increased. Therefore, the fiber length of the carbon fiber is preferably in the range of 10 to 500 μm, and particularly preferably 30 to 30 μm. 300μm range. If the blending amount of the inorganic compound powder and the organic compound material exceeds 3000 parts by mass relative to 100 parts by mass of component (A), the fluidity of the resulting composition will deteriorate, and the operability of the grease composition may deteriorate. , therefore, the blending amount of the inorganic compound powder and the organic compound material is preferably 0.1 to 3000 parts by mass, and particularly preferably 0.1 to 2000 parts by mass.

Manufacturing method The manufacturing method of the thermally conductive silicone composition of the present invention is not particularly limited as long as it follows a conventionally known manufacturing method of silicone grease compositions. For example, the above-mentioned components (A) to (E) and other components as needed can be mixed with a three-roller mixer, a two-roller mixer, or a planetary mixer (all mixers manufactured by Inoue Seisakusho Co., Ltd., Japan). , registered trademark), high-speed mixer (mixer manufactured by Nippon Mizuho Industrial Co., Ltd., registered trademark), three-axis planetary orbit dispersing, mixing and kneading machine (mixer manufactured by Nippon Special Machinery Chemical Industry Co., Ltd., registered trademark), etc. It is manufactured by mixing with a mixer for 30 minutes to 4 hours. In addition, if necessary, mixing can also be performed while heating under temperature conditions ranging from 30 to 100°C.

The absolute viscosity of the thermally conductive silicone composition of the present invention measured at 25°C is 10 to 1000 Pa·s, preferably 50 to 700 Pa·s, and more preferably 80 to 600 Pa·s. When the absolute viscosity is within the above range, a good grease can be provided, and the composition also has excellent operability. This absolute viscosity can be obtained by preparing each component in the above blending amount. The absolute viscosity is measured using a spiral viscometer model PC-1TL (10 rpm) manufactured by Malcom Co., Ltd.

Semiconductor device In the semiconductor device of the present invention, the thermally conductive silicone composition of the present invention is interposed between a heat-generating electronic component and a heat sink. The thermally conductive silicone composition of the present invention is preferably interposed between the heat-generating electronic component and the heat sink with a thickness of 10 to 200 μm. A representative structure is shown in FIG. 1 , but the present invention is not limited thereto. 1 is a schematic vertical cross-sectional view showing an example of a semiconductor device of the present invention. For example, the semiconductor device of the present invention is a heat-generating electronic component (CPU) mounted on a substrate 1 with a thermally conductive silicone composition layer 3 interposed therebetween. ) 2 and the heat sink (cover) 4, and the thermally conductive silicone composition layer 3 is a cured product of the thermally conductive silicone composition of the present invention.

In the process of manufacturing the semiconductor device of the present invention, it is preferable to heat the thermally conductive silicone composition of the present invention between the heat-generating electronic component and the heat sink while applying a pressure of 0.01 MPa or more. Method above 100℃. At this time, the applied pressure is preferably 0.01MPa or more, particularly preferably 0.05MPa to 100MPa, and more preferably 0.1MPa to 100MPa. The heating temperature needs to be above 100°C, preferably 100°C to 300°C, more preferably 120°C to 250°C, and still more preferably 140°C to 200°C. Example

Hereinafter, for the purpose of further clarifying the effects of the present invention, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited to these examples.

Component (A) A-1: Dimethylpolysiloxane with both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity of 600mm ² /s at 25°C (vinyl content: 0.014mol/100g)

