A curable thermally conductive composition containing diamond particles

Abstract

The curable thermally conductive composition comprises: (a) one or more vinyl dimethyl terminated polydimethylsiloxanes; (b) a silylhydride functional polysiloxane having at least two silylhydride groups per molecule; (c) a filler treating agent; and (d) 94-97 wt. % of a thermally conductive filler comprising diamond particles having a Dv50 in the range of 60-150 micrometers.

Description

[Technical Field]

[0001] The present invention relates to a curable thermally conductive composition containing a thermally conductive filler comprising diamond particles having a Dv50 particle size in the range of 60 to 150 micrometers. [Background technology]

[0002] The trend towards miniaturization and increased power in electronic devices across industry is driving a growing demand for thermally conductive compositions useful for dissipating the heat generated by such devices. For example, the telecommunications industry is experiencing a generational shift to 5G networks, requiring smaller, highly integrated electrical devices with a doubling of power requirements (from 600 watts to 1200 watts). If the heat generated by high power in small devices is not efficiently dissipated, the devices will be damaged. Thermally conductive interface materials are often used in electronic devices to thermally bond heat-generating components to heat-dissipating components.

[0003] The challenge for thermally conductive interface materials is to provide a combination of high thermal conductivity and easy extrusion, enabling precise application of the thermally conductive material onto small components. Specifically, having an extrusion rate exceeding 60 grams / min and at least 8 watts / meter, as measured using the extrusion rate test defined below herein. * It is desirable to provide a thermally conductive interface material that hardens to a material having a thermal conductivity of Kelvin. While thermal conductivity can be increased by increasing the amount of thermally conductive filler, this also reduces the extrusion rate of the composition. Therefore, satisfying these two performance parameters is particularly difficult. [Overview of the project]

[0004] The present invention has an extrusion rate exceeding 60 grams / min (g / min) and at least 8 watts / meter when measured using the extrusion rate test defined below herein. * Kelvin (W / m *The present invention provides a thermally conductive interface material that hardens to a material having a thermal conductivity of K.

[0005] Surprisingly, it has been found that such compositions can be prepared from a curable polysiloxane composition containing 94–97 weight percent (weight) of a thermally conductive filler, including 30–55 weight percent (weight) of diamond particles having a Dv50 in the range of 60–150 micrometers, where weight percent is relative to the weight of the curable polysiloxane composition.

[0006] In a first embodiment, the present invention relates to a curable thermally conductive composition comprising a vinyl functional silicone polymer in which, by weight percent, (a) one or a combination thereof of a plurality of vinyldimethyl-terminated polydimethylsiloxanes, and which has a viscosity of 30 to 2000 millipascals when measured by ASTM D445-21 using a glass capillary Cannon-Fenske viscometer at 25°C at concentrations ranging from 1 to 4.0 by weight percent, in the range of 1 to 4.0. *(b) a vinyl-functionalized silicone polymer having a viscosity in the range of seconds; (c) at least one silyl hydride-functionalized polysiloxane crosslinking agent having at least two silyl hydride groups per molecule and present at a concentration such that the molar ratio of silyl hydride groups to vinyl groups in the composition is in the range of 0.5 to 1.0; (d) a filler treatment agent in the range of 0.1 to 2.0 weight percent, comprising any one of a plurality of trialkoxysilyl compounds or any combination thereof; and (i) 30 A curable thermal conductive composition comprising: (ii) diamond particles having a Dv50 in the range of 60 to 150 micrometers with a concentration in the range of ~55 weight percent; (ii) a thermal conductive filler having a Dv50 in the range of more than 1 to ~10 micrometers with a concentration in the range of 25 to 35 weight percent; (iii) a thermal conductive filler having a Dv50 in the range of 0.1 to 1 micrometer with a concentration in the range of 10 to 20 weight percent; and (iv) optionally a thermal conductive filler having a Dv50 in the range of 20 to 60 micrometers with a concentration in the range of 0 to 20 weight percent.

[0007] In a second embodiment, the present invention is a process for using a curable thermal conductive composition of the first embodiment, comprising: applying the curable thermal conductive composition between and in contact with two components; and then heating the curable composition to cure it while it is in a predetermined position between the components.

