WO2003004567A1 - High thermal conductivity spin castable potting compound - Google Patents
High thermal conductivity spin castable potting compound Download PDFInfo
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- WO2003004567A1 WO2003004567A1 PCT/US2002/021250 US0221250W WO03004567A1 WO 2003004567 A1 WO2003004567 A1 WO 2003004567A1 US 0221250 W US0221250 W US 0221250W WO 03004567 A1 WO03004567 A1 WO 03004567A1
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- 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
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- 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
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- 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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- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- 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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- 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
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- 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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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
Definitions
- the invention is directed to addition-curable polysiloxane potting compounds used to encapsulate circuitry.
- a thermally conductive material is conventionally used to establish thermal contact between the heat sink and the heat-producing components and/or the circuit board.
- Illustrative disclosures relating to heat dissipation in circuit boards include Cipolla et al., U.S. Pat. No. 5,268,815 (1993); Kim et al., U.S. Pat. No. 5,552,635 (1996); and Shuff, U.S. Pat. No. 5,812,374 (1998).
- the present invention is directed to addition-curable silicone gels and readily adapted as pottants and encapsulants for preserving and protecting delicate electronic circuitry in severe environments. Additional applications of silicone gels according to the present invention include optical joint sealants, optical waveguides, keyboard handrests, and clean room HEPA filter sealants.
- Conventional addition- curable silicone gel compositions comprising an alkenyl-containing polydiorganosiloxane polymer, an organohydrogenpolysiloxane, and a hydrosiiylation catalyst are known in the art from U.S. Pat. No. 4,374,967 to Brown et al.; U.S. Pat. No. 4,529,789 to Kroupa; U.S. Pat. No. 5,332,795 to Fujiki et al.
- crosslinked silicone prepared by the platinum-catalyzed reaction between a vinyl-functionalized PDMS and a hydride- functionalized PDMS.
- Gelest, Inc. produces commercial curing packages useful with polydimethyisiloxane.
- Such gels can be formed in a number of ways.
- One method synthesizes the crosslinked polymer in the presence of a non-reactive extender fluid, e.g. trimethylsiloxy-terminated PDMS.
- the method according to the present invention fabricates the silicone gel by reacting a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone in such a fashion that a soft, fluid-extended system is obtained.
- a vinyl-rich sol fraction is obtained.
- Suitable examples of either of these gel systems are taught in, inter alia, Debbaut, U.S. Pat. No. 4,600,261 (1986); Debbaut, U.S. Pat. No. 4,634,207 (1987); Debbaut, U.S. Pat. No. 5,357,057 (1994); Dubrow et al., U.S. Pat. No. 5,079,300 (1992); Dubrow et al., U.S. Pat. No. 4,777,063 (1988); and Nelson, U.S. Pat. No. 3,020,260 (1962); the disclosures of which are incorporated herein by reference.
- U.S. Pat. No. 5,571 ,853 to Ikeno et al. discloses a gel-forming silicone composition comprising (A) an organopolysiloxane containing a silicon-bonded alkenyl group or groups in an average amount of from 0.15 to 0.35 mol % based on all silicon-bonded organic groups contained per molecule, (B) a non-functional organopolysiloxane, (C) an organohydrogenpolysiloxane containing an average of 2 silicon-bonded hydrogen atoms per molecule, and (D) an addition reaction catalyst.
- the silicone composition is able to give a gel-like cured silicone product with low modulus of elasticity while retaining flexibility.
- U.S. Pat. No. 6,225,433 discloses a curable silicon composition, comprising (A) 100 parts by weight of an organopolysiloxane containing silicon-bonded aryl groups and at least two alkenyl groups per molecule, and having a viscosity of from 0.01 to 1 ,000 Pa-s at 25° C, wherein the aryl groups comprise from 1 to 40 mole % of the total silicon-bonded organic groups in the organopolysiloxane; (B) an organopolysiloxane having a viscosity of from 0.001 to 10 Pa-sec. at 25° C.
- organopolysiloxane having a viscosity of from 0.01 to 10,000 Pa-s at 25° C. provided that when the organopolysiloxane contains aryl groups, the aryl groups comprise less than 1 mole % or more than 40 mole % of the total silicon-bonded organic groups in the organopolysiloxane.
- the organopolysiloxane cures to form a silicone having a complex modulus less than or equal to 1x10 8 Pa at -65 °C and a shear frequency of 10 Hz or a cured silicone having a Young's modulus less than or equal to 2.9x10 s Pa at -65° C.
- a potting compound for encapsulating circuitry having high thermoconductivity for dissipating heat and/or transferring heat to a heat sink, and away from the circuit assembly, while at the same time protecting the circuitry from mechanical stresses or avoiding the transmission of such stresses to the circuitry.
- a spin castable potting compound must be able to flow under its own weight when applied to a circuit module mounted on a turntable spinning at above 1000 rpm. The viscosity of a potting compound as measured by Brookfield DV-II, spindle 7 at 10 rpm after a 5-minute dwell of less than 150,000 cps.
- thermally conductive spin castable pottants exhibit a thermal conductivity of about 0.5 w/m°K. Higher thermal conductivity is desired.
- a thermally conductive silicone gel is produced by reacting a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone.
- the thermal conductive components are a combination of at least three conductive solid fillers, aluminum oxide, zinc oxide and boron nitride.
- a high thermal conductive spin castable potting compound is embodied in a two-part addition-crosslinkable compositions wherein a vinyl-terminated siloxane crosslinks with Si-bonded hydrogen (hydrosiiylation) in the presence of a platinum catalyst and contains a combination of thermal conductive materials comprising aluminum oxide, zinc oxide and boron nitride, in the substantial absence of aluminum nitride, as specified hereinbelow.
- thermal conductive materials comprising aluminum oxide, zinc oxide and boron nitride, in the substantial absence of aluminum nitride, as specified hereinbelow.
- aluminum oxide, zinc oxide, titanium dioxide and boron nitride comprise the thermal conductive fillers.
- a method for encapsulating circuitry comprising the steps of spin casting a precured silicone composition, said composition comprises: a mixture of a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone together with alumina, zinc oxide and optionally boron nitride, wherein the precured pottant exhibits a Brookfield DVII (#7 spindle) 1 / 10 rpm of less than 250,000 / 175,000 cps at 25° C, a thermal conductivity of at least 2.75 to 4 W/mK and a Shore A hardness after curing of from 30 to 80.
- a Brookfield DVII #7 spindle
- alkenyl-terminated diorganopolysiloxanes are known and commercially available globally.
- alkenyl groups which may be bonded to the silicon atoms in component (A) include vinyl groups, allyl groups, butenyl groups and hexenyl groups. Preferably, these groups are vinyl groups.
- substituents other than alkenyl groups which may be bonded to the silicon atoms in component (A) include substituted or unsubstituted monovalent hydrocarbon groups, e.g., alkyl groups such as methyl groups, ethyl groups and propyl groups, etc.; aryl groups such as phenyl groups and tolyl groups, etc.; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups, etc.
