Thermally conductive composition

Abstract

Provided is a composition comprising (A) an organopolysiloxane and (B) a thermal conductivity enhancer, the thermal conductivity enhancer (B) comprising a first thermal conductivity enhancer having a particle size in the range of 50 to about 200 μm; a second thermal conductivity enhancer having a particle size in the range of 0.5 to about 120 μm; and optionally a third thermal conductivity enhancer having a particle size in the range of 0.01 to less than 15 μm.

Description

Technical Field

[0001] The present invention relates to a composition comprising an organopolysiloxane and a thermal conductivity enhancer, wherein the thermal conductivity enhancer comprises a first thermal conductivity enhancer, a second thermal conductivity enhancer and a third thermal conductivity enhancer. Background Technology

[0002] As electronic devices become increasingly miniaturized, denser, and more integrated, heat generation is gradually increasing, and thermal failure has become a major obstacle to the performance, reliability, and lifespan of these devices. Therefore, effective thermal management is crucial to addressing this challenge. Thermal interface materials (TIMs) are widely used between the two solid contact surfaces of a heat source and a heat sink to increase heat removal (dissipation) in electronic devices. These materials come in various forms, such as greases, gap fillers, pre-cured gels, curable materials (one or two parts), phase change materials, elastic pads, adhesives, thermal tapes, metal alloys, and solders. The gap between two solid surfaces (chip and heat sink) is non-uniform and, if left untreated, can be filled with air with poor thermal conductivity. This gap is filled with a thermal interface material to provide a heat conduction path. Depending on the requirements, multiple thermal interface materials can be used between different solid surfaces to provide a continuous conduction path for heat removal.

[0003] The advent of 5G communication technology in the telecommunications space and the Internet of Things (IoT) in the consumer and industrial sectors will further increase the performance requirements for thermal conductivity (TIM). 5G and IoT devices (using 5G) operate at higher frequencies, higher device densities, higher bandwidth, lower latency, smaller feature sizes, and lower power consumption, while also requiring significantly higher reliability and availability. These factors have made the requirements for heat removal from electronic devices more stringent, and there is a general trend in industry towards higher performance (i.e., higher thermal conductivity TIM), for example, from low thermal conductivity of 3-5 W / mK to an average of 6-10 W / mK, and prompting the development of even higher thermal conductivity >10 W / mK. The development of next-generation integrated circuits (ICs), 3D integration, and ultrafast high-power-density communication devices makes thermal management requirements extremely stringent.

[0004] Conventional TIMs filled with thermally conductive particles require high volume fraction fillers (v>50%) such as alumina and ZnO to achieve a composite thermal conductivity (TC) in the range of 1-5 W / mK. When conductivity conditions are relaxed, many products also utilize metallic fillers such as aluminum. However, to achieve high TC (>10 W / mK), numerous patent applications disclose additional fillers such as BN, AlN, diamond, SiC, and combinations thereof. These fillers have the advantage of being electrically insulating and possessing significantly higher thermal conductivity (high TC fillers). In addition to thermal conductivity, TIM formulations must demonstrate a range of other key properties for use in the application. These may include low heat resistance, low volatility, pumpability, exudation, cracking, thermal stability, low build-up, and high dispensing flow rate for applications at defined viscosity, shear rate, and pump pressure. Performance stability during low-to-high temperature cycling / shock also needs to be demonstrated through testing for up to 500-1000 hours. These properties are achieved through the careful design of TIM formulations that combine high filler composition loadings with suitable polymer-resin-dispersant combinations, as disclosed below.

[0005] CN116814081A describes a composition comprising a filler combination of diamond, alumina, and cubic boron nitride filler, wherein the cubic boron nitride is a mixture of particles with a diameter of 5 μm and 30 μm, diamond has a particle diameter of 100 μm, and alumina nanoparticles have a particle size of 30 nm. This composition results in an ultra-high thermal conductivity, low dielectric interface material with a thermal conductivity greater than 7 and a dielectric constant less than 5.

[0006] CN112457673A describes a high thermal conductivity insulating silicone gasket containing at least one of nano-aluminum nitride, cubic boron nitride, and nano-silicon carbide, as well as spherical alumina modified with dodecyltrimethoxysilane. Through filler modification and compounding design, the silicone exhibits excellent properties such as high thermal conductivity, high insulation, and chemical stability, with a thermal conductivity coefficient reaching over 8 W / mK.