[0008] In a third aspect, the present invention relates to an article comprising a curable thermal conductive composition of the first aspect between and in contact with two components of the article, wherein the curable thermal conductive composition is in either a cured or uncured state.

[0009] The composition of the present invention is useful as a thermally conductive interface material for efficiently transferring heat between two components. The process of the present invention is useful for applying the composition of the present invention. The article of the present invention is useful as a device that benefits from efficient heat conduction between components.

Mode for Carrying Out the Invention

[0010] The test method refers to the most recent test method on the priority date of this document when the date is not indicated together with the test method number. References to test methods contain both a reference to the association of the test and the test method number. In this specification, the following abbreviations and identifiers for test methods apply. ASTM refers to ASTM International methods, EN refers to European Norm, DIN refers to the Deutsches Institut fur Normung, ISO refers to the International Organization for Standards, and UL refers to the Underwriters Laboratory.

[0011] Products identified by trade name refer to the compositions available under those trade names on the priority date of this document.

[0012] "Plurality" means two or more. "And / or" means "and, or alternatively". All ranges include the endpoints unless otherwise indicated.

[0013] The particle size (used interchangeably with "average particle size" and "Dv50") is determined as the volume-weighted median of the particle size distribution (Dv50) using a Mastersizer (trademark) 3000 laser diffraction particle size analyzer manufactured by Malvern Instruments (trademark of Malvern Instruments Limited).

[0014] Unless otherwise specified, the viscosity is measured at 25 °C using a glass capillary Cannon-Fenske type viscometer in accordance with ASTM D445-21.

[0015] The thermal conductivity of the cured composition sample is measured using a Hot Disk TPS 2500S instrument conforming to ISO22007-2. The sensor is a Model 5465 (3.189 mm Kapton sensor). A cured sample for thermal conductivity evaluation is prepared by curing a sample with dimensions of 25 mm × 25 mm square × 8 mm thickness at 120 degrees Celsius (°C) for 60 minutes.

[0016] The extrusion rate (ER) of a composition is measured using the following extrusion rate test with a Nordson EFD dispenser. The sample material is packaged in a 30 ml syringe (Nordson Company EFD syringe) with a 2.54 mm opening. The sample is dispensed from the opening by applying a pressure of 0.62 megapascals to the syringe plunger. The mass of sample discharged from the 2.54 mm opening per minute is recorded in grams to obtain the extrusion rate value as grams per minute (g / min).

[0017] In one embodiment, the present invention is a curable thermally conductive composition. In that respect, the present invention is a "curable composition." The curable composition can undergo a crosslinking reaction ("curing reaction"). In this composition, the crosslinking reaction is a hydrosilylation reaction between a vinyl-functionalized silicone polymer component and a silyl-hydride (Si-H) functionalized polysiloxane crosslinking agent.

[0018] Vinyl-functionalized silicone polymers have a viscosity of 30 to 2000 millipascals. * seconds (mPa) * Having a viscosity in the range of s), it contains or consists of one or any combination of multiple vinyldimethyl-terminated polydimethylsiloxanes. When the vinyl-functionalized silicone polymer is a combination of multiple vinyldimethyl-terminated polydimethylsiloxanes, the viscosity is the viscosity of the combined vinyldimethyl-terminated polydimethylsiloxanes. The viscosity of the vinyl-functionalized silicone polymer is 30 mPa. *s or more and 40 mPa * s or more, 50 mPa * s or more, 60 mPa * s or more, 70 mPa * s or more, 75 mPa * s or more, 78 mPa * s or more, 80 mPa * s or more, 100 mPa * s or more, 125 mPa * s or more, 150 mPa * s or more, 175 mPa * s or more, and further 200 mPa * s or more and may be 2000 mPa at the same time * s or less, 1500 mPa * s or less, 1000 mPa * s or less, 500 mPa * s or less, and preferably 400 mPa * s or less, 300 mPa * s or less, 200 mPa * s or less, 150 mPa * s or less, 100 mPa * s or less, 90 mPa * s or less, and further 80 mPa * s or less.