- the polymer may also contain extremely small amounts of hydroxy groups, as well as alkoxy groups such as methoxy groups, etc.
- the preferred vinyl content is from 0.3 to 0.6, preferably from 0.3 to 0.45 mol%.
- alkenyl-terminated diorganopolysiloxanes are available for example VS- 50 and VS-100 from Hanse-Chemie.
- Ethylenically-unsaturated organopolysiloxanes and organohydrogenpolysiloxanes are taught in U.S. Pat. No. 3,159,662; U.S. Pat. No. 3,220,972; and U.S. Pat. No. 3,410,886.
- Preferred ethylenically-unsaturated organopolysiloxanes are those containing higher alkenyl groups such as those described by Keryk et al., U.S. Pat. No. 4,609,574.
- the disclosures of these references with respect to the ethylenically-unsaturated organopolysiloxane base polymers and organohydrogenpolysiloxane crosslinking agents disclosed therein are incorporated herein by reference.
- the crosslinker is a hydrogen-functionalized (e.g. hydride-terminal) organopolysiloxane having a viscosity between 1 and 1 ,000,000 cP at 25. degree. C. and containing an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl in the alkenyl-functionalized diorganopolysiloxane (i).
- Hydride-terminated organopolysiloxane is commercially available from OSI, Inc. under the VXL designation.
- the crosslinker may be a relatively low-molecular-weight H-functional oligosiloxane, such as tetramethyldisiloxane, or a highly polymeric polydimethylsiloxane having SiH groups positioned along the chain or terminally, or a silicone resin having SiH groups.
- the structure of the molecules forming the crosslinker may vary.
- the structure of a higher-molecular-weight, i.e. oligomeric or polymeric, SiH-containing siloxane may be linear, cyclic, branched or else resin-like or network-like.
- Linear and cyclic polysiloxanes are preferably composed of units of the formula R 3 SiO ⁇ /2, HR 2 SiO ⁇ , HRSi0 2 /2 and R 2 Si0 2 /2, where R is as defined above.
- Branched and network-like polysiloxanes additionally contain trifunctional and/or tetrafunctional units, preferably those of the formulae RSiOs 2, HSi ⁇ 3 /2 and SiO ⁇ . It is, of course, also possible to use mixtures of different siloxanes meeting the criteria for the crosslinker (B).
- the molecules forming crosslinker (B) may, in addition to the obligatory SiH groups, if desired at the same time also contain aliphatic unsaturated groups.
- SiH-functional compounds such as tetrakis(dimethylsiloxy)silane and tetramethylcyclotetrasiloxane
- high-molecular-weight SiH-containing siloxanes such as poly(hydromethyl)siloxane and poly(dimethylhydromethyl)siloxane with a viscosity of from 10 to 10,000 mPa.cndot.s at 25 °C, or analogous SiH-containing compounds in which some of the methyl groups have been replaced by 3,3,3-trifluoropropyl or phenyl groups.
- Suitable retarding moderators include acetylene compounds; organo-phosphorus compounds or polyvinylvinyl siloxanes, etc.
- the preferred retarder is a homopolymer of vinyl methyl siloxane, commercially available as VMS T-11 , from Gelest, Inc..
- the curable pottant exhibits a Brookfield DVII (#7 spindle) 1 / 10 rpm of 250,000 / 75,000 cps at 25° C, a thermal conductivity of at least 2, preferably 2.75 to 4 W/mK and a Shore A hardness after curing of from 30 to 80, and comprising,
- (A) is an alkenyl-terminated diorganopolysiloxane usable herein will exhibit a Brookfield LVF viscosity of between 50 and 100,000 cP at 25 °C. and contain at least two silicon-bonded alkenyl groups in each molecule. Preferably the viscosity ranges from 50 to 200 cps at 25 °C at 99% solids;
- (B) as crosslinker will comprise a hydrogen-functionalized organopolysiloxane having a viscosity between 1 and 100 Centistokes at 25°C. and contain an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl -functionalized diorganopolysiloxane;
- the electro-negative group terminated siloxane oligomers contain an electro-negative substituent in the terminating portion of the oligomeric compound include dimethylacetoxy-terminated polydimethylsiloxanes (PDMS), methyldiacetoxy-terminated PDMS, dimethylethoxy-terminated PDMS, aminopropyldimethyl-terminated PDMS, carbinol-terminated PDMS, monocarbinol- terminated PDMS, dimethylchloro-terminated PDMS, dimethylamino-terminated PDMS, dimethylethoxy-terminated PDMS, dimethylmethoxy PDMS, methacryloxypropyl-terminated PDMS, monomethylacryloxypropyl-terminated PDMS, carboxypropyldimethyl-terminated PDMS, chloromethyldimethyl-terminated PDMS, carboxypropyldimethyl-terminated PDMS and silanol-terminated polymethyl-
- PDMS dimethylacet
- the catalyst is a typical platinum hydrosiiylation catalyst and used in an amount specified below which is sufficient to effect the cure of the silicone composition.
- Suitable platinum catalyst is available form Gelest, Inc. under the SIP 6830 designation.
- Thermal conducting fillers are used at from 50- 92%, preferably from 80 - 92% by volume of a combination comprising aluminum oxide, zinc oxide, and boron nitride in one embodiment.
- the thermal conductive fillers comprise aluminum oxide, zinc oxide, titanium dioxide and boron nitride.
- thermally conductive materials alumina, zinc oxide, titanium dioxide and boron nitride are widely available in industry.
- Alumina, available as alpha alumina has a percent retained on 200 mesh screen of 0.2%, and a 95% pass through at 325 mesh screen.
- each thermal conductive filler there is preferably 40-65 vol. % of aluminum oxide is used together with from 5-25 vol. % of zinc oxide, and from 1.2 - 5 vol. % of boron nitride.
- the preferred amount of aluminum 55 -65 vol.% of aluminum oxide.
- the preferred amount of zinc oxide is from 5 - 10 vol.%.
- the preferred amount of titanium dioxide is from 6-12%.
- a preferred amount of boron nitride is from 1.2 - 5 vol. %.
- Zinc oxide is available form Zinc Corp. of America as USP-2 grade. Titanium dioxide is available from Dupont under the Tipure® R-900. Boron nitride is available from Advanced Ceramics under the PT 110-S designation.
- the thermal conductive fillers comprise 55- 65 vol. % of aluminum oxide, from 5 to 10 vol. % of zinc oxide, from 6 to 12 vol.% of titanium dioxide and from 1.2 - 5 vol. % of boron nitride.
- thermal conductive fillers comprising aluminum oxide, zinc oxide, and boron nitride is from 65 - 70 vol. %.
- the preferred total volume percent of thermal conductive fillers comprising aluminum oxide, zinc oxide, titanium dioxide and boron nitride is from 80 -92 vol. %.