Component (B) B-1: Spherical silver powder produced by the atomization method with an average particle diameter of 3µm, a tap density of 6.5g/ ^cm3 , a specific surface area of ^0.3m2 /g, and an aspect ratio of 1 (atomized Silver powder) B-2: Spherical silver powder produced by the atomization method (atomized silver powder) with an average particle diameter of 0.8µm, a tap density of 4.3g/cm ³ , a specific surface area of 1.2m ² /g, and an aspect ratio of 1. ) B-3: Spherical silver powder produced by the atomization method (atomized silver powder) with an average particle diameter of 70µm, a tap density of 6.0g/cm ³ , a specific surface area of 0.2m ² /g, and an aspect ratio of 1. B -4: Silver powder B-5 produced by the wet reduction method with an average particle diameter of 1.5 µm, a tap density of 6.2 g/cm ³ , a specific surface area of 0.3 m ² /g, and an aspect ratio of 1 (comparative example) : Silver powder B-6 (comparative example) produced by the wet reduction method with an average particle diameter of 3 µm, a tap density of 6.3 g/cm ³ , a specific surface area of 0.3 m ² /g, and an aspect ratio of 1: Average particle size Aluminum powder with a diameter of 10µm B-7 (comparative example): Alumina powder with an average particle diameter of 10µm

Ingredients(C) C-1: Oleic acid C-2: Caprylic acid C-3: Behenic acid

Ingredients(D) D-1 (platinum catalyst): A-1 solution of platinum-divinyltetramethyldisiloxane complex, containing 1 wt% as platinum atoms

Component (E) E-1: Organohydrogen polysiloxane represented by the following general formula (Si-H group content: 0.0055 mol/g) [Chemical Formula 1]

Component (F) F-1: Organosilane represented by the following general formula [Chemical Formula 2]

Ingredients(G) G-1: 1-ethynyl-1-cyclohexanol

Examples 1 to 12 and Comparative Examples 1 to 7 The compositions shown in Table 1 and Table 2 below were mixed in the following method to obtain the compositions of Examples 1 to 12 and Comparative Examples 1 to 7. That is, the component (A), the component (B), the component (C) and the component (F) were added to a planetary mixer (manufactured by Japan Inoue Manufacturing Co., Ltd.) with a capacity of 5 liters, and mixed at 25°C. 1.5 hours. Then, component (D) and component (G) were added and mixed at 25°C for 15 minutes. Finally add ingredient (E) and mix until smooth.

Tests regarding the effects of the present invention were conducted by the following method. [viscosity] The absolute viscosity of the grease composition was measured at 25°C using a spiral viscometer model PC-1TL (10 rpm) manufactured by Malcom Co., Ltd. [Thermal conductivity] Each composition was cast into a 6 cm thick mold, covered with kitchen plastic wrap, and measured at 25°C using TPS-2500S manufactured by Kyoto Electronics Industry Co., Ltd., Japan. Thermal conductivity before heat curing. Each composition was cast into a 6 mm thick mold, heated at 150°C for 60 minutes with a pressure of 0.35 MPa applied, and cooled to room temperature. TPS-2500S manufactured by Co., Ltd. measured the thermal conductivity of each composition after heat curing at 25°C.

Table 1 Unit: parts by mass Example 1 2 3 4 5 6 7 8 9 10 11 12 A-1 100 100 100 100 100 100 100 100 100 100 100 100 B-1 1700 2800 2800 550 1700 1700 B-2 1700 B-3 1700 B-4 1700 1700 B-5 1700 1700 B-6 B-7 C-1 1.7 1.7 280 0.06 1.7 1.7 1.7 1.7 1.7 1.7 C-2 1.7 C-3 1.7 D-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 E-1 2.44 2.44 2.44 2.44 2.44 2.44 2.44 2.44 2.44 2.44 2.44 2.44 F-1 10 10 G-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 H/Vi 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Ingredient(C)/Ingredient(B) (%) 0.1 0.06 10 0.01 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Viscosity (Pa･s) 300 700 500 100 320 350 600 400 600 550 200 190 Thermal conductivity before heating and curing (W/m･K) 1 2 1 1 2 2 1 2 2 2 2 2 Thermal conductivity after heating and curing (W/m･K) 10 15 12 7 12 11 8 12 14 16 12 14