[0019] Each vinyl dimethyl terminated polydimethylsiloxane can have an average chemical structure (I). Vi(CH3)2SiO - ((CH3)2SiO) d -Si(CH3)2Vi (I) In the formula, the subscript d is the average number of ((CH3)2SiO) groups per molecule, and has values ​​of 25 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 120 or more, 140 or more, 160 or more, 180 or more, 200 or more, 220 or more, 240 or more, 260 or more, 280 or more, 300 or more, 320 or more, and even 340 or more, and at the same time 350 or less, 340 or less, 320 or less, 300 or less, 280 or less, 260 or less, 240 or less, 240 or less, 220 or less, 200 or less, 180 or less, 160 or less, 140 or less, 120 or less, 100 or less, 80 or less, 60 or less, and even 40 or less. For example, vinyl-functionalized silicone polymers, such as those sold by Gelest under the product name SMS-V21, have a pressure of 78 mPa. * It may be a vinyldimethyl-terminated polydimethylsiloxane having a viscosity of s and containing 1.25 wt% (wt%) of vinyl groups relative to its molecular weight.

[0020] The concentration of the vinyl-functionalized silicone polymer is 1% by weight or more relative to the weight of the curable thermal conductive composition, and may be 2.0% by weight or more, 2.5% by weight or more, 2.7% by weight or more, and even 3.0% by weight or more, while simultaneously being 4.0% by weight or less, 3.5% by weight or less, and even 3.3% by weight or less.

[0021] The curable thermally conductive composition further comprises at least one silyl hydride (SiH)-functionalized polysiloxane crosslinking agent. The SiH-functionalized crosslinking agent contains at least two SiH groups per molecule. The SiH groups may be pendant groups, terminal groups, or a combination of both pendant and terminal groups. A "terminal" group is located on a terminal siloxane group of the molecule. A "terminal" siloxane group is bonded to only one other siloxane group. A "pendant" group is located on an internal siloxane group of the molecule (a siloxane group bonded to at least two other siloxane groups). A "siloxane group" is a group containing SiO bonded to another Si via the oxygen of SiO.

[0022] SiH-functionalized polysiloxane crosslinking agents can have an average chemical structure (II). R (3-h) H h SiO-(HRSiO) a -(R2SiO) b -SiH h’ R (3-h’) (II) During the ceremony, R is independently selected from alkyl and aryl groups having 1 to 6 carbon atoms in each case. The R group can have 1 or more carbon atoms, 2 or more carbon atoms, 3 or more carbon atoms, 4 or more carbon atoms, and even 5 or more carbon atoms, and at the same time, it can have 6 or fewer carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or even 2 or fewer carbon atoms. Preferably, the R group is independently selected from methyl and phenyl groups in each case.

[0023] H represents a hydrogen atom.

[0024] The subscripts h and h' refer to the average number of terminal hydrogen atoms at either end, each independently selected from a value in the range of 0 to 3 in each case, provided that the combination of a, h, and h' is at least 2. Preferably, h and h' are independently 0 or greater, 1 or greater, and even 2 or greater in each case, and simultaneously 3 or less, 2 or less, or even 1 or less. More preferably, h and h' have the same value. Most preferably, both h and h' are 0.

[0025] The subscript 'a' is the average number of (HRSiO) groups per molecule. If both h and h' are 0, then 'a' is 2 or greater. If neither h nor h' is 0, then the subscript 'a' can be 0, assuming that the combination of a, h, and h' is 2 or greater. Preferably, the subscript 'a' is 1 or greater, may be 2 or greater, may be 3 or greater, 4 or greater, 5 or greater, 6 or greater, 7 or greater, 8 or greater, and even 9 or greater, and at the same time typically 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, and even 2 or less.

[0026] The subscript b represents the average number of (R2SiO) groups per molecule. Generally, the subscript b is 5 or greater, 10 or greater, 20 or greater, 25 or greater, 30 or greater, 40 or greater, 50 or greater, and may be 75 or greater, 100 or greater, 125 or greater, 150 or greater, 175 or greater, and even 190 or greater, while typically being 200 or less, 175 or less, 150 or less, 125 or less, 100 or less, 75 or less, 50 or less, 40 or less, 30 or less, even 25 or less, or even 20 or less.