- the potting compound may preferredly further include an organosiloxane resin other than en alkenyl-functional silane having of the average formula A
- R is a monovalent hydrocarbon group other than alkenyl and a is a numeral between 2.0 and 2.2 and b is a numeral between 0.9 and 1.0.
- the organofunctional siloxanes may be partially or completely hydrolyzed silanes. These provide viscosity control, wetting of fillers and to the substrate.
- the weight % is based on the amount of the organosiloxane resin plus (A) alkenyl-functionalized diorganopolysiloxane (B) and hydrogen-functionalized organopolysiloxane.
- organosiloxane include propyl trimethoxy silane, Dynasylan PTMO, from Degussa (Sivento).
- the Ethylenically-unsaturated organopolysiloxanes or organohydrogenpolysiloxanes are present along with other silanes or siloxanes absent ethylenic unsaturated group. These are groups as epoxy-, hydroxy, and alkyl-, halo-, aryl-functional silanes and siloxanes.
- the epoxy-substituted organosilanes are adaptable and are present as silane or a polyorganosiloxane and contain at least one epoxy group and a hydrolyzable group, each bonded to a silicon atom.
- the epoxy group is bound by means of an alkylene radical containing at least 1 carbon atom.
- the epoxide group can be part of a carbocyclic ring that is bonded to a silicon atom through an alkylene group.
- a preferred silane is represented by the formula R 1 - Si-R 2 m-R 3"m where R 1 represents an epoxyalkyl radical or an epoxy-substituted cycloalkyl radical, R 2 represents an alkyl radical, R 3 represents a hydrolyzable group and m is 0 or 1.
- suitable hydrolyzable groups represented by R 3 include but are not limited to alkoxy, carboxy, i.e. R'C(0)O- and ketoximo. In preferred embodiments the hydrolyzable groups are alkoxy groups containing from 1 to 4 carbon atoms.
- epoxy-fu nctional silanes are described in U.S. Pat. No. 3,455,877, which is incorporated herein by reference.
- Specific examples of epoxy-functional silane are mono(epoxyhydrocarbyl) trialkoxysilane wherein the carbon atoms of the epoxy group are separated form the silicon atom by an alkylene radical.
- One example is 3-glycidoxypropyltrialkoxysilane where the alkoxy group is methoxy or ethoxy.
- R in all instances herein is a divalent aliphatic, cycloaliphatic or aromatic saturated or unsaturated radical having from 1 to 20 carbon atoms, and is preferably an alkylene radical having from 1 to 9, most preferably 2 to 4 carbon atoms;
- R 1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, cycloalkyl radicals having from 4 to 7 ring carbon atoms, and aryl radicals having 6, 10, or 14 nuclear carbon atoms and including such aryl radicals containing one or more substituent alkyl groups having from 1 to 4 carbon atoms;
- R 2 is a monovalent aliphatic, cycloaliphatic or aromatic organic radical containing from 1 to 8 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, R 3 -
- R 3 is an alkylene group having from 1 to 4 carbon atoms (methyl, ethyl, propyl, butyl) and R 4 is an alkyl group having from 1 to 4 carbon atoms; and a is zero or 1 , preferably zero.
- Representative alkyl, halo- or aryl functional trialkoxysilanes include include: fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotnisopropoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri- tert-butoxysilane, and fluorotriphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n- propoxys
- Preferred alkyl trialkoxysilanes are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, , n-propyltrimethoxysilane, n- propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n- propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, and n-propyltri-tert- butoxysilane.
- the curing catalyst ( C) is a hydrosiiylation catalyst.
- the catalyst contains at least one of the following elements: Pt, Rh, Ru, Pd, Ni, e.g. Raney Nickel, and their combinations.
- the catalyst is optionally coupled to an inert or active support.
- preferred catalysts which can be used include platinum type catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of platinum and olefins, complexes of platinum and 1 ,3-divinyl-1 ,1 ,3,3- tetramethyldisiloxane, and powders on which platinum is supported, etc.
- the platinum catalysts are fully described in the literature.
- platinum type catalysts are especially desirable.
- An exemplary commercially available platinum catalyst is SIP 6830, available from Gelest, Inc.
- the amount of platinum metal of this catalyst that is contained is in the range of from 0.01 to 1 ,000 ppm (in weight units), with an amount of platinum metal in the range of 0.1 to 500 ppm being preferred, alternatively, in terms of volume percent to total components, catalyst amount can range from 0.0001 to 0.1 volume % of the potting compound.
- a dispersing agent which is an oligomer of n-propyltrimethoxysilane (PTMO) .
- PTMO n-propyltrimethoxysilane
- Commercial PTMO is available from Degussa-Huls, under the DYNASYLAN® mark, in particular Dynasylan PTMO.
- the gel composition is soft, i.e., it has a Shore A hardness of from 25 to 85, preferably from 50 to 60, and as a preformed pad embodiment, has a compression modulus, of less than 2 MPa , preferably less than 1 MPa.
- Compression modulus is the modulus at 10% compression as measured per ASTM D 575 (1991), using a 25.4 mm (1 in.) disk, 3 mm thick, at 0.1 mm/min compression rate.
- the gel precursor (procured compound) composition can be applied by conventional spin casting methods well known in the art to coat and encapsulate electronic circuitry.
- a pad of the potting compound may be applied by conventional printing processes such as gravure or flexographic printing or, alternatively, by methods which allow a thicker layer to be applied, such as screen printing or stencil printing, for example greater than 0.25 mm in thickness.
- a thicker layer may also be achieved by dispensing disconnected beads, lenses, ribbons, or dots of precursor composition which knit together during cure to form a continuous body of gel composition.
- a combination of dispensing and stencil printing may be employed to control final material size (area) and thickness.
- the preferred embodiment is a two-part compound containing the parts as follows: A -Side TABLE A
- Optional coloring pigments are preferably used to color one of the A or B sides.
- iron oxide such as available as Kroma Red, from Harcros Pigments Inc. is included the A- side.
- Method to make the compound is included the A- side.
- the B-side is prepared by mixing the components from Table B:
- This potting compound is usable as a room temp stable two-component meter mixed potting compound. It exhibits a viscosity as measured by Brookfield DV-2, spindle 7 at 10 rpm after a 5 minute dwell of 140,000 cps.
Abstract
Disclosed is a thermally conductive silicone gel is produced by reacting a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone. The thermal conductive components comprise at least three conductive solid fillers, aluminum oxide, zinc oxide and boron nitride. The invention is adaptable to spin casting for encapsulating electronic circuitry, among other uses.
Description
High Thermal Conductivity Spin Castable Potting Compound
Field of the Invention
[001] The invention is directed to addition-curable polysiloxane potting compounds used to encapsulate circuitry.
