WO2020075411A1 - 付加硬化型シリコーン組成物及びその製造方法 - Google Patents
付加硬化型シリコーン組成物及びその製造方法 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to an addition-curable silicone composition and a method for producing the same. More particularly, it relates to a highly heat-conductive addition-curable silicone composition, and an addition-curable silicone composition having good adhesion to various adherends even if it contains a large amount of a heat-conductive filler, and a method for producing the same.
- Patent Document 9 discloses a thermally conductive silicone grease composition containing an organopolysiloxane having a specific structure, an alkoxysilane having a specific substituent, and a thermally conductive filler. It is described that the composition has good thermal conductivity, good fluidity and excellent workability.
- Patent Documents 10 and 11 disclose a sheet having adhesiveness and thermal conductivity, and an addition-curable silicone rubber composition contains a thermally conductive filler and an aliphatic unsaturated hydrocarbon group.
- a thermally conductive composition containing a non-silicone resin is disclosed.
- Patent Document 10 and Patent Document 11 disclose that a thermally conductive cured product having appropriate adhesiveness and good thermal conductivity in a thin film state can be provided.
- Some heat-dissipating greases have adhesive properties added to the grease in order to firmly bond the semiconductor chip and heat spreader. This is because if the semiconductor chip and the heat spreader are not sufficiently adhered via the grease, the heat dissipation performance is not fully exhibited and the performance is significantly reduced. Therefore, it is important to firmly bond the semiconductor chip and the heat spreader with grease.
- Patent Document 12 JP 2012-102283A discloses an alkenyl group-containing organopolysiloxane, a hydrolyzable methylpolysiloxane, a heat conductive filler, an organohydrogenpolysiloxane, a triazine ring- and alkenyl group-containing adhesion aid, And a thermally conductive silicone grease composition containing a platinum-based catalyst as an essential component.
- Patent Document 12 describes that the composition can provide a heat-dissipating grease that has a small increase in hardness when subjected to heat aging at a high temperature after curing and has a suppressed decrease in elongation.
- Patent Document 13 JP 2012-96361 A discloses a thermally conductive silicone composition containing a peroxide having a 10-hour half-life temperature of 80 ° C. or higher and lower than 130 ° C. as a curing agent. States that it can provide a heat-dissipating grease that can be easily cured on the surface of a substrate having a noble metal layer such as gold.
- the present invention has been made in view of the above circumstances, and provides a silicone heat-dissipating grease which has a higher thermal conductivity than conventional silicone heat-dissipating grease and has good adhesiveness to various adherends. It is an object of the present invention to provide an addition-curable silicone composition capable of producing and a method for producing the same.
- the present inventor has conducted extensive studies to achieve the above object, and as a result, an aliphatic unsaturated hydrocarbon group-containing organopolysiloxane, a thermally conductive filler, an organohydrogenpolysiloxane having a specific structure, and an organic peroxide.
- the present invention has been completed by finding that an addition-curable silicone composition having good adhesiveness to an adherend can be obtained.
- the present invention provides the following addition-curable silicone composition and a method for producing the same. [1].
- (A) Organopolysiloxane having at least two aliphatic unsaturated hydrocarbon groups in one molecule and having a kinematic viscosity at 25 ° C.
- R 2 is an epoxy Group, an acryloyl group, a methacryloyl group, an alkoxysilyl group, X is an alkylene group having 1 to 20 carbon atoms and optionally containing a hetero atom, and n is an integer of 0 to 2.
- the hydrolyzable organopolysiloxane compound represented by the following general formula (2) is contained in an amount of 1 to 200 parts by mass per 100 parts by mass of the components (A) and (B) [1] or The addition-curable silicone composition according to [2].
- R 1 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and each R 1 may be the same or different.
- M is 5 to Indicates an integer of 100.
- a hydrolyzable organopolysiloxane compound represented by the following general formula (3) is contained in an amount of 1 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B) [1] to The addition-curable silicone composition according to any one of [3].
- R 1 represents a monovalent hydrocarbon group having 1-10 1 carbon atoms which may have a substituent, each of R 1 good .R 3 be different even for the same carbon It is an alkenyl group of the numbers 2 to 6.
- p and q are numbers satisfying 1 ⁇ p ⁇ 50, 1 ⁇ q ⁇ 99, and 5 ⁇ p + q ⁇ 100.
- the addition-curable silicone composition of the present invention has good adhesiveness to various adherends even if it contains a large amount of thermally conductive filler, it is possible to achieve both high thermal conductivity and strong adhesiveness. . That is, it is possible to provide a silicone heat-dissipating grease that can cope with the recent increase in heat generation and size increase of semiconductor devices.
- Component (A) has at least 2, preferably 2 to 100, more preferably 2 to 50 aliphatic unsaturated hydrocarbon groups in one molecule and has a kinematic viscosity at 25 ° C. Is 60 to 100,000 mm 2 / s.
- the aliphatic unsaturated hydrocarbon group is preferably a monovalent hydrocarbon group having an aliphatic unsaturated bond and having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably an alkenyl group.
- alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, and octenyl group.
- a vinyl group is particularly preferred.
- the aliphatic unsaturated hydrocarbon group may be bonded to either a silicon atom at the end of the molecular chain or a silicon atom in the middle of the molecular chain, or may be bonded to both.
- the organopolysiloxane as the component (A) preferably has 0.00001 to 0.01 mol / g, particularly 0.0001 to 0.01 mol / g, of an aliphatic unsaturated hydrocarbon group in one molecule. .
- Examples of the organic group other than the aliphatic unsaturated hydrocarbon group bonded to the silicon atom of the organopolysiloxane include a fatty acid having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. It is an unsubstituted or substituted monovalent hydrocarbon group having no group unsaturated bond.
- alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group and decyl group;
- An aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group, or a part or all of the hydrogen atoms of these groups such as fluorine, bromine, chlorine, etc.