[0027] SiH-functionalized polysiloxane crosslinking agent: (i) 14 millipascal * (ii) a trimethyl-terminated dimethyl-co-hydrogen methylpolysiloxane having a viscosity of 1 / 2 and containing 0.36 weight percent hydrogen in the silyl hydride group, and (ii) 7-10 millipascal * It may be one or a combination of both polymers selected from the group consisting of hydride-terminated polydimethylsiloxanes having a viscosity in the range of seconds and containing 0.16 weight percent hydrogen in the silyl hydride group.

[0028] The concentration of the SiH-functionalized polysiloxane crosslinking agent is sufficient to provide a molar ratio (SiH / Vi ratio) of 0.5 or higher, which may be 0.6 or higher, 0.7 or higher, 0.8 or higher, or even 0.9 or higher, and simultaneously 1.0 or lower, which may be 0.9 or lower, 0.8 or lower, 0.7 or lower, or even 0.6 or lower. The SiH / Vi ratio determines the degree of crosslinking that occurs when the curable thermal conductive composition hardens. If the SiH / vinyl ratio is too low, the composition will not harden sufficiently, and sufficient vertical stability will not be obtained. If the SiH / vinyl ratio is too high, the composition will harden too much, become brittle, and be prone to surface cracking.

[0029] The curable thermal conductive composition contains a filler treatment agent. The filler treatment agent is a trialkoxysilyl compound, which is a compound having a -Si(OR)3 group. However, each R is independently defined in its respective case as described above in this specification.

[0030] The filler treatment agent is preferably one component or any combination of multiple components selected from the group consisting of alkyltrialkoxysilanes and monotrialkoxysiloxy-terminated diorganopolysiloxanes.

[0031] A suitable alkyltrialkoxysilane is one with the chemical formula R a (R b Examples include those having O)3Si (wherein R a and R b Each of these independently has, in each case, one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more, and even eleven or more carbon atoms, and at the same time is an alkyl which typically has 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 12 or fewer carbon atoms, and may have 10 or fewer carbon atoms. b It is preferable that the molecule is methyl so as to form a methoxyl group bonded to the silicon atom. A particularly desirable alkyltrialkoxysilane is n-decyltrimethoxysilane.

[0032] A suitable monotrialkoxysiloxy-terminated diorganopolysiloxane is one with an average chemical formula of R c 3SiO[R] d 2[SiO] g Si(OR e )Those having 3 are examples (in the formula, each R c , R d and R eIndependently in each case, these can have one or more carbon atoms, and can have two or more, three or more, four or more, five or more, six or more, seven or more, and even eight or more carbon atoms, and at the same time, they are selected from hydrocarbyls that typically have 10 or fewer, eight or fewer, six or fewer, four or fewer, and even two or fewer carbon atoms, where the subscript g typically has a value of 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, and at the same time, typically has a value of 200 or less, 150 or less, 125 or less, 120 or less, or even 110 or less). Particularly desirable monotrialkoxysiloxy-terminated diorganopolysiloxanes have the average chemical formula (CH3)3SiO[(CH3)2[SiO] 30 It contains Si(OCH3)3.

[0033] The concentration of the filler treatment agent is, in weight percent relative to the weight of the curable composition, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, 0.5% by weight or more, 0.6% by weight or more, 0.7% by weight or more, 0.8% by weight or more, 0.9% by weight or more, 1.0% by weight or more, 1.2% by weight or more, 1.3% by weight or more, and more specifically, 1.4% by weight or more, while typically being 2.0% by weight or less, 1.8% by weight or less, 1.6% by weight or less, 1.4% by weight or less, 1.3% by weight or less, or more specifically, 1.2% by weight or less.