Background of the Invention
[002] A thermally conductive material is conventionally used to establish thermal contact between the heat sink and the heat-producing components and/or the circuit board. Illustrative disclosures relating to heat dissipation in circuit boards include Cipolla et al., U.S. Pat. No. 5,268,815 (1993); Kim et al., U.S. Pat. No. 5,552,635 (1996); and Shuff, U.S. Pat. No. 5,812,374 (1998).
[003] The present invention is directed to addition-curable silicone gels and readily adapted as pottants and encapsulants for preserving and protecting delicate electronic circuitry in severe environments. Additional applications of silicone gels according to the present invention include optical joint sealants, optical waveguides, keyboard handrests, and clean room HEPA filter sealants. Conventional addition- curable silicone gel compositions comprising an alkenyl-containing polydiorganosiloxane polymer, an organohydrogenpolysiloxane, and a hydrosiiylation catalyst are known in the art from U.S. Pat. No. 4,374,967 to Brown et al.; U.S. Pat. No. 4,529,789 to Kroupa; U.S. Pat. No. 5,332,795 to Fujiki et al.
[004] Specifically, there is provide in the art crosslinked silicone prepared by the platinum-catalyzed reaction between a vinyl-functionalized PDMS and a hydride- functionalized PDMS. Gelest, Inc. produces commercial curing packages useful with polydimethyisiloxane. Such gels can be formed in a number of ways. One method synthesizes the crosslinked polymer in the presence of a non-reactive
extender fluid, e.g. trimethylsiloxy-terminated PDMS. The method according to the present invention fabricates the silicone gel by reacting a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone in such a fashion that a soft, fluid-extended system is obtained.
[005] In the reaction of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone, a vinyl-rich sol fraction is obtained. Suitable examples of either of these gel systems are taught in, inter alia, Debbaut, U.S. Pat. No. 4,600,261 (1986); Debbaut, U.S. Pat. No. 4,634,207 (1987); Debbaut, U.S. Pat. No. 5,357,057 (1994); Dubrow et al., U.S. Pat. No. 5,079,300 (1992); Dubrow et al., U.S. Pat. No. 4,777,063 (1988); and Nelson, U.S. Pat. No. 3,020,260 (1962); the disclosures of which are incorporated herein by reference.
[006] U.S. Pat. No. 5,571 ,853 to Ikeno et al. discloses a gel-forming silicone composition comprising (A) an organopolysiloxane containing a silicon-bonded alkenyl group or groups in an average amount of from 0.15 to 0.35 mol % based on all silicon-bonded organic groups contained per molecule, (B) a non-functional organopolysiloxane, (C) an organohydrogenpolysiloxane containing an average of 2 silicon-bonded hydrogen atoms per molecule, and (D) an addition reaction catalyst. The silicone composition is able to give a gel-like cured silicone product with low modulus of elasticity while retaining flexibility.
[007] U.S. Pat. No. 6,225,433 discloses a curable silicon composition, comprising (A) 100 parts by weight of an organopolysiloxane containing silicon-bonded aryl groups and at least two alkenyl groups per molecule, and having a viscosity of from 0.01 to 1 ,000 Pa-s at 25° C, wherein the aryl groups comprise from 1 to 40 mole % of the total silicon-bonded organic groups in the organopolysiloxane; (B) an organopolysiloxane having a viscosity of from 0.001 to 10 Pa-sec. at 25° C. and containing at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity sufficient to cure the composition; (C) a platinum catalyst in a quantity sufficient to
cure the composition; and (D) 0.00001 to 100 parts by weight of an organopolysiloxane having a viscosity of from 0.01 to 10,000 Pa-s at 25° C. provided that when the organopolysiloxane contains aryl groups, the aryl groups comprise less than 1 mole % or more than 40 mole % of the total silicon-bonded organic groups in the organopolysiloxane. The organopolysiloxane cures to form a silicone having a complex modulus less than or equal to 1x108 Pa at -65 °C and a shear frequency of 10 Hz or a cured silicone having a Young's modulus less than or equal to 2.9x10s Pa at -65° C.
[008] Thus, it is desirable to develop a potting compound for encapsulating circuitry having high thermoconductivity for dissipating heat and/or transferring heat to a heat sink, and away from the circuit assembly, while at the same time protecting the circuitry from mechanical stresses or avoiding the transmission of such stresses to the circuitry. A spin castable potting compound must be able to flow under its own weight when applied to a circuit module mounted on a turntable spinning at above 1000 rpm. The viscosity of a potting compound as measured by Brookfield DV-II, spindle 7 at 10 rpm after a 5-minute dwell of less than 150,000 cps.
[009] Exemplary of the current state of the art, thermally conductive spin castable pottants exhibit a thermal conductivity of about 0.5 w/m°K. Higher thermal conductivity is desired.
[010] In attempts to increase the amount of thermally conductive filler loadings an unacceptable rise in viscosity occurs which would prohibit the application of the spin casting method. Improved thermal conductivity in the use of high loadings of conductive filler in a spin castable composition is desired.
Summary Of The Invention
[011] In a basic aspect of the invention a thermally conductive silicone gel is produced by reacting a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone. The thermal conductive components are a combination of at least three conductive solid fillers, aluminum oxide, zinc oxide and boron nitride.
[012] In another aspect of the invention there is provided a high thermal conductive spin castable potting compound is embodied in a two-part addition-crosslinkable compositions wherein a vinyl-terminated siloxane crosslinks with Si-bonded hydrogen (hydrosiiylation) in the presence of a platinum catalyst and contains a combination of thermal conductive materials comprising aluminum oxide, zinc oxide and boron nitride, in the substantial absence of aluminum nitride, as specified hereinbelow. In an alternative aluminum oxide, zinc oxide, titanium dioxide and boron nitride comprise the thermal conductive fillers.
[013] In another aspect there is provided a method for encapsulating circuitry , comprising the steps of spin casting a precured silicone composition, said composition comprises: a mixture of a stoichiometric excess of a multifunctional vinyl-substituted silicone with a multifunctional hydride-substituted silicone together with alumina, zinc oxide and optionally boron nitride, wherein the precured pottant exhibits a Brookfield DVII (#7 spindle) 1 / 10 rpm of less than 250,000 / 175,000 cps at 25° C, a thermal conductivity of at least 2.75 to 4 W/mK and a Shore A hardness after curing of from 30 to 80.
Detailed Description of the Preferred Embodiments
[014] The spin castable potting compound components (A) - (F) are described hereinbelow.