[0007] However, there is room for improvement in the thermal conductivity and hardness of such compositions. Summary of the Invention

[0008] This invention provides compositions comprising a mixture of polymers and thermally conductive fillers, wherein the deposition of the thermally conductive filler in the composition provides high thermal conductivity while maintaining low hardness accumulation at very high temperatures of 150°C. This invention incorporates cubic boron nitride as a key filler into the thermal formulations. Here, we demonstrate that combinations of cubic boron nitride with alumina, AlN, BN, SiC, ZnO, and fillers, along with silicone polymers and resins, form ideal combinations to achieve thermal conductivity >12 W / mK, accompanied by low hardness accumulation. All of these formulations are non-conductive.

[0009] The following summary of the invention is presented to provide a basic understanding of some aspects of the invention. This summary is not intended to identify key or essential elements, nor is it intended to limit the implementation or any restrictions on the claims. Furthermore, the summary provides a simplified overview of some aspects that can be described in more detail in other parts of this disclosure.

[0010] In one aspect, a composition is provided comprising: (A) An organopolysiloxane, wherein the organopolysiloxane comprises (i) Alkenyl-functionalized diorganopolysiloxanes of formula (Ia) M 1 a M 2 b D 1 c D 2 d T 1 e T 2 fQ g (Ia) in: M 1 = R 1 R 2 R 3 SiO 1 / 2 M 2 = R 4 R 5 R 6 SiO 1 / 2 D 1 = R 7 R 8 SiO 2 / 2 D 2 = R 9 R 10 SiO 2 / 2 T1 = R 11 SiO 3 / 2 T 2 = R 12 SiO 3 / 2 Q = SiO 4 / 2 Where R 2 R 3 R 4 R 5 R 6 R 8 R 9 R 10 R 12 Each is independently selected from aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms, or alkoxy groups; R 1 R 7 R 11 Each is independently selected from aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms and containing at least one terminal olefinic bond; and The subscripts a, b, c, d, e, f, and g are zero or positive integers subject to the following restrictions: 1 ≤ a + b + c + d + e + f + g ≤ 6000, and a + c + e ≥ 1; and (ii) Hydrogen-functionalized organopolysiloxanes of formula (Ib)

[0011] in: M 1 = R 13 R 14 R 15 SiO 1 / 2 M 2 = R 16 R 17 R 18 SiO 1 / 2 D 1 = R 19 R 20 SiO 2 / 2 D 2 = R 21 R 22 SiO 2 / 2 T 1 = R 23 SiO 3 / 2 T2 = R 24 SiO 3 / 2 Q = SiO 4 / 2 Where R 14 R 15 R 16 R 17 R 18 R 20 R 21 R 22 R 24 Aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms; R 13 R 19 R 23 It is hydrogen; The subscripts a', b', c', d', e', f', and g' are zero or positive integers subject to the following restrictions: 1 ≤ a'+b'+c'+d'+e'+f'+g' ≤ 6000, and a'+c'+e' ≥ 1; The condition is that when a'+c'+e'=1, then a+c+e>1, and when a+c+e=1, then a'+c'+e'>1; Or the cross-linked products of (i) and (ii), and (B) A thermal conductivity enhancer comprising a first thermal conductivity enhancer having a particle size in the range of 50 to 200 μm; a second thermal conductivity enhancer having a particle size in the range of 0.5 to 120 μm; and a third thermal conductivity enhancer having a particle size in the range of 0.01 to 15 μm. As used herein, unless the context otherwise requires, “particle size” refers to volume average particle size.

[0012] In one embodiment, the composition further comprises a dispersant represented by Formula II.

[0013] in

[0014] R 25 It is an alkoxysilyl group having 1 to 4 carbon atoms; R 26 It is a linear organosilyloxy(III) group: (III) Each R 28 Independently, it is a monovalent hydrocarbon group having 1 to 12 carbon atoms; L is selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms and alkoxysilyl groups having 1 to 4 carbon atoms; and k is an integer from 10 to 500; Each X is independently a divalent hydrocarbon group having 2 to 10 carbon atoms; h and i are each an independent integer of 1 or greater; j is an integer of 0 or greater; h+i+j is an integer of 4 or greater; and Each R 27 Independently selected from hydrogen and monovalent hydrocarbon groups having 1 to 6 carbon atoms; or represented by formula IV.

[0015] Formula IV

[0016] Among them, R 29 Indicates unsubstituted or substituted alkyl, alkenyl or aryl groups, each R 30 Independently representing unsubstituted or substituted alkyl, alkenyl, or aryl groups, R 31 and R 32 Each represents the same or different unsubstituted or substituted monovalent hydrocarbon group, each R 33 Each R represents a hydrogen atom independently or an unsubstituted or substituted monovalent hydrocarbon group. 34 Independently represents an unsubstituted or substituted alkyl, alkoxyalkyl, alkenyl or acyl group, and n represents an integer from 2 to 20.