[0034] For example, curable compositions, n-decyltrimethoxysilane and (CH3)3SiO[(CH3)2SiO] 30 The curable composition may contain one or a combination of any of the Si(OCH3)3 compounds. Preferably, the curable composition contains 0.2 wt percent n-decyltrimethoxysilane and 0.10 to 0.12 wt percent of an average chemical structure (CH3)3SiO[(CH3)2SiO] 30 It may include monotrimethoxysiloxy and trimethylsiloxy-terminated polydimethylsiloxanes having Si(OCH3)3.

[0035] The curable thermally conductive composition further comprises a thermally conductive filler. The concentration of the thermally conductive filler is 94% by weight or more, 94.5% by weight or more, 95% by weight or more, and even 95.5% by weight or more, in weight percent relative to the weight of the curable composition, and at the same time, typically 97% by weight or less, 96% by weight or less, 95.5% by weight or less, and even 95% by weight or less.

[0036] The thermally conductive filler may consist of a combination of at least three, and possibly four, different thermally conductive fillers.

[0037] The first thermally conductive filler is a diamond particle having a Dv50 of 60 micrometers or more, and may have a Dv50 of 70 micrometers or more, 80 micrometers or more, 90 micrometers or more, 100 micrometers or more, 110 micrometers or more, 120 micrometers or more, 130 micrometers or more, and even 140 micrometers or more, and at the same time having a Dv50 of 150 micrometers or less, and may have a Dv50 of 140 micrometers or less, 130 micrometers or less, 120 micrometers or less, 110 micrometers or less, 100 micrometers or less, 90 micrometers or less, 80 micrometers or less, or even 70 micrometers or less. The concentration of the first thermally conductive filler is 30% by weight or more, 34% by weight or more, 35% by weight or more, 40% by weight or more, and even 50% by weight or more, and at the same time 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, or even 35% by weight or less.

[0038] The second thermally conductive filler has a Dv50 of 1 micrometer or more, may have a Dv50 of 2 micrometers or more, 3 micrometers or more, 4 micrometers or more, and even 5 micrometers or more, and at the same time has a Dv50 of 10 micrometers or less, may have a Dv50 of 9 micrometers or less, 8 micrometers or less, 7 micrometers or less, 6 micrometers or less, or even 5 micrometers or less. The concentration of the second thermally conductive filler is 25% by weight or more relative to the weight of the curable thermally conductive composition, may be 26% by weight or more, 28% by weight or more, 30% by weight or more, 32% by weight or more, and even 34% by weight or more, and at the same time is 35% by weight or less, may be 33% by weight or less, 31% by weight or less, 29% by weight or less, and even 27% by weight or less.

[0039] The third thermally conductive filler has a Dv50 of 0.1 or more, may have a Dv50 of 0.3 or more, 0.5 or more, 0.7 or more, and even 0.9 or more, and at the same time may have a Dv50 of 1 or less, 0.8 or less, 0.6 or less, 0.4 or less, or even 0.2 or less. The concentration of the third thermally conductive filler is 10% by weight or more, in weight percent relative to the weight of the curable thermally conductive composition, may be 12% by weight or more, 14% by weight or more, 16% by weight or more, or even 18% by weight or more, and at the same time may be 20% by weight or less, 19% by weight or less, 17% by weight or less, 15% by weight or less, 13% by weight or less, or even 11% by weight or less.

[0040] The fourth thermally conductive filler has a Dv50 of 20 micrometers or more, and may have a Dv50 of 25 micrometers or more, 30 micrometers or more, 35 micrometers or more, 40 micrometers or more, 45 micrometers or more, and even 50 micrometers or more, and at the same time may have a Dv50 of 60 micrometers or less, 55 micrometers or less, 50 micrometers or less, or even 45 micrometers or less. The concentration of the fourth thermally conductive filler is expressed in weight percent relative to the weight of the curable thermally conductive composition as 0% by weight or more, and may be 2% by weight or more, 4% by weight or more, 6% by weight or more, 8% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, and even 18% by weight or more, and at the same time may be 20% by weight or less, 19% by weight or less, 17% by weight or less, 15% by weight or less, 13% by weight or less, or even 11% by weight or less.