(A) Alkenyl-terminated Diorganopolysiloxane
(B) Crosslinker
(C) electronegative group terminated PDMS
(D) Hydrosilation catalyst
(E) Curing Rate Retarder
(F) Thermal conductive Fillers
(A) Alkenyl-Terminated Diorαanobolvsiloxane
[015] The alkenyl-terminated diorganopolysiloxanes are known and commercially available globally. Examples of alkenyl groups which may be bonded to the silicon atoms in component (A) include vinyl groups, allyl groups, butenyl groups and hexenyl groups. Preferably, these groups are vinyl groups. Examples of substituents other than alkenyl groups which may be bonded to the silicon atoms in component (A) include substituted or unsubstituted monovalent hydrocarbon groups, e.g., alkyl groups such as methyl groups, ethyl groups and propyl groups, etc.; aryl groups such as phenyl groups and tolyl groups, etc.; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups, etc. The polymer may also contain extremely small amounts of hydroxy groups, as well as alkoxy groups such as methoxy groups, etc. The preferred vinyl content is from 0.3 to 0.6, preferably from 0.3 to 0.45 mol%. Commercial alkenyl-terminated diorganopolysiloxanes are available for example VS- 50 and VS-100 from Hanse-Chemie. Ethylenically-unsaturated organopolysiloxanes
and organohydrogenpolysiloxanes are taught in U.S. Pat. No. 3,159,662; U.S. Pat. No. 3,220,972; and U.S. Pat. No. 3,410,886. Preferred ethylenically-unsaturated organopolysiloxanes are those containing higher alkenyl groups such as those described by Keryk et al., U.S. Pat. No. 4,609,574. Specific examples include siloxane polymers of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n- propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec- butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane. The disclosures of these references with respect to the ethylenically-unsaturated organopolysiloxane base polymers and organohydrogenpolysiloxane crosslinking agents disclosed therein are incorporated herein by reference.
(B) Crosslinker
[016] The crosslinker is a hydrogen-functionalized (e.g. hydride-terminal) organopolysiloxane having a viscosity between 1 and 1 ,000,000 cP at 25. degree. C. and containing an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl in the alkenyl-functionalized diorganopolysiloxane (i). Hydride-terminated organopolysiloxane is commercially available from OSI, Inc. under the VXL designation.
[017] The crosslinker may be a relatively low-molecular-weight H-functional oligosiloxane, such as tetramethyldisiloxane, or a highly polymeric polydimethylsiloxane having SiH groups positioned along the chain or terminally, or a silicone resin having SiH groups. The structure of the molecules forming the crosslinker may vary. In particular, the structure of a higher-molecular-weight, i.e. oligomeric or polymeric, SiH-containing siloxane may be linear, cyclic, branched or else resin-like or network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formula R3 SiOι/2, HR2 SiO^, HRSi02/2 and R2 Si02/2, where R is as defined above. Branched and network-like polysiloxanes additionally
contain trifunctional and/or tetrafunctional units, preferably those of the formulae RSiOs 2, HSiθ3/2 and SiO^. It is, of course, also possible to use mixtures of different siloxanes meeting the criteria for the crosslinker (B). In particular, the molecules forming crosslinker (B) may, in addition to the obligatory SiH groups, if desired at the same time also contain aliphatic unsaturated groups. Particular preference is given to the use of low-molecular-weight SiH-functional compounds, such as tetrakis(dimethylsiloxy)silane and tetramethylcyclotetrasiloxane, and also high-molecular-weight SiH-containing siloxanes, such as poly(hydromethyl)siloxane and poly(dimethylhydromethyl)siloxane with a viscosity of from 10 to 10,000 mPa.cndot.s at 25 °C, or analogous SiH-containing compounds in which some of the methyl groups have been replaced by 3,3,3-trifluoropropyl or phenyl groups.
(E) a curing rate retarder
[018] The cure rate of the potting compound must be moderated. Suitable retarding moderators include acetylene compounds; organo-phosphorus compounds or polyvinylvinyl siloxanes, etc. The preferred retarder is a homopolymer of vinyl methyl siloxane, commercially available as VMS T-11 , from Gelest, Inc..
Preferred components
[019] In a preferred embodiment, the curable pottant exhibits a Brookfield DVII (#7 spindle) 1 / 10 rpm of 250,000 / 75,000 cps at 25° C, a thermal conductivity of at least 2, preferably 2.75 to 4 W/mK and a Shore A hardness after curing of from 30 to 80, and comprising,
[020] In preference, (A) is an alkenyl-terminated diorganopolysiloxane usable herein will exhibit a Brookfield LVF viscosity of between 50 and 100,000 cP at 25 °C. and contain at least two silicon-bonded alkenyl groups in each molecule. Preferably the
viscosity ranges from 50 to 200 cps at 25 °C at 99% solids;
[021] In preference, (B) as crosslinker will comprise a hydrogen-functionalized organopolysiloxane having a viscosity between 1 and 100 Centistokes at 25°C. and contain an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl -functionalized diorganopolysiloxane;
[022] In preference, ( C) the electro-negative group terminated siloxane oligomers contain an electro-negative substituent in the terminating portion of the oligomeric compound include dimethylacetoxy-terminated polydimethylsiloxanes (PDMS), methyldiacetoxy-terminated PDMS, dimethylethoxy-terminated PDMS, aminopropyldimethyl-terminated PDMS, carbinol-terminated PDMS, monocarbinol- terminated PDMS, dimethylchloro-terminated PDMS, dimethylamino-terminated PDMS, dimethylethoxy-terminated PDMS, dimethylmethoxy PDMS, methacryloxypropyl-terminated PDMS, monomethylacryloxypropyl-terminated PDMS, carboxypropyldimethyl-terminated PDMS, chloromethyldimethyl-terminated PDMS, carboxypropyldimethyl-terminated PDMS and silanol-terminated polymethyl- 3,3,3-trifIuoropropylsiloxanes with monocarbinol-terminated PDMS being preferred. Electro-negative group terminated siloxane oligomers are available form Gelest, Inc. under the MCR C-22 designation.
(D) Catalyst
[023] The catalyst is a typical platinum hydrosiiylation catalyst and used in an amount specified below which is sufficient to effect the cure of the silicone composition. Suitable platinum catalyst is available form Gelest, Inc. under the SIP 6830 designation.
(F) Thermal conducting fillers.
[024] Thermally conductive fillers are used at from 50- 92%, preferably from 80 - 92% by volume of a combination comprising aluminum oxide, zinc oxide, and boron nitride in one embodiment. In a preferred embodiment the thermal conductive fillers comprise aluminum oxide, zinc oxide, titanium dioxide and boron nitride.
[025] The thermally conductive materials, alumina, zinc oxide, titanium dioxide and boron nitride are widely available in industry. Alumina, available as alpha alumina has a percent retained on 200 mesh screen of 0.2%, and a 95% pass through at 325 mesh screen. With respect to each thermal conductive filler, there is preferably 40-65 vol. % of aluminum oxide is used together with from 5-25 vol. % of zinc oxide, and from 1.2 - 5 vol. % of boron nitride. The preferred amount of aluminum 55 -65 vol.% of aluminum oxide. The preferred amount of zinc oxide is from 5 - 10 vol.%. The preferred amount of titanium dioxide is from 6-12%. A preferred amount of boron nitride is from 1.2 - 5 vol. %.