[0017] In another embodiment, the dispersant comprises two or more hydrolyzable organopolysiloxane compounds of formula (II).

[0018] In another embodiment, the dispersant comprises a first hydrolyzable organopolysiloxane represented by formula (II) and having a k value in the range of 10 to 50, and a second hydrolyzable organopolysiloxane represented by formula (II) and having a k value in the range of 100 to 500.

[0019] In one embodiment, the organopolysiloxane contains an H / Vi ratio greater than 0.4.

[0020] In another embodiment, the composition comprises a first thermal conductivity enhancer in an amount of about 15% to about 50% by weight, based on the total weight of the composition. The first thermal conductivity enhancer has an average particle size in the range of 50 to about 200 μm, preferably 80 to 150 μm.

[0021] In another embodiment, the first thermal conductivity enhancer is cubic boron nitride.

[0022] In another embodiment, cubic boron nitride has a surface oxygen content of more than 5%.

[0023] In another embodiment, the composition contains a second thermal conductivity enhancer in an amount of about 20% to about 50% by weight, based on the total weight of the composition.

[0024] In another embodiment, the second thermal conductivity enhancer is selected from alumina, boron nitride, cubic boron nitride, and aluminum nitride.

[0025] In another embodiment, the second thermal conductivity enhancer is present with a first average particle size in the range of 0.5 to less than 2 μm, a second average particle size in the range of 2 μm to less than 10 μm, and a third average particle size in the range of 10 μm to about 120 μm.

[0026] In another embodiment, a second thermal conductivity enhancer having the first average particle size is present in an amount of about 5% to about 25% by weight, based on the total weight of the composition; a second thermal conductivity enhancer having the second average particle size is present in an amount of about 3% to about 10% by weight, based on the total weight of the composition; and a second thermally conductive filler having the third average particle size is present in an amount of about 5% to about 25% by weight, based on the total weight of the composition.

[0027] In another embodiment, the second thermal conductivity enhancer is selected from aluminum nitride.

[0028] In another embodiment, the third thermal conductivity enhancer is selected from alumina, zinc oxide, SiC, and aluminum nitride.

[0029] In another embodiment, the third thermal conductivity enhancer is present in an amount of about 1% to about 10% by weight, based on the total weight of the composition.

[0030] In another embodiment, the third thermal conductivity enhancer is zinc oxide having a particle size in the range of 0.01 to 15 μm.

[0031] In another aspect, a device is provided comprising a first substrate, a second substrate, and an interface material bridging the interface between the first and second substrates, wherein the thermal interface material comprises a single-component thermal gel composition as described in any of the foregoing embodiments.

[0032] In another aspect, the present invention provides a heat dissipation material comprising the composition of the present invention.

[0033] In another aspect, the present invention provides a method for dissipating heat from a substrate, the method comprising contacting the substrate with a composition of the present invention.

[0034] In another aspect, the present invention provides a method for preparing a treated substrate, comprising applying the composition of the present invention to the surface of the substrate.

[0035] In another aspect, the present invention provides a device comprising a treated substrate, wherein the treated substrate comprises the composition of the present invention.

[0036] The following description and figures disclose various illustrative aspects. Some improvements and novel aspects can be clearly identified, while others become apparent from the description and figures. Attached Figure Description

[0037] Figure 1 The graph shows the cumulative hardness data (Shore E) of the thermal composition based on 1-part pre-cured silicone gel CBN under aging at 150°C (Examples 3-7). Detailed Implementation

[0038] Reference will now be made to exemplary embodiments, examples of which are illustrated in the accompanying drawings. It should be understood that other embodiments may be utilized, and structural and functional changes may be made. Furthermore, features of various embodiments may be combined or modified. Therefore, the following description is presented by way of illustration only and should not in any way limit the various alternatives and modifications that may be made to the illustrated embodiments. Numerous specific details in this disclosure provide a thorough understanding of the subject matter. It should be understood that aspects of this disclosure may be practiced, etc., with other embodiments, not necessarily including all aspects described herein.

[0039] As used herein, the terms “example” and “exemplary” mean an instance or illustration. The terms “example” or “exemplary” do not indicate a critical or preferred aspect or implementation. Unless the context otherwise requires, the word “or” is intended to be inclusive rather than exclusive. As an example, the phrase “A employs B or C” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). On the other hand, unless the context otherwise requires, the article “a (type)” generally means “one or more (types)”.