Table 2 Comparative example 1 2 3 4 5 6 7 A-1 100 100 100 100 100 100 100 B-1 450 3300 1700 1700 1700 B-2 B-3 B-4 B-5 B-6 1200 B-7 1200 C-1 0.4 3.3 1.2 1.2 0.1 250 C-2 C-3 D-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 E-1 2.44 2.44 2.44 2.44 2.44 2.44 2.44 F-1 G-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 H/Vi 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Ingredient(C)/Ingredient(B) (%) 0.09 0.1 0.1 0.1 0.006 14.7 0 Viscosity (Pa･s) 80 Failed to form into grease 300 350 320 150 320 Thermal conductivity before heating and curing (W/m･K) 0.5 4 3 1 0.5 1 Thermal conductivity after heating and curing (W/m･K) 2 4 3 2 0.5 2 Comparative Example 1: The blending amount of silver powder is small, resulting in low thermal conductivity. Comparative Example 2: The blending amount of the silver powder was large and the grease was not formed into grease. Comparative Examples 3 and 4: Since they are not silver powder, the thermal conductivity is low. Comparative Example 5: The blending amount of fatty acid is small, resulting in low thermal conductivity. Comparative Example 6: The compounding amount of fatty acid is large, resulting in low thermal conductivity. Comparative Example 7: The compounding amount of fatty acid is zero, resulting in low thermal conductivity.

1:Substrate 2: Heating electronic components (CPU) 3: Thermal conductive silicone composition layer 4: Heat sink (cover)

FIG. 1 is a schematic vertical cross-sectional view showing an example of the semiconductor device of the present invention.

Claims (6)

A thermally conductive silicone composition comprising the following component (A), component (B), component (C), component (D) and component (E), wherein (A) organopolysiloxane, which is in 1 The molecule contains at least 2 alkenyl groups bonded to silicon atoms, and the kinematic viscosity at 25°C is 10~100000mm ² /s (B) Silver powder: relative to 100 parts by mass of component (A), it is 500 ~3000 parts by mass (C) Fatty acid: 0.01~10.0 parts by mass relative to 100 parts by mass of component (B) (D) Platinum-based catalyst: Catalyst amount (E): Organohydrogen polysiloxane: It is in 1 molecule It contains at least 2 hydrogen atoms bonded to silicon atoms, and {number of Si-H groups of component (E)/number of alkenyl groups of component (A)} is a blending amount of 0.8 to 6.0. The thermally conductive silicone composition according to claim 1, wherein, The silver powder of component (B) is atomized silver powder with an aspect ratio of 1 to 2. The thermally conductive silicone composition according to claim 1, wherein, Component (C) is a fatty acid with 2 to 24 carbon atoms. The thermally conductive silicone composition according to any one of claims 1 to 3, further comprising as component (F) a kinematic viscosity at 25°C represented by the following average composition formula (1) is an organopolysiloxane or an organosilane represented by the following general formula (2) of 10 to 100000 mm ² /s, R ¹ _a SiO _{(4-a) /2} (1) In the average composition formula (1), R ¹ is a hydrogen atom and/or a saturated monovalent hydrocarbon group with 1 to 18 carbon atoms, a is 1.8≤a≤2.2, R ² _b Si(OR ³ ) _4-b (2) In the general formula (2) , R ² is one or more groups selected from the group consisting of saturated or unsaturated monovalent hydrocarbon groups that may have substituents, epoxy groups and (meth)acrylic acid groups, and R ³ represents a monovalent group. Hydrocarbon group, b is 1≤b≤3, and the component (F) is 0.1 to 20 parts by mass relative to 100 parts by mass of the component (A). A semiconductor device characterized by: This is a semiconductor device including a heat-generating electronic component and a heat sink, and the thermally conductive silicone composition according to claim 1 is interposed between the heat-generating electronic component and the heat sink. A method for manufacturing a semiconductor device according to claim 5, characterized in that: It has the following steps: The thermally conductive silicone composition according to claim 1 is heated to 100° C. or higher while a pressure of 0.1 MPa or higher is applied between the heat-generating electronic component and the heat sink.