[026] Aluminum oxide is available from Whittaker Clark and Daniels. Zinc oxide is available form Zinc Corp. of America as USP-2 grade. Titanium dioxide is available from Dupont under the Tipure® R-900. Boron nitride is available from Advanced Ceramics under the PT 110-S designation.
[027] In a more preferred embodiment, the thermal conductive fillers comprise 55- 65 vol. % of aluminum oxide, from 5 to 10 vol. % of zinc oxide, from 6 to 12 vol.% of titanium dioxide and from 1.2 - 5 vol. % of boron nitride.
[028] The preferred total volume percent of thermal conductive fillers comprising aluminum oxide, zinc oxide, and boron nitride is from 65 - 70 vol. %.
[029] The preferred total volume percent of thermal conductive fillers comprising aluminum oxide, zinc oxide, titanium dioxide and boron nitride is from 80 -92 vol. %.
At this filler loading a surprising result is that the viscosity of the precured potting compound is in a flowable range, that can flow under only the centrifugal force from a spin casting turntable, enabling the potting compound to encapsulate the part to be coated.
[030] The potting compound may preferredly further include an organosiloxane resin other than en alkenyl-functional silane having of the average formula A
Ra Si02 (A)
where R is a monovalent hydrocarbon group other than alkenyl and a is a numeral between 2.0 and 2.2 and b is a numeral between 0.9 and 1.0. The organofunctional siloxanes may be partially or completely hydrolyzed silanes. These provide viscosity control, wetting of fillers and to the substrate. The weight % is based on the amount of the organosiloxane resin plus (A) alkenyl-functionalized diorganopolysiloxane (B) and hydrogen-functionalized organopolysiloxane. Examples of organosiloxane include propyl trimethoxy silane, Dynasylan PTMO, from Degussa (Sivento).
[031] Optionally and preferredly the Ethylenically-unsaturated organopolysiloxanes or organohydrogenpolysiloxanes are present along with other silanes or siloxanes absent ethylenic unsaturated group. These are groups as epoxy-, hydroxy, and alkyl-, halo-, aryl-functional silanes and siloxanes.
[032] The epoxy-substituted organosilanes are adaptable and are present as silane or a polyorganosiloxane and contain at least one epoxy group and a hydrolyzable group, each bonded to a silicon atom. The epoxy group is bound by means of an alkylene radical containing at least 1 carbon atom. Alternatively, the epoxide group can be part of a carbocyclic ring that is bonded to a silicon atom through an alkylene
group. A preferred silane is represented by the formula R1- Si-R2m-R3"m where R1 represents an epoxyalkyl radical or an epoxy-substituted cycloalkyl radical, R2 represents an alkyl radical, R3 represents a hydrolyzable group and m is 0 or 1. Examples of suitable hydrolyzable groups represented by R3 include but are not limited to alkoxy, carboxy, i.e. R'C(0)O- and ketoximo. In preferred embodiments the hydrolyzable groups are alkoxy groups containing from 1 to 4 carbon atoms.
[033] Numerous epoxy-fu nctional silanes are described in U.S. Pat. No. 3,455,877, which is incorporated herein by reference. Specific examples of epoxy-functional silane are mono(epoxyhydrocarbyl) trialkoxysilane wherein the carbon atoms of the epoxy group are separated form the silicon atom by an alkylene radical. One example is 3-glycidoxypropyltrialkoxysilane where the alkoxy group is methoxy or ethoxy.
[034] Representative hydroxyl group-containing silanes are also adaptable herein have the general structure:
(R')a
HO- R— Si- (OR2) 3-a (A)
wherein R in all instances herein is a divalent aliphatic, cycloaliphatic or aromatic saturated or unsaturated radical having from 1 to 20 carbon atoms, and is preferably an alkylene radical having from 1 to 9, most preferably 2 to 4 carbon atoms; R1 is a monovalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 20 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, cycloalkyl radicals having from 4 to 7 ring carbon atoms, and aryl radicals having 6, 10, or 14 nuclear carbon atoms and including such aryl radicals containing one or more substituent alkyl groups having from 1 to 4 carbon atoms; R2 is a monovalent aliphatic, cycloaliphatic or aromatic
organic radical containing from 1 to 8 carbon atoms, and is preferably selected from the group consisting of alkyl radicals having from 1 to 4 carbon atoms, R3-0-R4,
C - R, and where R3 is an alkylene group having from 1 to 4 carbon atoms (methyl, ethyl, propyl, butyl) and R4 is an alkyl group having from 1 to 4 carbon atoms; and a is zero or 1 , preferably zero.
[035] Representative alkyl, halo- or aryl functional trialkoxysilanes include include: fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotnisopropoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri- tert-butoxysilane, and fluorotriphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n- propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec- butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n- propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n- propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n- propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert- butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n- butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri- n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n- butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec- butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec- butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-
n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri- sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, γ-trifluoropropyltrimethoxysilane, and γ-trifluoropropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n- propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec- butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n- propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n- propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec- butoxysilane, di-n-propyldi-tert-butoxysilane, di-n-propyldiphenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec- butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n- butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n- butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di- n-butyldi-tert-butoxysilane, di-n-butyldiphenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec- butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec- butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldiphenoxysilane, di-tert- butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di- tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec- butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldiphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, and diphenyldiphenoxysilane.
[036] Preferred alkyl trialkoxysilanes are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, , n-propyltrimethoxysilane, n- propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n- propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, and n-propyltri-tert- butoxysilane.
[037] The curing catalyst ( C) is a hydrosiiylation catalyst. The catalyst contains at least one of the following elements: Pt, Rh, Ru, Pd, Ni, e.g. Raney Nickel, and their combinations. The catalyst is optionally coupled to an inert or active support. Examples of preferred catalysts which can be used include platinum type catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of platinum and olefins, complexes of platinum and 1 ,3-divinyl-1 ,1 ,3,3- tetramethyldisiloxane, and powders on which platinum is supported, etc. The platinum catalysts are fully described in the literature. Mention may in particular be made of the complexes of platinum and of an organic product described in United States Patents U.S. Pat. No. 3,159,601 , U.S. Pat. No. 3,159,602 and U.S. Pat. No. 3,220,972 and European Patents EP-A-057,459, EP-188,978 and EP-A-190,530 and the complexes of platinum and of vinylated organopolysiloxane described in United States Patents U.S. Pat. No. 3,419,593, U.S. Pat. No. 3,715,334, U.S. Pat. No. 3,377,432, U.S. Pat. No. 3,814,730, and U.S. Pat. No. 3,775,452, to Karstedt. . In particular, platinum type catalysts are especially desirable. An exemplary commercially available platinum catalyst is SIP 6830, available from Gelest, Inc. In the use of a platinum type catalyst the amount of platinum metal of this catalyst that is contained is in the range of from 0.01 to 1 ,000 ppm (in weight units), with an amount of platinum metal in the range of 0.1 to 500 ppm being preferred, alternatively, in terms of volume percent to total components, catalyst amount can range from 0.0001 to 0.1 volume % of the potting compound.