- a halogen atom, a cyano group or the like for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like. It is particularly preferably a methyl group.
- the organopolysiloxane has a kinematic viscosity at 25 ° C. of 60 to 100,000 mm 2 / s, preferably 100 to 30,000 mm 2 / s. If the kinematic viscosity is less than 60 mm 2 / s, the physical properties of the silicone composition will deteriorate, and if it exceeds 100,000 mm 2 / s, the extensibility of the silicone composition will be poor.
- the kinematic viscosity is a value at 25 ° C. measured by an Ubbelohde-type Ostwald viscometer (hereinafter the same).
- the molecular structure of the organopolysiloxane is not particularly limited as long as it has the above properties, and examples thereof include a linear structure, a branched structure, a partially branched structure, or a linear structure having a cyclic structure. .
- the main chain is composed of repeating diorganosiloxane units and both ends of the molecular chain have a linear structure blocked with triorganosiloxy groups.
- the organopolysiloxane having the linear structure may partially have a branched structure or a cyclic structure.
- the organopolysiloxane may be used alone or in combination of two or more.
- Component (B) is a silicone resin.
- the silicone resin as the component (B) has at least one aliphatic unsaturated hydrocarbon group in one molecule.
- the component (B) may not be blended, but when the silicone resin as the component (B) is contained, the adhesive strength of the cured product obtained from the addition-curable silicone composition of the present invention can be improved.
- the component (B) is preferably a SiO 4/2 unit, an R 4 2 R 5 SiO 1/2 unit, and an R 4 3 SiO 1/2 unit (in the formula, R 4 is independently an aliphatic group).
- R 4 is independently an aliphatic group.
- a silicone resin containing a monovalent hydrocarbon group having no unsaturated bond and R 5 is a monovalent aliphatic unsaturated hydrocarbon group.
- R 4 s independently of each other have 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, unsubstituted or substituted 1 It is a valent hydrocarbon group.
- R 4 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, an octyl group, a nonyl group or a decyl group.
- a halogen atom such as bromine or chlorine, a cyano group and the like, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like.
- a methyl group is particularly preferable.
- R 5 is a monovalent aliphatic unsaturated hydrocarbon group, preferably a monovalent hydrocarbon group having an aliphatic unsaturated bond and having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and It is preferably an alkenyl group.
- alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and an octenyl group.
- a vinyl group is particularly preferred.
- the component (B) has at least one silicone resin in one molecule, preferably 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 mol / g, and more preferably 1 ⁇ 10 ⁇ 4 to 2 ⁇ 10 ⁇ 3 mol / g. Having an aliphatic unsaturated hydrocarbon group.
- the molar ratio of the SiO 4/2 unit (Q unit) to the R 4 2 R 5 SiO 1/2 unit and the R 4 3 SiO 1/2 unit (M unit) is (M unit).
- ) / (Q unit) is a number satisfying 0.1 to 3
- (M unit) / (Q unit) is preferably a number satisfying 0.3 to 2.5, and particularly (M unit). It is preferable that / (Q unit) is a number satisfying 0.5 to 2.
- the silicone resin according to the present invention does not impair the properties of the addition-curable silicone composition of the present invention with R 2 SiO 2/2 units (D units) and RSiO 3/2 units (T units) in the molecule.
- R 2 SiO 2/2 units D units
- RSiO 3/2 units T units
- R for example, 1 to 50 mol% in the component (B) silicone resin
- R is R 4 or R 5 .
- the silicone resin used in the present invention is a solid or viscous liquid at room temperature.
- the average molecular weight of the silicone resin is not particularly limited, but the kinematic viscosity when the silicone resin is dissolved in xylene to form a 50 mass% solution has a kinematic viscosity of 0.5 to 10 mm 2 / s, preferably 1 to 5 mm 2 / s.
- a molecular weight such that When the kinematic viscosity of the silicone resin is within the above range, deterioration of physical properties of the composition can be prevented, which is preferable.
- the amount of the silicone resin as the component (B) is 0 to 100 parts by mass with respect to 100 parts by mass of the component (A), but when blended, it is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass. Is. If the amount of the component (B) is less than the above lower limit, it may be insufficient to develop adhesiveness, and if it is more than the above upper limit, the extensibility may be poor.
- 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.
- metals metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon.
- metals metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon.
- aluminum, silver, copper, metallic silicon, alumina, 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 and the like can be mentioned. These may be used alone or in combination of two or more, and are preferably a combination of a large particle component and a small particle component.
- the average particle size of the large particle component is smaller than 0.1 ⁇ m, the viscosity of the obtained composition may be too high, resulting in poor extensibility, and if it is larger than 100 ⁇ m, the obtained composition may be non-uniform. Therefore, the range of 0.1 to 100 ⁇ m is preferable, the range of 10 to 50 ⁇ m is more preferable, and the range of 10 to 45 ⁇ m is more preferable. If the average particle size of the small particle component is less than 0.01 ⁇ m, the viscosity of the obtained composition may be too high, and the extensibility may be poor. If it is 10 ⁇ m or more, the obtained composition is not uniform.
- the range is preferably 0.01 ⁇ m or more and less than 10 ⁇ m, and more preferably 0.1 to 4 ⁇ m.
- the ratio of the large particle component and the small particle component is not particularly limited, and is preferably in the range of 9: 1 to 1: 9 (mass ratio).
- the shapes of the large particle component and the small particle component are not particularly limited, and may be spherical, irregular shape, needle-like, or the like.
- the average particle size can be obtained as, for example, a volume-based average value (or median size) in particle size distribution measurement by a laser light diffraction method.
- the blending amount of the component (C) is 10 to 95% by mass, preferably 20 to 90% by mass, more preferably 30 to 88% by mass, and even 50 to 85% by mass, based on the entire composition.
- the composition has poor extensibility, and when it is less than 10% by mass, it has poor thermal conductivity.