[0040] As used herein, the term "thermal conductivity enhancer" means a solid compound or mixture of compounds that enhances the thermal conductivity of a composition. Examples of thermal conductivity enhancers include, but are not limited to, solid inorganic compounds such as boron nitride, aluminum nitride, alumina, zinc oxide, aluminum metal, silicon carbide, carbon-based fillers such as graphite, and cubic boron nitride, metallic fillers such as aluminum, silver, or mixtures thereof.

[0041] As used herein, the terms "pre-cured gel" or "crosslinked silicone gel" refer to fluid-extended polymer systems that may include a continuous polymer phase or network (which may be chemically, for example, ionicly or covalently, or physically crosslinked), and oils such as silicone or other oils, plasticizers, unreacted monomers, or other fluid extenders that swell or otherwise fill the gaps in the network. The crosslinking density of such a network and the proportion of extenders can be controlled to adjust the modulus (i.e., softness) and other properties of the gel. The term "pre-cured gel" should also be understood to encompass materials that may alternatively be broadly classified as pseudogels or gels because they exhibit viscoelasticity similar to gels, for example, through a "loose" crosslinked network formed by relatively long crosslinked chains, but lack, for example, a fluid extender.

[0042] The term "monovalent hydrocarbon" refers to any hydrocarbon group from which one or more hydrogen atoms have been removed, and includes alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl, cyclic alkynyl, aryl, aralkyl and arenyl, and may contain heteroatoms.

[0043] The term "alkyl" refers to any monovalent, saturated, straight-chain, branched, or cyclic hydrocarbon group; the term "alkenyl" refers to any monovalent, straight-chain, branched, or cyclic hydrocarbon group containing one or more carbon-carbon double bonds, wherein the linkage site of the group may be at a carbon-carbon double bond or at other positions therein; and the term "alkynyl" refers to any monovalent, straight-chain, branched, or cyclic hydrocarbon group containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, wherein the linkage site of the group may be at a carbon-carbon triple bond, a carbon-carbon double bond, or at other positions therein. Examples of alkyl groups include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl groups include vinyl, propenyl, allyl, methylallyl, ethylidenylnorbornane, ethylidene norbornyl, ethylidenylnorbornene, and ethylidene norbornenyl. Examples of alkynyl groups include ethynyl, propynyl, and methylethynyl.

[0044] The terms "cyclic alkyl," "cyclic alkenyl," and "cyclic alkynyl" encompass bicyclic, tricyclic, and higher cyclic structures, as well as those further substituted with alkyl, alkenyl, and / or alkynyl groups. Representative examples include norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecanetrienyl.

[0045] The term "aryl" means any monovalent aromatic hydrocarbon group; the term "aralkyl" means any alkyl group (as defined herein) in which one or more hydrogen atoms are replaced by the same number of the same and / or different aryl groups (as defined herein); and the term "alkylaryl" means any aryl group (as defined herein) in which one or more hydrogen atoms are replaced by the same number of the same and / or different alkyl groups (as defined herein). Examples of aryl groups include phenyl and naphthyl. Examples of aralkyl groups include benzyl and phenethyl. Examples of alkylaryl groups include tolyl and xylyl.

[0046] This disclosure provides reprocessable pre-cured thermosensitive gel compositions comprising a crosslinked silicone gel, an alkenyl-functionalized diorganopolysiloxane fluid, a hydrogen-functionalized organopolysiloxane, an alkoxy-functionalized surface wetting agent (dispersant) or a hydrolyzable organopolysiloxane, thermally conductive fillers, additives, and pigments. Ultra-high thermal conductivity is achieved by using dispersants and organofunctionalized silicone fluids with cubic boron nitride and other thermally conductive fillers. Although these thermal compositions consist of hard fillers such as cubic boron nitride and AlN fillers, they exhibit remarkable thermal stability exceeding 1000 hours at very high temperatures (150°C), not only due to optimization of the fillers and filler ratios but also due to optimization of the composition of the organofunctionalized silicone fluid and the dispersant.

[0047] In a one-part pre-cured thermogel composition, a thermal conductivity of >12 W / mK and low hardness accumulation were achieved (Shore E is below 25 even after aging at 150°C for 1000 hours).