[0041] The thermally conductive filler may include fillers in addition to these four thermally conductive fillers, or it may not include any thermally conductive fillers other than these four.

[0042] The particles can have any shape, such as spherical, irregular, crushed, or plate-like. Preferably, the second thermally conductive filler is one or both of spherical aluminum oxide and irregular aluminum nitride. Preferably, the third thermally conductive filler is pulverized zinc oxide. Preferably, the fourth thermally conductive filler is spherical aluminum nitride.

[0043] Preferably, each thermally conductive filler is independently selected from the group consisting of diamond particles, aluminum nitride particles, aluminum oxide particles, zinc oxide particles, and boron nitride particles. Preferably, the first thermally conductive filler is selected from 34 wt percent diamond particles having a Dv50 of 120 micrometers, or 30.5 wt percent diamond particles having a Dv50 of 120 micrometers and 20 wt percent diamond particles having a Dv50 of 20 micrometers, or 50.4 to 50.8 wt percent diamond particles having a Dv50 of 60 micrometers.

[0044] Preferably, the second thermally conductive filler is a combination of aluminum nitride and / or aluminum oxide. Preferably, the second thermally conductive filler is selected from 30 wt percent spherical aluminum oxide particles having a Dv50 in the range of 2 to 5 micrometers, or a combination of 19 wt percent spherical aluminum oxide particles having a Dv50 of 2 micrometers and 10 wt percent irregular aluminum nitride particles having a Dv50 of 1.5 micrometers.

[0045] Preferably, the third thermally conductive filler is zinc oxide. Preferably, the third thermally conductive filler is 15 weight percent irregular zinc oxide particles having a Dv50 of 0.2 micrometers.

[0046] Preferably, the fourth thermally conductive filler is aluminum nitride. Preferably, the fourth thermally conductive filler, if present, is 16.50 weight percent spherical aluminum nitride particles having a Dv50 in the range of 30 to 50 micrometers.

[0047] Typically, a curable thermally conductive composition further comprises a platinum-based hydrosilylation catalyst. Examples of platinum-based hydrosilylation catalysts include compounds and complexes, such as platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (karstedt catalyst), H2PtCl6, di-μ-carbonyldi-π-cyclopentadienyldinickel, platinum-carbonyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, platinum acetylacetonate (acac), platinum black, platinum compounds, such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum dichloride, and complexes of platinum compounds with olefins or low molecular weight organopolysiloxanes, or platinum compounds microencapsulated in a matrix or core-shell structure. The hydrosilylation catalyst may be part of a solution containing a complex of platinum and a low molecular weight organopolysiloxane, including a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. These complexes may be microencapsulated in a resin matrix. The catalyst may be a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. Typically, the platinum-based hydrosilylation catalyst is present in a concentration sufficient to give a platinum concentration of 0.03% by weight or more, 0.04% by weight or more, 0.05% by weight or more, and even 0.06% by weight or more, in weight percent of the curable thermal conductive composition, and at the same time, typically 0.4% by weight or less, or 0.3% by weight or less, 0.2% by weight or less, 0.1% by weight or less, 0.09% by weight or less, 0.08% by weight or less, 0.07% by weight or less, 0.06% by weight or less, 0.05% by weight or less, or even 0.04% by weight or less, in weight percent of the curable thermal conductive composition.

[0048] The curable thermal conductive composition may further contain a curing inhibitor. The curing inhibitor can stabilize the curable thermal conductive composition from premature curing and provide storage stability to the composition. Examples of suitable curing inhibitors include acetylene compounds such as 2-methyl-3-butyne-2-ol, 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 2-phenyl-3-butyne-2-ol, 3-phenyl-1-butyne-3-ol, 1-ethynyl-1-cyclohexanol, 1,1-dimethyl-2-propynyl)oxy)trimethylsilane, and methyl(tris(1,1-dimethyl-2-propynyloxy))silane; 3-methyl-3-penten-1-yne, and Examples include one or more combinations of any and more of the following: en-yine compounds such as 3,5-dimethyl-3-hexen-1-yine; triazoles such as benzotriazole; hydrazine compounds; phosphine compounds; mercaptan compounds; and cycloalkenylsiloxanes, including methylvinylcyclosiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane.