[038] Optionally up to 10 volume % preferably included in the potting compound is a dispersing agent (G) which is an oligomer of n-propyltrimethoxysilane (PTMO) . Commercial PTMO is available from Degussa-Huls, under the DYNASYLAN® mark, in particular Dynasylan PTMO.
General application methods
[039] The gel composition is soft, i.e., it has a Shore A hardness of from 25 to 85, preferably from 50 to 60, and as a preformed pad embodiment, has a compression modulus, of less than 2 MPa , preferably less than 1 MPa. Compression modulus is the modulus at 10% compression as measured per ASTM D 575 (1991), using a 25.4 mm (1 in.) disk, 3 mm thick, at 0.1 mm/min compression rate.
[040] The gel precursor (procured compound) composition can be applied by conventional spin casting methods well known in the art to coat and encapsulate electronic circuitry. Alternatively, a pad of the potting compound may be applied by conventional printing processes such as gravure or flexographic printing or, alternatively, by methods which allow a thicker layer to be applied, such as screen printing or stencil printing, for example greater than 0.25 mm in thickness. A thicker layer may also be achieved by dispensing disconnected beads, lenses, ribbons, or dots of precursor composition which knit together during cure to form a continuous body of gel composition. A combination of dispensing and stencil printing may be employed to control final material size (area) and thickness.
[041] The preferred embodiment is a two-part compound containing the parts as follows:
A -Side TABLE A
Chemical Description Material Manufacturer (Distributor) Range
(Vol%)
* Optional coloring pigments are preferably used to color one of the A or B sides.
Preferably iron oxide, such as available as Kroma Red, from Harcros Pigments Inc. is included the A- side.
Method to make the compound
[042] Using a double Planetary mixer, the A-side is prepared by mixing the components from table A:
1) adding 1 , 2, 3, 4, and 5 to a Ross® planetary mixer, and mixed for 5-10 min.
2) adding 6, and 1/3 of 7 and 8 to the mix and mixing for 10-15 min (at 30 RPM)
3) adding 1/3 of 7 and 8 to Ross, Mix 10-15 min. at 30 RPM)
4) add final 1/3 of 7 and 8 to Ross. Mix 30-35 min. at 30 RPM)
5) add 9, Mix 3-5 min to wet out, stop mixer, scrape blades
6) mix 60-65 min at < 2 torr (at 30 RPM)
7) remove and package.
[043] Using a double planetary mixer, the B-side is prepared by mixing the components from Table B:
1 ) adding 1 , 2, 3, and 4 to Ross, mix 5-10 min
2) add 1/3 of 5 and 6 to Ross, Mix 10-15 min (at 30 RPM)
3) add 1/3 of 5 and 6 to Ross, Mix 10-15 min (at 30 RPM)
4) add final 1/3 of 5 and 6 to Ross. Mix 30-35 min ( at 30 RPM)
5) add 7, Mix 3-5 min to wet out, stop mixer, scrape blades
6) mix 60-65 min at < 2 torr (at 30 RPM)
7) Remove and package.
[044] This potting compound is usable as a room temp stable two-component meter mixed potting compound. It exhibits a viscosity as measured by Brookfield DV-2, spindle 7 at 10 rpm after a 5 minute dwell of 140,000 cps.
Thermal Conductivity
[045] Thermal conductivity was measured using a Mathis® Hot Disk thermal conductivity tester. Three tests were repeated for an example which contained
[046] The average of three runs was 2.98 W/mk, which was unexpected for a material that provided a spin castable viscosity and a Shore A hardness of 55.
Claims
1. A method for encapsulating circuitry , comprising the steps of spin casting a silicone gel composition, said gel composition comprises: a mixture of a stoichiometric excess of an alkenyl functionalized silicone with a hudrogen-functionalized organopolysiloxane, together with alumina, zinc oxide and boron nitride.
2. The method according to claim 1 , wherein the gel composition has a bulk thermal conductivity greater than 2 W/mK.
3. The method according to claim 2, wherein the gel composition is made by the curing of said gel composition characterized by:
(A) an alkenyl-functionalized diorganopolysiloxane having a viscosity of between 50 and 100,000 cP at 25°C. and having at least two silicon-bonded alkenyl groups in each molecule; and
(B) a hydrogen-functionalized organopolysiloxane having a viscosity between 1 and 1 ,000,000 cP at 25° C. and containing an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl in the alkenyl- functionalized diorganopolysiloxane (A);
(B) a hydrosilation catalyst,
( C) an electro-negative group terminated siloxane oligomers contain an electronegative substituent in the terminating portion of the oligomeric compound ; (D) a hydrosiiylation catalyst;
(E) a curing rate retarder, and
(F) from 40-65 vol. % of aluminum oxide, 10-25 vol. % of zinc oxide, and 1.2 - 5 vol. % of boron nitride.
4. The method of claim 1 wherein said mixture further comprises titanium dioxide.
5. The method of claim 5 wherein the thermal conductive fillers are characterized by 55-65 vol. % of aluminum oxide, from 5 to 10 vol. % of zinc oxide, from 6 to 12 vol.% of titanium dioxide and from 1.2 - 5 vol. % of boron nitride.