[0048] The filler combination is optimized to achieve an optimal mix that provides high thermal conductivity (TC) and a dispensable formulation. It can be noted that while any two, three, or more fillers can be combined to obtain a formulation, this approach rarely works and results in powdery or low-TC formulations. Only after performing DOE and optimization can we obtain the optimal filler combination that enhances filler packing, thereby providing high thermal conductivity while maintaining paste-like rheological properties, viscosity, and flowability. The filler combination can be described as consisting of three or more fillers: (C-1) is the largest filler type (50-200 μm), which provides the largest domain size to provide high thermal conductivity pathways and thus enhanced thermal conductivity. For the largest filler, inherently high-TC materials such as BN, cubic BN, SiC, diamond, and AlN are utilized, which enhance the overall conductivity of the formulation. The next filler (C-2) is a medium-sized filler of ~0.5-120 μm, which provides enhanced contact and gap filling between the larger fillers. These fillers are composed of alumina, cubic BN, or aluminum nitride powder, or combinations thereof. The smallest filler (C-3) with a D50 of ~0.01-15 μm can be composed of ZnO, alumina, SiC, and / or aluminum nitride fillers, or combinations thereof. Even with their large surface area, these fillers enhance the overall thermal conductivity (TC) by creating numerous filler-polymer-dispersant contacts, as well as filler-filler and filler-substrate contacts. They also provide the desired lubrication and thixotropic effects to the formulation. As a result of careful experimental studies, we have demonstrated here that specific fillers and filler combinations can be used as thermally conductive fillers to achieve thermally conductive formulations with excellent thermal conductivity (>12 W / mK), flexibility, and moldability, and can be easily manufactured at low cost, thus completing this invention.

[0049] In this paper, to achieve ultra-high thermal conductivity, good and stable distributability, and good thermal stability, the filler (cubic boron nitride and other fillers) and organofunctional silicone fluids (organosilicone hydrides, vinyl silicones, pre-cured silicone gels) were optimized, and the dispersant was also optimized.

[0050] This disclosure can define many different ranges for one or more components in a composition. It will be understood that the values ​​of the individual ranges can be combined to form new and unspecified ranges.

[0051] In one aspect, a composition is provided comprising: (A) An organopolysiloxane, wherein the organopolysiloxane comprises (i) Alkenyl-functionalized diorganopolysiloxanes of formula (Ia) M 1 a M2 b D 1 c D 2 d T 1 e T 2 fQ g (Ia) in: M 1 = R 1 R 2 R 3 SiO 1 / 2 M 2 = R 4 R 5 R 6 SiO 1 / 2 D 1 = R 7 R 8 SiO 2 / 2 D 2 = R 9 R 10 SiO 2 / 2 T 1 = R 11 SiO 3 / 2 T 2 = R 12 SiO 3 / 2 Q = SiO 4 / 2 Where R 2 R 3 R 4 R 5 R 6 R 8 R 9 R 10 R 12 Each is independently selected from aliphatic, aromatic, or fluorinated monovalent hydrocarbon groups, or alkoxy groups, having 1 to 60 carbon atoms; R 1 R 7 R 11 It is a monovalent group containing at least one terminal olefinic bond; and The subscripts a, b, c, d, e, f, and g are zero or positive integers subject to the following restrictions: 1 ≤ a + b + c + d + e + f + g ≤ 6000, and a + c + e ≥ 1; and (ii) Hydrogen-functionalized organopolysiloxanes of formula (Ib)

[0052] in: M 1 = R 13 R 14 R 15 SiO 1 / 2 M 2 = R 16 R 17 R 18 SiO 1 / 2 D 1 = R 19 R 20 SiO 2 / 2 D 2 = R 21 R 22 SiO 2 / 2 T 1 = R 23 SiO 3 / 2 T 2 = R 24 SiO 3 / 2 Q = SiO 4 / 2 Where R 14 R 15 R 16 R 17 R 18 R 20 R 21 R 22 R 24 It is an aliphatic, aromatic, or fluorinated monovalent hydrocarbon group having 1 to 60 carbon atoms; R 13 R 19 R 23 It is hydrogen; The subscripts a', b', c', d', e', f', and g' are zero or positive integers subject to the following restrictions: 1 ≤ a'+b'+c'+d'+e'+f'+g' ≤ 6000, and a'+c'+e' ≥ 1; The condition is that when a'+c'+e'=1, then a+c+e>1, and when a+c+e=1, then a'+c'+e'>1; Or the cross-linked products of (i) and (ii), and (B) A thermal conductivity enhancer comprising a first thermal conductivity enhancer having a particle size in the range of 50 to 200 μm; a second thermal conductivity enhancer having a particle size in the range of 0.5 to 120 μm; and a third thermal conductivity enhancer having a particle size in the range of 0.01 to 15 μm.