- the component (D) is an organohydrogenpolysiloxane having two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, preferably 2 to 100, and more preferably 2 to 20. Is.
- the SiH group in the molecule undergoes an addition reaction with the aliphatic unsaturated hydrocarbon group contained in the components (A) and (B) in the presence of a platinum group metal catalyst to form a crosslinked structure. Any material that can be formed may be used.
- the molecular structure of the organohydrogenpolysiloxane is not particularly limited as long as it has the above-mentioned properties, and a linear structure, a branched structure, a cyclic structure, a partially branched structure or a linear structure having a cyclic structure. A structure etc. are mentioned. A linear structure and a cyclic structure are preferred.
- the organohydrogenpolysiloxane has a kinematic viscosity at 25 ° C. of preferably 1 to 1,000 mm 2 / s, more preferably 10 to 100 mm 2 / s. If the kinematic viscosity is 1 mm 2 / s or more, the physical properties of the silicone composition may not be deteriorated, and if it is 1,000 mm 2 / s or less, the extensibility of the silicone composition may be poor. There is no.
- Examples of the organic group bonded to the silicon atom of the organohydrogenpolysiloxane include unsubstituted or substituted monovalent hydrocarbon groups other than the aliphatic unsaturated hydrocarbon group. Particularly, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms.
- an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, an aryl group such as a phenyl group, an aralkyl group such as a 2-phenylethyl group and a 2-phenylpropyl group, and hydrogen thereof.
- halogen atoms such as fluorine, bromine, chlorine, cyano group, epoxy ring-containing organic group (glycidyl group or glycidyloxy group-substituted alkyl group), for example, chloromethyl group, chloropropyl Group, bromoethyl group, trifluoropropyl group, cyanoethyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group and the like. Of these, a methyl group and a 3-glycidoxypropyl group are preferable.
- the organohydrogenpolysiloxane may be used alone or in combination of two or more.
- the amount of the organohydrogenpolysiloxane as the component (D) is such that the total number of the aliphatic unsaturated hydrocarbon groups in the components (A) and (B) is 0.
- the amount is 5 to 5, preferably 0.7 to 4.5, and more preferably 1 to 4. If the amount of component (D) is less than the above lower limit, the addition reaction will not proceed sufficiently and crosslinking will be insufficient. On the other hand, if the amount exceeds the upper limit, the cross-linked structure may become non-uniform, or the storage stability of the composition may be significantly deteriorated.
- the number of aliphatic unsaturated hydrocarbon groups in the composition is 0.5 to 5, and particularly 1 to 4 relative to the total of the above.
- Component (E) The component (E) is decomposed under specific conditions selected from peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and peroxydicarbonate to generate free radicals. It is an organic peroxide which is generated, and can be used alone or in combination of two or more kinds as a reaction initiator for introducing a silalkylene structure into the siloxane crosslinked structure of the silicone composition obtained by the present invention. To work.
- peroxyketals such as 1,1-di (tert-butylperoxy) cyclohexane and 2,2- (4,4-di- (tert-butylperoxy) cyclohexyl) propane, p-menthane hydro Hydroperoxides such as peroxides and diisopropylbenzene hydroperoxides, dialkyl peroxides such as dicumyl peroxide, tert-butylcumyl peroxide, and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane , Dibenzoyl peroxide, diacyl peroxide such as disuccinic acid peroxide, peroxy ester such as tert-butyl peroxyacetate and tert-butyl peroxybenzoate, peroxy ester such as diisopropyl peroxydicarbonate Siji carbonate is preferably used. Particularly, it is preferable to use peroxyketal, hydro
- the decomposition temperature for obtaining the one-hour half-life is preferably in the range of 50 to 200 ° C, more preferably in the range of 80 to 170 ° C. If the decomposition temperature for obtaining a one-hour half-life is less than 50 ° C, the reaction may be explosive, which makes it difficult to handle. The introduction efficiency of the silalkylene structure may decrease. Further, these organic peroxides may be diluted with any organic solvent, hydrocarbon, liquid paraffin, inert solid or the like.
- the blending amount of the component (E) is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending amount is less than 0.01 parts by mass, the introduction efficiency of the silalkylene structure into the structure of the silicone composition decreases, and if it exceeds 10 parts by mass, the storage stability of the silicone composition may decrease. There is a nature.
- Component (F) is a hydrolyzable organosilane compound represented by the following general formula (1), which may be used alone or in combination of two or more, and is obtained in the present invention. It acts as an adhesion aid for improving the adhesiveness of the silicone composition.
- R 1 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and each R 1 may be the same or different.
- R 2 is an epoxy Group, an acryloyl group, a methacryloyl group, an alkoxysilyl group, X is an alkylene group having 1 to 20 carbon atoms and optionally containing a hetero atom, and n is an integer of 0 to 2.
- R 1 in the above formula (1) is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, preferably a monovalent saturated aliphatic hydrocarbon which may have a substituent.
- Branched-chain alkyl groups such as alkyl groups, isopropyl groups, isobutyl groups, tert-butyl groups, isopentyl groups, neopentyl groups, cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, chloromethyl groups, 3-chloropropyl groups And halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl group and bromopropyl group, etc., having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. .
- Examples of the monovalent unsaturated aliphatic hydrocarbon group which may have a substituent include alkenyl groups such as ethenyl group, 1-methylethenyl group and 2-propenyl group, ethynyl group and 2-propynyl group.
- An alkynyl group or the like having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms.
- aryl groups such as phenyl group and tolyl group
- aralkyl groups such as benzyl group and 2-phenylethyl group
- ⁇ , ⁇ , ⁇ -A halogen-substituted aryl group such as a trifluorotolyl group and a chlorobenzyl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and more preferably 6 carbon atoms.
- R 1 is preferably a methyl group, an ethyl group, a 3,3,3-trifluoropropyl group or a phenyl group, more preferably a methyl group, an ethyl group or a phenyl group, and particularly preferably a methyl group. Is.