6. An addition-crosslinkable precured potting composition comprising:
(A) an alkenyl-functionalized diorganopolysiloxane having a viscosity of between 50 and 100,000 cP at 25°C. and having at least two silicon-bonded alkenyl groups in each molecule and in a stoichiometric excess over (B); and
(B) a hydrogen-functionalized organopolysiloxane having a viscosity between 1 and 1 ,000,000 cP at 25° C. and containing an average of at least 2 silicon-bonded hydrogen atoms per molecule, in a quantity that provides between 0.2 and 5.0 moles of silicon-bonded hydrogen per mole of silicon-bonded alkenyl in the alkenyl- functionalized diorganopolysiloxane (A);
(B) a hydrosilation catalyst, ( C) an electro-negative group terminated siloxane oligomer containing an electronegative substituent in the terminating portion of the oligomeric compound ;
(D) a hydrosiiylation catalyst;
(E) a curing rate retarder, and
(F) from 40-65 vol. % of aluminum oxide, 10-25 vol. % of zinc oxide, and 1.2 - 5 vol. % of boron nitride.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US30271101P | 2001-07-03 | 2001-07-03 | |
US60/302,711 | 2001-07-03 |
Publications (1)
Publication Number | Publication Date |
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WO2003004567A1 true WO2003004567A1 (en) | 2003-01-16 |
Family
ID=23168903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2002/021250 WO2003004567A1 (en) | 2001-07-03 | 2002-07-03 | High thermal conductivity spin castable potting compound |
Country Status (3)
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US (1) | US6770326B2 (en) |
TW (1) | TWI242584B (en) |
WO (1) | WO2003004567A1 (en) |
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CN107849354A (en) * | 2015-07-01 | 2018-03-27 | 昭和电工株式会社 | Thermocurable polysiloxane resin composition containing boron nitride, the dispersant for polysiloxane resin composition and inorganic filler |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0382188A1 (en) * | 1989-02-08 | 1990-08-16 | Dow Corning Corporation | Thermally conductive organosiloxane compositions |
US5021494A (en) * | 1988-10-03 | 1991-06-04 | Toshiba Silicone Co., Ltd | Thermal conductive silicone composition |
EP0496419A2 (en) * | 1991-01-24 | 1992-07-29 | Shin-Etsu Chemical Co., Ltd. | Curable silicone composition and cured product thereof |
EP0896031A2 (en) * | 1997-08-06 | 1999-02-10 | Shin-Etsu Chemical Co., Ltd. | Thermally conductive silicone composition |
US6069201A (en) * | 1997-09-12 | 2000-05-30 | Shin-Etsu Chemical Co., Ltd. | Zinc oxide-filled addition-curable silicone rubber compositions |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3020260A (en) | 1960-08-18 | 1962-02-06 | Dow Corning | Organosiloxane potting compound |
US3159602A (en) | 1962-06-07 | 1964-12-01 | Olin Mathieson | Preparation of polymeric phosphates |
US3159601A (en) | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
US3220972A (en) | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
NL133821C (en) | 1964-07-31 | |||
NL131800C (en) | 1965-05-17 | |||
US3814730A (en) | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3715334A (en) | 1970-11-27 | 1973-02-06 | Gen Electric | Platinum-vinylsiloxanes |
US3775452A (en) | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US4394317A (en) | 1981-02-02 | 1983-07-19 | Sws Silicones Corporation | Platinum-styrene complexes which promote hydrosilation reactions |
US4374967A (en) | 1981-07-06 | 1983-02-22 | Dow Corning Corporation | Low temperature silicone gel |
JPS58219034A (en) * | 1982-06-14 | 1983-12-20 | Toray Silicone Co Ltd | Manufacture of electrical insulating heat dissipation rubber sheet |
US4634207A (en) | 1982-10-12 | 1987-01-06 | Raychem Corporation | Apparatus and method for protection of a substrate |
US4600261A (en) | 1982-10-12 | 1986-07-15 | Raychem Corporation | Apparatus and method for protection of electrical contacts |
US5357057A (en) | 1982-10-12 | 1994-10-18 | Raychem Corporation | Protected electrical connector |
US4529789A (en) | 1984-03-23 | 1985-07-16 | Dow Corning Corporation | Liquid curable polyorganosiloxane compositions |
FR2575086B1 (en) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | PLATINUM-ALCENYLCYCLOHEXENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PROCESS FOR PREPARING THE SAME |
FR2575085B1 (en) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | PLATINUM-TRIENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PREPARATION METHOD THEREOF |
US4777063A (en) | 1985-05-02 | 1988-10-11 | Raychem Corporation | Curable organopolysiloxane composition |
JPH04503825A (en) | 1989-03-01 | 1992-07-09 | レイケム・コーポレイション | Method for curing organopolysiloxane compositions and articles made therefrom |
JP2582690B2 (en) | 1991-09-13 | 1997-02-19 | 信越化学工業株式会社 | Silicone gel composition with excellent anti-vibration properties |
US5268815A (en) | 1992-02-14 | 1993-12-07 | International Business Machines Corporation | High density, high performance memory circuit package |
JP2739407B2 (en) | 1993-02-09 | 1998-04-15 | 信越化学工業株式会社 | Low elastic modulus silicone gel composition and gel-like cured product |
KR970005712B1 (en) | 1994-01-11 | 1997-04-19 | 삼성전자 주식회사 | High heat sink package |
US5818564A (en) * | 1996-09-13 | 1998-10-06 | Raychem Corporation | Assembly including an active matrix liquid crystal display module |
US5812374A (en) | 1996-10-28 | 1998-09-22 | Shuff; Gregg Douglas | Electrical circuit cooling device |
JP3482115B2 (en) | 1997-10-13 | 2003-12-22 | 東レ・ダウコーニング・シリコーン株式会社 | Curable silicone composition and electronic component |
JP4727017B2 (en) * | 1999-11-15 | 2011-07-20 | 東レ・ダウコーニング株式会社 | Thermally conductive silicone rubber composition |
-
2002
- 2002-07-02 TW TW091114610A patent/TWI242584B/en not_active IP Right Cessation
- 2002-07-03 US US10/190,110 patent/US6770326B2/en not_active Expired - Lifetime
- 2002-07-03 WO PCT/US2002/021250 patent/WO2003004567A1/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5021494A (en) * | 1988-10-03 | 1991-06-04 | Toshiba Silicone Co., Ltd | Thermal conductive silicone composition |
EP0382188A1 (en) * | 1989-02-08 | 1990-08-16 | Dow Corning Corporation | Thermally conductive organosiloxane compositions |
EP0496419A2 (en) * | 1991-01-24 | 1992-07-29 | Shin-Etsu Chemical Co., Ltd. | Curable silicone composition and cured product thereof |
EP0896031A2 (en) * | 1997-08-06 | 1999-02-10 | Shin-Etsu Chemical Co., Ltd. | Thermally conductive silicone composition |
US6069201A (en) * | 1997-09-12 | 2000-05-30 | Shin-Etsu Chemical Co., Ltd. | Zinc oxide-filled addition-curable silicone rubber compositions |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009038712A1 (en) * | 2007-09-20 | 2009-03-26 | Momentive Performance Materials Inc. | Boron nitride-containing silicone gel composition |
JP2010540435A (en) * | 2007-09-20 | 2010-12-24 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Boron nitride-containing silicone gel composition |
CN103333494A (en) * | 2013-05-28 | 2013-10-02 | 东莞上海大学纳米技术研究院 | Thermal-conductive insulation silicone rubber thermal interface material and preparation method thereof |
CN103333494B (en) * | 2013-05-28 | 2015-08-05 | 东莞上海大学纳米技术研究院 | A kind of Thermal-conductive insulation silicone rubber thermal interface material and preparation method thereof |
CN107849354A (en) * | 2015-07-01 | 2018-03-27 | 昭和电工株式会社 | Thermocurable polysiloxane resin composition containing boron nitride, the dispersant for polysiloxane resin composition and inorganic filler |
EP3318605A4 (en) * | 2015-07-01 | 2019-01-23 | Showa Denko K.K. | Thermosetting silicone resin composition containing boron nitride, dispersant for silicone resin compositions, and inorganic filler |
Also Published As
Publication number | Publication date |
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US20030050419A1 (en) | 2003-03-13 |
TWI242584B (en) | 2005-11-01 |
US6770326B2 (en) | 2004-08-03 |
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