[0053] Component (i) is an organopolysiloxane represented by formula (Ia) and having at least two alkenyl groups bonded to silicon atoms in one molecule. The viscosity of component (i) at 25°C is in the range of 0.01 to 10 Pa·s, preferably 0.06 to 1 Pa·s. If the viscosity at 25°C is below 0.01 Pa·s, the storage stability of the composition deteriorates, and if it exceeds 10 Pa·s, it cannot maintain fluidity. The viscosity values ​​mentioned above and elsewhere in this application are measured using a Brookfield rotational viscometer. There are no particular limitations on the organopolysiloxane, as long as it meets the above viscosity and alkenyl content requirements, and known organopolysiloxanes can be used. The molecular structure of the organopolysiloxane can be linear, branched, partially branched linear, dendritic, etc. Preferably, the structure is linear or partially branched linear. Component (i) can be a single polymer having such a structure, a copolymer having such a structure, or a mixture of two or more organopolysiloxanes with different viscosities. Furthermore, component (i) can be used in combination with a monoalkenyl-terminated organopolysiloxane having one alkenyl group bonded to a silicon atom per molecule. This organopolysiloxane has a viscosity range of 0.001 to 1 Pa·s, preferably 0.006 to 0.1 Pa·s, at 25°C. Combining the organopolysiloxane with component (i) (an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom per molecule) improves flowability and, in the case of the cured product, facilitates achieving the low hardness required for thermal interface materials.

[0054] Component (ii) is an organohydrogen polysiloxane represented by formula (Ib) and having hydrogen atoms directly bonded to silicon atoms. Specifically, it is an organohydrogen polysiloxane having at least two hydrogen atoms (hydrosilyl groups) directly bonded to silicon atoms in one molecule and acts as a crosslinking agent for component (i). The hydrosilyl groups of component (ii) and the alkenyl groups of component (i) are added together by a hydrosilylation reaction (described later) promoted by a platinum-based metal catalyst to produce a three-dimensional network structure including a crosslinked structure. If the number of hydrosilyl groups in component (ii) is less than two, curing cannot be obtained. The amount of component (ii) added is such that the hydrosilyl groups of component (ii) are 0.1 to 5.0 moles of alkenyl groups relative to 1 mole of component (i) (i.e., the molar amount of hydrogen atoms directly bonded to silicon atoms is 0.1 to 5.0 times the molar amount of alkenyl groups of component (i), preferably 0.2 to 2.0 moles, and more preferably 0.3 to 1.0 moles. If the amount of silyl group in component (ii) is less than 0.1 moles of alkenyl group in 1 mole of component (i), curing may not be achieved or the strength of the cured product may be insufficient, making it difficult to handle as a molded object. If it exceeds 5.0 moles, the cured product loses its flexibility and becomes brittle.

[0055] In one embodiment, the composition further comprises a dispersant represented by Formula II.

[0056] in

[0057] R 25 It is a group having an alkoxysilyl group having 1 to 4 carbon atoms; R 26 It is a linear organosilyloxy(III) group: (III) Each R 28 Independently, it is a monovalent hydrocarbon group having 1 to 12 carbon atoms; L is selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms and alkoxysilyl groups having 1 to 4 carbon atoms; and k is an integer from 10 to 500; Each X is independently a divalent hydrocarbon group having 2 to 10 carbon atoms; h and i are each an independent integer of 1 or greater; j is an integer of 0 or greater; h+i+j is an integer of 4 or greater; and Each R 27 Independently selected from hydrogen and monovalent hydrocarbon groups having 1 to 6 carbon atoms; or represented by formula IV.

[0058] Formula IV

[0059] Among them, R 29 Indicates unsubstituted or substituted alkyl, alkenyl or aryl groups, each R 30 Independently representing unsubstituted or substituted alkyl, alkenyl, or aryl groups, R 31 and R 32 Each represents the same or different unsubstituted or substituted monovalent hydrocarbon group, each R 33 Each R represents a hydrogen atom independently or an unsubstituted or substituted monovalent hydrocarbon group. 34 Independently represents an unsubstituted or substituted alkyl, alkoxyalkyl, alkenyl or acyl group, where m represents an integer from 0 to 4 and n represents an integer from 2 to 20.

[0060] In another embodiment, the dispersant comprises two or more hydrolyzable organopolysiloxane compounds of formula (II).

[0061] In another embodiment, the dispersant comprises a first hydrolyzable organopolysiloxane represented by formula (III) and having a k value in the range of 10 to 50, and a second hydrolyzable organopolysiloxane represented by formula (III) and having a k value in the range of 100 to 500.

[0062] In one embodiment, the organopolysiloxane contains an H / Vi ratio greater than 0.4.