- R 2 is a group selected from an epoxy group, an acryloyl group, a methacryloyl group, and an alkoxysilyl group.
- an epoxy group or an alkoxysilyl group examples include a trimethoxy group, a dimethoxymethyl group, a methoxydimethylsilyl group, a triethoxy group, a diethoxymethyl group, an ethoxydimethylsilyl group, and among these, a trimethoxy group and a triethoxy group are preferable.
- X is an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom, and is a spacer connecting R 2 and the silicon atom.
- the structure of X is not particularly limited and may be linear or branched, but is preferably linear. Specific examples of X include those shown below. -CH 2 OCH 2 CH 2 CH 2- —CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 — -(CH 2 ) x- (X is an integer from 1 to 20.)
- N is an integer of 0 to 2 and defines the number of alkoxy groups of the alkoxysilyl group of the hydrolyzable organosilane compound as the component (F).
- n is preferably 0 or 1, and more preferably 0. is there.
- the blending amount of the component (F) is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). If the blending amount is less than 0.1 part by mass, the coating amount on the surface of the thermally conductive filler will be reduced, so that the adhesiveness may not be sufficiently exhibited. If the amount exceeds 30 parts by mass, the strength of the cured product of the silicone composition may be reduced, and the adhesiveness may not be sufficiently exhibited, which is not preferable.
- Component (G) is a platinum group metal catalyst and functions to accelerate the addition reaction of the above-mentioned components.
- the platinum group metal catalyst a conventionally known catalyst used for an addition reaction can be used. Examples thereof include platinum-based, palladium-based, and rhodium-based catalysts, and among them, platinum or a platinum compound that is relatively easily available is preferable. For example, simple substance of platinum, platinum black, chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, platinum coordination compound and the like can be mentioned.
- the platinum group metal catalysts may be used alone or in combination of two or more.
- the blending amount of the component (G) may be an effective amount as a catalyst, that is, an effective amount necessary for promoting the addition reaction and curing the addition-curable silicone composition of the present invention.
- the amount is preferably 0.1 to 500 ppm, and more preferably 1 to 200 ppm, based on the mass of platinum group metal atoms, based on the total mass of the components (A) and (B). If the amount of the catalyst is less than the above lower limit, the effect as the catalyst may not be obtained. Further, even if the upper limit is exceeded, the catalytic effect does not increase and it is uneconomical, which is not preferable.
- the addition-curable silicone composition of the present invention may further contain the following optional components in addition to the above components, if necessary.
- the component (H) is a reaction control agent that suppresses the progress of the hydrosilylation reaction at room temperature, and can be added to extend the shelf life and the pot life.
- a reaction control agent a conventionally known control agent used in addition-curable silicone compositions can be used.
- acetylene compounds such as acetylene alcohols (eg, ethynylmethyldecylcarbinol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol), tributylamine, tetra
- acetylene alcohols eg, ethynylmethyldecylcarbinol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol
- tributylamine tetra
- nitrogen compounds such as methylethylenediamine and benzotriazole
- organic phosphorus compounds such as triphenylphosphine, oxime compounds and organic chloro compounds.
- the blending amount is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of the components (A) and (B). Is. If the amount of the reaction control agent is less than 0.05 parts by mass, the desired sufficient shelf life and pot life may not be obtained, and if it is more than 5 parts by mass, the curability of the silicone composition may be poor. It may decrease. Further, the reaction control agent may be diluted with an organo (poly) siloxane, toluene or the like and used in order to improve dispersibility in the silicone composition.
- the addition-curable silicone composition of the present invention may further contain a hydrolyzable organopolysiloxane compound (I) represented by the following general formula (2).
- the hydrolyzable organopolysiloxane compound as the component (I) is used for treating the surface of the thermally conductive filler, and plays a role of assisting the high filling of the filler.
- R 1 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and each R 1 may be the same or different.
- M is 5 to Indicates an integer of 100.
- R 1 in the above formula (2) is the same as described above, and is particularly preferably a methyl group.
- m is an integer of 5 to 100, preferably 10 to 60. If the value of m is less than 5, oil bleeding derived from the silicone composition may be severe and the reliability may be deteriorated. If the value of m is greater than 100, the wettability with the filler may be insufficient.
- the blending amount is preferably 1 to 200 parts by mass, and particularly preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B). If the amount of component (I) is less than 1 part by mass, sufficient wettability may not be exhibited. Further, if the amount of the component (I) is more than 200 parts by mass, bleeding from the composition may be severe.
- the addition-curable silicone composition of the present invention may further contain a hydrolyzable organopolysiloxane compound (J) represented by the following general formula (3).
- the hydrolyzable organopolysiloxane compound as the component (J) has a reinforcing effect of treating the surface of the thermally conductive filler and enhancing the strength of the silicone composition.
- R 1 represents a monovalent hydrocarbon group having 1-10 1 carbon atoms which may have a substituent, each of R 1 good .R 3 be different even for the same carbon It is an alkenyl group of the numbers 2 to 6.
- p and q are numbers satisfying 1 ⁇ p ⁇ 50, 1 ⁇ q ⁇ 99, and 5 ⁇ p + q ⁇ 100.
- R 1 in the above formula (3) is the same as described above, and is particularly preferably a methyl group.
- R 3 is an alkenyl group having 2 to 6 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group, with vinyl being particularly preferable. It is a base.
- P is 1 to 50, preferably 1 to 10, and q is 1 to 99, preferably 4 to 50. If p is small, the silicone composition may not have a sufficient reinforcing effect, and if p is large, crosslinking may be non-uniform. If q is small, oil bleeding may be severe, and when q is large. The treatment of the surface of the thermally conductive filler may be insufficient. Further, p + q is 5 ⁇ p + q ⁇ 100, and preferably 5 ⁇ p + q ⁇ 60. If p + q is less than 5, oil bleeding of the composition may be severe and reliability may be deteriorated. If p + q is larger than 100, the wettability with the filler may be insufficient.