[0049] The concentration of the curing inhibitor is expressed as a weight percent relative to the weight of the curable thermal conductive composition and is 0% by weight or more, may be 0.001% by weight or more, 0.002% by weight or more, and more likely 0.003% by weight or more, and at the same time, is typically 0.5% by weight or less, or more likely 0.3% by weight or less, 0.1% by weight or less, 0.05% by weight or less, 0.01% by weight or less, or more likely 0.005% by weight or less, 0.004% by weight or less, or more likely 0.003% by weight or less.

[0050] The present invention also includes a process for using a curable thermal conductive composition, comprising: applying the curable thermal conductive composition between and in contact with two components; and then heating the curable composition to cure it while it is in a predetermined position between the components.

[0051] The present invention further includes an article comprising a curable thermal conductive composition and at least two components, wherein the curable thermal conductive composition is located between and in contact with the two components. The curable thermal conductive composition may be in a cured or uncured form. [Examples]

[0052] Table 1 shows the materials used in the following examples and comparative examples.

[0053] [Table 1]

[0054] Each sample is characterized for its extrusion speed using an extrusion speed test, and for its thermal conductivity using the method described herein. Extrusion speeds exceeding 60 g / min and at least 8 W / m * The objective is to obtain the thermal conductivity K. Table 2 shows the results of the characterization of each sample composition.

[0055] [Table 2]

[0056] Samples without diamond fillers having a Dv50 in the range of 60-150 micrometers will not have an ER greater than 60 g / min and at least 8 W / m², even if the sample contains diamond fillers (only diamond fillers smaller than 60-150 micrometers). * None of the thermal conductivity values ​​(TC) for K can be achieved.

Claims

1. A curable thermal conductive composition, wherein the weight percentage is relative to the weight of the curable thermal conductive composition, a. A vinyl-functional silicone polymer which is one or a combination thereof of several vinyldimethyl-terminated polydimethylsiloxanes, and which has a viscosity of 30 to 2000 millipascals when measured by ASTM D445-21 using a glass capillary Cannon-Fenske viscometer at 25°C at concentrations ranging from 1 to 4.0 weight percent. ＊ A vinyl-functionalized silicone polymer having a viscosity in the range of seconds, b. A silyl hydride-functional polysiloxane crosslinking agent having at least two silyl hydride groups per molecule and present at a concentration such that the molar ratio of silyl hydride groups to vinyl groups in the composition is in the range of 0.5 to 1.0, c. A filler treatment agent having a concentration in the range of 0.1 to 2.0 weight percent, which is one of a plurality of compounds selected from trialkoxysilyl compounds or any combination thereof, d. A thermally conductive filler having a concentration in the range of 94 to 96% by weight, i. Diamond particles having a Dv50 in the range of 60 to 150 micrometers and a concentration in the range of 30 to 55 weight percent. ii. A thermally conductive filler having a concentration in the range of 25 to 35 weight percent and a Dv50 in the range of greater than 1 to 10 micrometers, iii. A thermally conductive filler having a concentration in the range of 10 to 20 weight percent and a Dv50 in the range of 0.1 to 1 micrometer, iv. Depending on the case, a thermally conductive filler having a Dv50 in the range of 20 to 60 micrometers with a concentration in the range of 0 to 20 weight percent, comprising a thermally conductive filler, It is a curable thermally conductive composition.

2. The curable thermal conductive composition is e. The curable thermal conductive composition according to claim 1, further comprising a platinum-based hydrosilylation catalyst in a concentration in the range of 0.03 to 0.4 weight percent, where weight percent refers to the weight of platinum relative to the weight of the curable thermal conductive composition.

3. The curable thermal conductive composition is f. The curable thermal conductive composition according to claim 1 or 2, further comprising a curing inhibitor in a concentration in the range of 0.001 to 0.005 weight percent, where weight percent is relative to the weight of the curable thermal conductive composition.