[0063] In another embodiment, the composition comprises a first thermal conductivity enhancer in an amount of about 15% to about 50% by weight, based on the total weight of the composition. The first thermal conductivity enhancer has an average particle size in the range of 50 to about 200 μm, preferably 80 to 150 μm.

[0064] In another embodiment, the first thermal conductivity enhancer is cubic boron nitride.

[0065] In another embodiment, cubic boron nitride has a surface oxygen content of more than 5%.

[0066] In another embodiment, the composition contains a second thermal conductivity enhancer in an amount of about 20% to about 50% by weight, based on the total weight of the composition.

[0067] In another embodiment, the second thermal conductivity enhancer is selected from alumina, boron nitride, cubic boron nitride, and aluminum nitride.

[0068] In another embodiment, the second thermal conductivity enhancer is present with a first average particle size in the range of 0.5 to less than 2 μm, a second average particle size in the range of 2 μm to less than 10 μm, and a third average particle size in the range of 10 μm to about 120 μm.

[0069] In another embodiment, a second thermal conductivity enhancer having the first average particle size is present in an amount of about 5% to about 25% by weight, based on the total weight of the composition; a second thermal conductivity enhancer having the second average particle size is present in an amount of about 3% to about 10% by weight, based on the total weight of the composition; and a second thermally conductive filler having the third average particle size is present in an amount of about 5% to about 25% by weight, based on the total weight of the composition.

[0070] In another embodiment, the second thermal conductivity enhancer is selected from aluminum nitride.

[0071] In another embodiment, the third thermal conductivity enhancer is selected from alumina, zinc oxide, SiC, and aluminum nitride.

[0072] In another embodiment, the third thermal conductivity enhancer is present in an amount of about 1% to about 10% by weight, based on the total weight of the composition.

[0073] In another embodiment, the third thermal conductivity enhancer is zinc oxide having a particle size in the range of 0.01 to 15 μm.

[0074] In another aspect, a device is provided comprising a first substrate, a second substrate, and an interface material bridging the interface between the first and second substrates, wherein the interface material comprises a single-component thermogel composition as described in any of the foregoing embodiments.

[0075] In another aspect, the present invention provides a heat dissipation material comprising the composition of the present invention.

[0076] In another aspect, the present invention provides a method for dissipating heat from a substrate, the method comprising contacting the substrate with a composition of the present invention.

[0077] In another aspect, the present invention provides a method for preparing a treated substrate, the method comprising applying a composition of the present invention to the surface of the substrate.

[0078] In another aspect, the present invention provides a device comprising a treated substrate, wherein the treated substrate comprises the composition of the present invention.

[0079] It will be understood that thermal conductivity enhancers may comprise mixtures of compounds of a single type, wherein the mixture includes compounds of different average particle sizes. In one embodiment, the thermal conductivity enhancer comprises aluminum nitride, boron nitride, SiC, and aluminum oxide.

[0080] The particle size of the thermal conductivity enhancer can be selected according to the needs of a specific purpose or intended application. It will be understood that the composition may comprise a combination of thermal conductivity enhancers with different average particle sizes. Such a combination can be selected according to the needs of a specific purpose or intended application. In one embodiment, the composition comprises a first thermal conductivity enhancer having an average particle size of about 50 to about 200 μm; a second thermal conductivity enhancer having an average particle size of about 0.5 μm to about 120 μm; and optionally a third thermal conductivity enhancer having an average particle size of about 0.01 μm to less than 15 μm. The first, second, and third thermal conductivity enhancers may be the same as or different from each other in terms of the chemical composition of the filler. Particle size can be determined by any suitable method. The average particle size is often provided or reported by the material supplier. The average particle size can be determined by measuring the particle size distribution via laser diffraction and scattering according to JIS R1629. In this study, the median particle size (D50) based on a volumetric datum obtained by measurement is used as the average particle size.

[0081] The filler may be present in an amount of about 80% to about 99% by weight, about 82% to about 96% by weight, or about 85% to about 95% by weight, based on the total weight of the composition.