- the blending amount is 1 to 50 parts by mass, preferably 2 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B). If the amount of component (J) is less than the above lower limit value, sufficient wettability and reinforcing effect may not be exhibited. If the amount of the component (J) is more than the above upper limit, oil bleeding from the composition may become severe.
- the addition-curable silicone composition of the present invention may contain a non-reactive organo (poly) siloxane such as methylpolysiloxane in order to adjust the strength and viscosity of the composition. Further, in order to prevent the deterioration of the silicone composition, a conventionally known antioxidant such as 2,6-di-tert-butyl-4-methylphenol may be contained if necessary. Furthermore, a dye, a pigment, a flame retardant, an anti-settling agent, a thixotropy improving agent, or the like can be added if necessary.
- Step of producing silicone composition The method for producing the silicone composition of the present invention will be described.
- the method for producing the silicone composition according to the present invention is not particularly limited, but contains the above-mentioned components (A) to (G), and optionally (H), (I) and (J). And a step of producing a silicone composition.
- the above-mentioned components (A) to (G) and, if necessary, the components (H), (I), and (J) are mixed, for example, with a Trimix, a Twin Mix, a planetary mixer (all are mixers manufactured by Inoue Co., Ltd.). No.), an ultramixer (registered trademark of a mixer manufactured by Mizuho Industry Co., Ltd.), and a mixer such as Hibis Dispermix (registered trademark of a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.). Is mentioned.
- the addition-curable silicone composition of the present invention may be mixed while heating.
- the heating conditions are not particularly limited, but the temperature is usually 25 to 220 ° C., preferably 40 to 200 ° C., particularly preferably 50 to 200 ° C., and the time is usually 3 minutes to 24 hours, preferably 5 minutes to It is 12 hours, particularly preferably 10 minutes to 6 hours.
- deaeration may be performed during heating.
- the components (A) to (C) and (F) are heated and mixed at 50 to 200 ° C. in advance, and then the components (D), (E) and (G) are mixed. It is preferable from the viewpoint that the product exhibits good adhesive strength.
- the components (A) to (C), (F), (I) and (J) should be added at 50 to 200 ° C in advance. It is preferable that the components (D), (E), (G) and (H) are mixed by heating and mixing.
- the addition-curable silicone composition of the present invention has a viscosity measured at 25 ° C. of preferably 1 to 1,000 Pa ⁇ s, more preferably 20 to 700 Pa ⁇ s, still more preferably 40 to 600 Pa ⁇ s. . If the viscosity is less than 1 Pa ⁇ s, it may be difficult to maintain the shape and the workability may be deteriorated. Further, when the viscosity exceeds 1,000 Pa ⁇ s, workability may be deteriorated, such as difficulty in discharging or applying.
- the viscosity can be obtained by adjusting the blending amount of each component described above.
- the addition-curable silicone composition of the present invention is heat conductive and usually has a heat conductivity of 0.5 to 10 W / m ⁇ K.
- the viscosity is a value measured at 25 ° C by a rotational viscometer
- the thermal conductivity is a value measured by a hot disk method.
- the addition-curable silicone composition of the present invention is suitable as a composition that is interposed between a heat generating member such as an electronic component such as an LSI or the like and a cooling member to transfer heat from the heat generating member to the cooling member to radiate the heat.
- a heat generating member such as an electronic component such as an LSI or the like
- a cooling member to transfer heat from the heat generating member to the cooling member to radiate the heat.
- the addition-curable silicone composition of the present invention can be cured by heat generated from a heat-generating member such as an electronic component, and after the addition-curable silicone composition of the present invention is applied, it is positively heat-cured. May be. This makes it possible to provide a semiconductor device in which a cured product of the addition-curable silicone composition of the present invention is interposed between a heat generating member and a cooling member.
- the curing conditions for heat-curing the addition-curable silicone composition of the present invention are not particularly limited, but are usually 80 to 200 ° C., preferably 100 to 180 ° C., 30 minutes to 4 hours, preferably 30. Minutes to 2 hours.
- the addition-curable silicone composition of the present invention has good adhesiveness to various adherends even if it contains a large amount of a thermally conductive filler, and thus can achieve both high thermal conductivity and strong adhesiveness. Therefore, it can be particularly suitably used as a heat-dissipating grease used for a large-sized or large-sized semiconductor device.
- the kinematic viscosity is a value at 25 ° C. measured by an Ubbelohde Ostwald viscometer.
- Component A-1 Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25 ° C. of 600 mm 2 / s: SiVi group amount: 0.00014 mol / g
- Component B-1 Silicone resin represented by the following average composition formula: Kinematic viscosity of a solution of 50% by mass in a xylene solvent, 3.0 mm 2 / s, SiVi group amount: 0.0004 mol / g (SiO 4/2 ) 1.0 ((CH 2 ⁇ CH) (CH 3 ) 2 SiO 1/2 ) 0.12 ((CH 3 ) 3 SiO 1/2 ) 0.75
- Component C-1 Aluminum powder having an average particle size of 20.0 ⁇ m and aluminum powder having an average particle size of 2.0 ⁇ m premixed at a mass ratio of 60:40
- C-2 Average particle size of 1.0 ⁇ m Zinc oxide powder
- F Component F-1: 3-glycidoxypropyltrimethoxysilane represented by the following formula (9)
- G-1 Platinum-divinyltetramethyldisiloxane complex dissolved in the same dimethylpolysiloxane as A-1 (platinum atom content: 1% by mass)
- Examples 1 to 10 and Comparative Examples 1 to 8 Preparation of Silicone Composition
- the components (A) to (J) described above were blended in the blending amounts shown in Tables 1 to 4 below by the method shown below to prepare a silicone composition.