4. The vinyl-functionalized silicone polymer has an average chemical structure (I): Vi(CH ３ ) ２ SiO-((CH ３ ) ２ SiO) ｄ -Si(CH ３ ) ２ Vi (I) [wherein, d is the average number of ((CH ３ )) ２ SiO) groups and has a value of 25 or more and simultaneously 350 or less], the curable thermally conductive composition according to any one of claims 1 to 3.

5. Assuming the viscosity is determined by ASTM D445-21 using a glass capillary Cannon-Fenske viscometer at 25°C, the silylhydride-functionalized polysiloxane crosslinking agent has a viscosity of (i) 14 millipascals. ＊ A trimethyl-terminated dimethyl-co-hydrogen methylpolysiloxane having a viscosity of 1 / 2 and containing 0.36 wt percent hydrogen in the silyl hydride group, and (ii) 7-10 millipascal ＊ A curable thermally conductive composition according to any one of claims 1 to 4, comprising one or a combination of polymers selected from the group consisting of a hydride-terminated polydimethylsiloxane having a viscosity in the range of seconds and containing 0.16 weight percent hydrogen in the silyl hydride group.

6. a. The thermally conductive filler having a Dv50 in the range of greater than 1 to 5 micrometers is one or more selected from the group consisting of aluminum nitride and aluminum oxide. b. The thermally conductive filler having a Dv50 in the range of 0.1 to 1 micrometer is zinc oxide. c. The curable thermal conductive composition according to any one of claims 1 to 5, wherein an aluminum nitride thermal conductive filler having a Dv50 in the range of 40 to 60 micrometers is present.

7. As weight percent relative to the weight of the curable thermal conductive composition, a. 75-80 millipascals at a concentration in the range of 2.7-3.3 weight percent. ＊ A vinyldimethyl-terminated polydimethylsiloxane having a viscosity in the range of seconds, b. 14 millipascals ＊ 0.04 wt percent trimethyl-terminated dimethyl-co-hydrogen methylpolysiloxane with a viscosity of 7 to 10 millipascals ＊ A blend of 0.5 to 0.6 weight percent hydride-terminated polydimethylsiloxane having a viscosity in the range of seconds, c. 0.2 weight percent of n-decyltrimethoxysilane and 0.10 to 0.12 weight percent of the average chemical structure (CH ３ ) ３ SiO[(CH ３ ) ２ SiO] ３０ Si(OCH) ３ ) ３ A filler treatment agent comprising monotrimethoxysiloxy and trimethylsiloxy-terminated polydimethylsiloxane having d. A thermally conductive filler, i. 34% by weight of diamond particles having a Dv50 of 120 micrometers, or 30.5% by weight of diamond particles having a Dv50 of 120 micrometers and 20% by weight of diamond particles having a Dv50 of 20 micrometers, or 50.4 to 50.8% by weight of diamond particles having a Dv50 of 60 micrometers. ii. A combination of 30% by weight spherical aluminum oxide particles having a Dv50 in the range of 2 to 5 micrometers, or 19% by weight spherical aluminum oxide particles having a Dv50 of 2 micrometers and 10% by weight irregular aluminum nitride particles having a Dv50 of 1.5 micrometers. iii. 15% by weight of irregular zinc oxide particles having a Dv50 of 0.2 micrometers, and iv. A thermally conductive filler consisting of 16.50 weight percent spherical aluminum nitride particles having a Dv50 in the range of 30 to 50 micrometers, e. 0.06 weight percent of platinum hydrosilylation catalyst, f. 0.002 weight percent of methyl (tris(1,1'-dimethyl-2-propynyloxy))silane, A curable thermally conductive composition according to claim 1, comprising the above.

8. A process for using the curable thermal conductive composition according to any one of claims 1 to 7, comprising: applying the curable thermal conductive composition between and in contact with two components; and then heating the curable composition to cure it while it is in a predetermined position between the components.

9. The process according to claim 8, wherein applying the curable thermal conductive composition includes extruding the curable thermal conductive composition.

10. An article comprising a curable thermal conductive composition according to any one of claims 1 to 7 between and in contact with two components of the article, wherein the curable thermal conductive composition is in either a cured or uncured state.

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