- the mass of the component (G) in the table is the mass of a solution (platinum atom content: 1 mass%) in which a platinum-divinyltetramethyldisiloxane complex is dissolved in dimethylpolysiloxane.
- 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 components (A), (B), and (J).
- Components (A), (B), (C), (I) and (J) were added to a 5 liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) and mixed at 170 ° C. for 1 hour. The mixture was cooled to 40 ° C or lower, then the component (F) was added and mixed at 70 ° C for 1 hour. The mixture was cooled to 40 ° C. or lower, and then the components (G), (H), (D), and (E) were added and mixed so as to be uniform to prepare a silicone composition.
- the silicone compositions of Examples 1 to 10 satisfying the requirements of the present invention have a large adhesive force to the nickel-plated copper plate. That is, it can be judged that the adhesiveness is excellent.
- the silicone compositions of Comparative Examples 1 to 8 have low adhesive strength to the nickel-plated copper plate. That is, it can be determined that the adhesiveness is poor. Therefore, since the addition-curable silicone composition of the present invention has good adhesiveness to various adherends even if it contains a large amount of a thermally conductive filler, it is possible to achieve both high thermal conductivity and strong adhesiveness. I was able to confirm. Due to such characteristics, the addition-curable silicone composition of the present invention can be particularly suitably used as a heat-dissipating grease used for large-scale or large-scale semiconductor devices.
- the present invention is not limited to the above embodiment.
- the above-described embodiments are merely examples, and the present invention has substantially the same configuration as the technical idea described in the scope of claims of the present invention, and has any similar effects to the present invention. It is included in the technical scope of.
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Abstract
Description
[1].
(A)1分子中に少なくとも2個の脂肪族不飽和炭化水素基を有し、25℃での動粘度が60~100,000mm2/sであるオルガノポリシロキサン: 100質量部、
(B)1分子中に少なくとも1個の脂肪族不飽和炭化水素基を有するシリコーンレジン:
(A)成分100質量部に対して0~100質量部、
(C)金属、金属酸化物、金属水酸化物、金属窒化物、金属炭化物、及び炭素の同素体からなる群より選ばれる少なくとも1種の熱伝導性充填剤: 組成物全体に対し10~95質量%となる量、
(D)1分子中に2個以上のケイ素原子に結合した水素原子を有するオルガノハイドロジェンポリシロキサン: (A)及び(B)成分中の脂肪族不飽和炭化水素基の個数の合計に対するSiH基の個数が0.5~5となる量、
(E)パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、及びパーオキシジカーボネートから選ばれる有機過酸化物: (A)成分と(B)成分の合計100質量部に対して0.01~10質量部、
(F)下記一般式(1)で示される加水分解性オルガノシラン化合物: (A)成分と(B)成分の合計100質量部に対して0.1~30質量部、
(G)白金族金属触媒: 有効量
を必須成分とする付加硬化型シリコーン組成物。
[2].
さらに、(H)反応制御剤を(A)成分と(B)成分の合計100質量部に対して0.05~5質量部含む[1]に記載の付加硬化型シリコーン組成物。
[3].
さらに、(I)下記一般式(2)で表される加水分解性オルガノポリシロキサン化合物を(A)成分と(B)成分の合計100質量部に対して1~200質量部含む[1]又は[2]に記載の付加硬化型シリコーン組成物。
[4].
さらに、(J)下記一般式(3)で表される加水分解性オルガノポリシロキサン化合物を(A)成分と(B)成分の合計100質量部に対して1~50質量部含む[1]~[3]のいずれかに記載の付加硬化型シリコーン組成物。
[5].
[1]~[4]のいずれかに記載の付加硬化型シリコーン組成物の製造方法であって、予め(A)~(C)及び(F)成分を50~200℃で加熱混合し、その後、(D)、(E)及び(G)成分を混合することを特徴とする付加硬化型シリコーン組成物の製造方法。
(A)成分
(A)成分は、1分子中に少なくとも2個、好ましくは2~100個、より好ましくは2~50個の脂肪族不飽和炭化水素基を有し、25℃での動粘度が60~100,000mm2/sであるオルガノポリシロキサンである。
なお、(A)成分のオルガノポリシロキサンは、1分子中に0.00001~0.01mol/g、特には0.0001~0.01mol/gの脂肪族不飽和炭化水素基を有することが好ましい。
本発明において、動粘度は、ウベローデ型オストワルド粘度計により測定した25℃における値である(以下、同じ)。
(B)成分はシリコーンレジンである。(B)成分のシリコーンレジンは、1分子中に少なくとも1個の脂肪族不飽和炭化水素基を有するものである。(B)成分は配合しなくてもよいが、(B)成分のシリコーンレジンを含有した場合、本発明の付加硬化型シリコーン組成物より得られる硬化物の接着強度を向上することができる。
(C)成分は、金属、金属酸化物、金属水酸化物、金属窒化物、金属炭化物、及び炭素の同素体からなる群より選ばれる1種以上の熱伝導性充填剤である。例えば、アルミニウム、銀、銅、金属ケイ素、アルミナ、酸化亜鉛、酸化マグネシウム、酸化アルミニウム、二酸化ケイ素、酸化セリウム、酸化鉄、水酸化アルミニウム、水酸化セリウム、窒化アルミニウム、窒化ホウ素、炭化ケイ素、ダイヤモンド、グラファイト、カーボンナノチューブ、グラフェン等が挙げられる。これらは1種単独で又は2種以上を適宜組み合わせて用いることができ、大粒子成分と小粒子成分を組み合わせたものであることが好ましい。
また、小粒子成分の平均粒径は、0.01μmより小さいと得られる組成物の粘度が高くなりすぎ、伸展性の乏しいものとなるおそれがあり、10μm以上だと得られる組成物が不均一となるおそれがあるため、0.01μm以上10μm未満の範囲、好ましくは0.1~4μmの範囲がよい。
大粒子成分と小粒子成分の割合は特に限定されず、9:1~1:9(質量比)の範囲が好ましい。また、大粒子成分及び小粒子成分の形状は、球状、不定形状、針状等、特に限定されるものではない。
なお、平均粒径は、例えば、レーザー光回折法による粒度分布測定における体積基準の平均値(又はメジアン径)として求めることができる。
(D)成分は、ケイ素原子に結合した水素原子(SiH基)を1分子中に2個以上、好ましくは2~100個、さらに好ましくは2~20個有するオルガノハイドロジェンポリシロキサンである。該オルガノハイドロジェンポリシロキサンは、分子中のSiH基が、上述した(A)及び(B)成分が有する脂肪族不飽和炭化水素基と白金族金属触媒の存在下に付加反応し、架橋構造を形成できるものであればよい。
(E)成分は、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、及びパーオキシジカーボネートから選ばれる、特定の条件下で分解して遊離ラジカルを生じる有機過酸化物であり、1種単独で又は2種以上を適宜組み合わせて用いることができ、本発明で得られるシリコーン組成物のシロキサン架橋構造内中にシルアルキレン構造を導入する反応開始剤として作用する。
(F)成分は、下記一般式(1)で示される加水分解性オルガノシラン化合物であり、1種単独で又は2種以上を適宜組み合わせて用いることができ、本発明で得られるシリコーン組成物の接着性を向上するための接着助剤として作用する。
置換基を有してもよい1価飽和脂肪族炭化水素基として、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖アルキル基、イソプロピル基、イソブチル基、tert-ブチル基、イソペンチル基、ネオペンチル基等の分岐鎖アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、クロロメチル基、3-クロロプロピル基、3,3,3-トリフルオロプロピル基、ブロモプロピル基等のハロゲン置換アルキル基などの、炭素数1~10、好ましくは炭素数1~8、さらに好ましくは炭素数1~6のものである。
置換基を有してもよい1価不飽和脂肪族炭化水素基として、具体的には、エテニル基、1-メチルエテニル基、2-プロペニル基等のアルケニル基、エチニル基、2-プロピニル基等のアルキニル基などの、炭素数2~10、好ましくは炭素数2~8、さらに好ましくは炭素数2~6のものである。
置換基を有してもよい1価芳香族炭化水素基として、具体的には、フェニル基、トリル基等のアリール基、ベンジル基、2-フェニルエチル基等のアラルキル基、α,α,α-トリフルオロトリル基、クロロベンジル基等のハロゲン置換アリール基などの、炭素数6~10、好ましくは炭素数6~8、さらに好ましくは炭素数6のものである。
R1としては、これらの中でも、メチル基、エチル基、3,3,3-トリフルオロプロピル基、フェニル基が好ましく、さらに好ましくはメチル基、エチル基、フェニル基であり、特に好ましくはメチル基である。
ここで、アルコキシシリル基としては、トリメトキシ基、ジメトキシメチル基、メトキシジメチルシリル基、トリエトキシ基、ジエトキシメチル基、エトキシジメチルシリル基等が例示でき、これらの中でもトリメトキシ基、トリエトキシ基が好ましい。
-CH2OCH2CH2CH2-
-CH2OCH2CH2CH2CH2CH2CH2CH2CH2-
-(CH2)x-
(xは1~20の整数。)
(G)成分は白金族金属触媒であり、上述した成分の付加反応を促進するために機能する。白金族金属触媒は、付加反応に用いられる従来公知のものを使用することができる。例えば、白金系、パラジウム系、ロジウム系の触媒が挙げられるが、中でも比較的入手しやすい白金又は白金化合物が好ましい。例えば、白金の単体、白金黒、塩化白金酸、白金-オレフィン錯体、白金-アルコール錯体、白金配位化合物等が挙げられる。白金族金属触媒は1種単独でも2種以上を組み合わせて使用してもよい。
(H)成分は室温でのヒドロシリル化反応の進行を抑える反応制御剤であり、シェルフライフ、ポットライフを延長させるために添加することができる。該反応制御剤は、付加硬化型シリコーン組成物に使用される従来公知の制御剤を使用することができる。これには、例えば、アセチレンアルコール類(例えば、エチニルメチルデシルカルビノール、1-エチニル-1-シクロヘキサノール、3,5-ジメチル-1-ヘキシン-3-オール)等のアセチレン化合物、トリブチルアミン、テトラメチルエチレンジアミン、ベンゾトリアゾール等の各種窒素化合物、トリフェニルホスフィン等の有機リン化合物、オキシム化合物、有機クロロ化合物等が挙げられる。
また反応制御剤は、シリコーン組成物への分散性をよくするために、オルガノ(ポリ)シロキサンやトルエン等で希釈して使用してもよい。
本発明の付加硬化型シリコーン組成物には、さらに、下記一般式(2)で表される加水分解性オルガノポリシロキサン化合物(I)を配合することができる。(I)成分の加水分解性オルガノポリシロキサン化合物は、熱伝導性充填剤表面を処理するために用いるものであり、充填剤の高充填化を補助する役割を担う。
本発明の付加硬化型シリコーン組成物には、さらに、下記一般式(3)で表される加水分解性オルガノポリシロキサン化合物(J)を配合することができる。(J)成分の加水分解性オルガノポリシロキサン化合物は、熱伝導性充填剤表面を処理するとともに、シリコーン組成物の強度を高める補強効果を有する。
本発明の付加硬化型シリコーン組成物は、組成物の強度や粘度を調整するために、メチルポリシロキサン等の反応性を有さないオルガノ(ポリ)シロキサンを含有してもよい。さらに、シリコーン組成物の劣化を防ぐために、2,6-ジ-tert-ブチル-4-メチルフェノール等の、従来公知の酸化防止剤を必要に応じて含有してもよい。さらに、染料、顔料、難燃剤、沈降防止剤、又はチクソ性向上剤等を、必要に応じて配合することができる。
本発明におけるシリコーン組成物の製造方法について説明する。本発明におけるシリコーン組成物の製造方法は特に限定されるものではないが、上述の(A)~(G)成分、必要によりこれに加えて(H)、(I)、(J)成分を含有するシリコーン組成物を作製する工程を有する。
本発明においては、予め(A)~(C)及び(F)成分を50~200℃で加熱混合し、その後、(D)、(E)及び(G)成分を混合することが、シリコーン組成物が良好な接着力を発現する観点から好ましい。なお、任意成分である(H)、(I)、(J)成分を配合する場合は、予め(A)~(C)、(F)、(I)及び(J)成分を50~200℃で加熱混合し、その後、(D)、(E)、(G)及び(H)成分を混合することが好ましい。
また本発明の付加硬化型シリコーン組成物は熱伝導性であり、通常、0.5~10W/m・Kの熱伝導率を有する。
なお、本発明において、粘度は、回転粘度計により測定した25℃における値であり、熱伝導率は、ホットディスク法により測定した値である。
初めに、本発明の付加硬化型シリコーン組成物を調製する以下の各成分を用意した。
A-1:両末端がジメチルビニルシリル基で封鎖され、25℃における動粘度が600mm2/sのジメチルポリシロキサン:SiVi基量0.00014mol/g
B-1:下記平均組成式で示されるシリコーンレジン:キシレン溶媒中50質量%溶液とした時の動粘度3.0mm2/s、SiVi基量0.0004mol/g
(SiO4/2)1.0((CH2=CH)(CH3)2SiO1/2)0.12((CH3)3SiO1/2)0.75
C-1:平均粒径20.0μmのアルミニウム粉末と平均粒径2.0μmのアルミニウム粉末を60:40の質量比で予め混合したアルミニウム粉末
C-2:平均粒径1.0μmの酸化亜鉛粉末
G-1:白金-ジビニルテトラメチルジシロキサン錯体を上記A-1と同じジメチルポリシロキサンに溶解した溶液(白金原子含有量:1質量%)
シリコーン組成物の調製
上記(A)~(J)成分を、下記表1~4に示す配合量で、下記に示す方法で配合してシリコーン組成物を調製した。なお、表において(G)成分の質量は、白金-ジビニルテトラメチルジシロキサン錯体をジメチルポリシロキサンに溶解した溶液(白金原子含有量:1質量%)の質量である。また、SiH/SiViは(A)成分、(B)成分、及び(J)成分中のアルケニル基の個数の合計に対する(D)成分のSiH基の個数の合計の比である。
5リットルのプラネタリーミキサー((株)井上製作所製)に、(A)、(B)、(C)、(I)及び(J)成分を加え、170℃で1時間混合した。40℃以下になるまで冷却し、次に(F)成分を加え、70℃で1時間混合した。40℃以下になるまで冷却し、次に(G)、(H)、(D)、及び(E)成分を加え均一になるように混合し、シリコーン組成物を調製した。
各シリコーン組成物の絶対粘度を、マルコム粘度計(タイプPC-1T)を用いて25℃で測定した(ロータAで10rpm、ズリ速度6[1/s])。
各シリコーン組成物をキッチンラップで包み、熱伝導率を京都電子工業(株)製TPS-2500Sで測定した。
各シリコーン組成物を10mm×10mmのシリコンウェハと20mm×20mmのニッケルめっき銅板の間に挟み込み、1.8kgfのクリップによって加圧しながら150℃にて60分間加熱硬化した。その後、Dage series-4000PXY(Dage Deutchland GmbH製)を用いてせん断接着強度を測定した。
従って、本発明の付加硬化型シリコーン組成物は、熱伝導性充填剤を多量に含有しても各種被着体に対し良好な接着性を有するため、高熱伝導率と強接着性の両立が可能であると確認できた。このような特性を有するため、本発明の付加硬化型シリコーン組成物は、発熱量が多い、又は大型の半導体装置に使用する放熱グリースとして特に好適に利用することができる。
Claims (5)
- (A)1分子中に少なくとも2個の脂肪族不飽和炭化水素基を有し、25℃での動粘度が60~100,000mm2/sであるオルガノポリシロキサン: 100質量部、
(B)1分子中に少なくとも1個の脂肪族不飽和炭化水素基を有するシリコーンレジン:
(A)成分100質量部に対して0~100質量部、
(C)金属、金属酸化物、金属水酸化物、金属窒化物、金属炭化物、及び炭素の同素体からなる群より選ばれる少なくとも1種の熱伝導性充填剤: 組成物全体に対し10~95質量%となる量、
(D)1分子中に2個以上のケイ素原子に結合した水素原子を有するオルガノハイドロジェンポリシロキサン: (A)及び(B)成分中の脂肪族不飽和炭化水素基の個数の合計に対するSiH基の個数が0.5~5となる量、
(E)パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、及びパーオキシジカーボネートから選ばれる有機過酸化物: (A)成分と(B)成分の合計100質量部に対して0.01~10質量部、
(F)下記一般式(1)で示される加水分解性オルガノシラン化合物: (A)成分と(B)成分の合計100質量部に対して0.1~30質量部、
(G)白金族金属触媒: 有効量
を必須成分とする付加硬化型シリコーン組成物。 - さらに、(H)反応制御剤を(A)成分と(B)成分の合計100質量部に対して0.05~5質量部含む請求項1に記載の付加硬化型シリコーン組成物。
- 請求項1~4のいずれか1項に記載の付加硬化型シリコーン組成物の製造方法であって、予め(A)~(C)及び(F)成分を50~200℃で加熱混合し、その後、(D)、(E)及び(G)成分を混合することを特徴とする付加硬化型シリコーン組成物の製造方法。
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JP7476795B2 (ja) | 2018-10-22 | 2024-05-01 | 信越化学工業株式会社 | 付加硬化型シリコーン組成物 |
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