[0082] Crosslinked silicone gels may also be referred to herein as pre-cured gels or polymer gels. Crosslinked silicone gels are prepared by reacting an alkenyl-functionalized diorganopolysiloxane with a hydrogen-functionalized organopolysiloxane. The reaction can be carried out using a suitable catalyst via hydrosilylation reaction conditions. Conventional hydrosilylation catalysts are platinum-based catalysts (e.g., but not limited to Karstedt catalysts). In one embodiment, the pre-cured gel can be prepared by Pt-catalyzed hydrosilylation of a linear vinyl-terminated polysiloxane with a side-terminated poly(hydrosiloxane) or poly(methylhydrosiloxane) copolymer (crosslinking agent) or a crosslinked MT or MQ resin containing Si-H reactive groups. Similar gel networks can also be achieved by reacting a side-terminated vinyl silicone polymer with a terminally terminated poly(hydrosiloxane) or poly(methylhydrosiloxane) copolymer or a crosslinked MT or MQ resin containing Si-H reactive groups via a Pt-catalyzed hydrosilylation pathway. The effective Si-H / Si-olefin molar ratio [r] for forming Si-C bonds must satisfy r ≤ 0.3. The final "gel rheology" must meet the following condition: a) 0.2≤G'≤1000 (Pa); b) 0.1≤G” / G'≤10; The term G' represents the "storage shear modulus" of the final pre-cured gel composition for use in thermal interface material formulations, measured by a stress- or strain-controlled rheometer at an oscillation frequency of 1 Hz or 6.28 rad / s at T=25°C, and the term G'' represents the "loss shear modulus" of the final pre-cured gel composition for use in thermal interface material formulations, measured by a stress- or strain-controlled rheometer at an oscillation frequency of 1 Hz or 6.28 rad / s at T=25°C. G'' and G' are measured together in their respective viscoelastic regions.

[0083] The following examples are intended to illustrate aspects and implementations of the technology. Unless otherwise expressly stated, all parts and percentages are by weight, and all temperatures are in degrees Celsius. All patents, other publications, and US patent applications mentioned in this application are incorporated herein by reference in their entirety.

[0084] Example

[0085] Stable shear viscosity and thixotropy were determined using a rheometer (RS-600) with a parallel plate geometry (measuring geometric gap of 500 μm).

[0086] Hardness testing: The hardness of the gel was measured using an ASTM D2240 hardness tester (Shore E) and an ASTM D-217 penetrometer (penetration range: 0-400 Pen~40 mm; penetration time: 5 seconds).

[0087] Hardness tests of the pre-cured (part 1) and post-cured (part 2) formulations were performed using an ASTM D2240 hardness tester (Shore E).

[0088] The volumetric thermal conductivity of the thermal composition was measured at 22°C using a hot plate instrument, and thermal resistance and thermal conductivity were also measured using ASTM D5470.

[0089] Dispensability was measured by filling an Optimum 30cc syringe with an EFD nozzle of 2 mm with the sample and dispensing it at 90 psi using an automatic dispenser (Nordson EFD), and measuring the volume dispensed per minute.

[0090] BLT was determined by applying a compression of 1 MPa for 30 seconds on a 10 × 10 × 0.5 mm Si chip.

[0091] The crystallite size was measured by XRD using an X-ray diffractometer system with the following parameters: a copper target (Kα line) at a wavelength of 1.54 Å, an accelerating voltage of 40 kV, a tube current of 30 mA, a scan rate of 4 ° / min, and a step size of 0.02 °.

[0092] Surface oxygen content was measured by XPS using an X-ray photoelectron spectrometer with the following features: Al Kα source, 2 × 10⁻⁹ Torr vacuum level, hemispherical analyzer, 0.7 s residence time, 1 eV energy step, and 0.1 eV HR scan.

[0093] The pre-cured gel thermal formulation was prepared in a Thinky mixer. First, specific amounts of dispersant, Vinyl PDMS fluid, and gel were weighed into a plastic container and mixed at 2000 rpm for 30 seconds. A filler with variable particle size was gradually added to the mixture, and at each step, all materials were mixed at 2000 rpm for 30 seconds using the Thinky mixer. In each step, after mixing for 30 seconds, the formulation was manually mixed for 2 minutes using a wide-bladed spatula. Finally, the mixture was mixed 1-2 times at 2000 rpm for 30 seconds each time to obtain a homogeneous paste.

[0094] A two-part curable formulation similar to a pre-cured gel formulation was also prepared. Part A and Part B were prepared separately, mixed in equal amounts, and cured at 70°C for 1 hour.

[0095] The two-part addition-curing composition was prepared according to Examples 1 and 2.

[0096] The thermally conductive pre-cured gel composition was prepared according to Examples 3 to 7.

[0097] Table 1 provides the properties of the two-part addition-curing thermocomposition.

[0098] Table 2 provides the properties of the thermally conductive pre-cured gel compositions.

[0099] The divinyl-terminated organopolysiloxane (A-1a) has a viscosity of 0.1 Pa·s and is expressed by the following formula:

[0100] Each X represents vinyl, and n ranges from 20 to 400.

[0101] The divinyl-terminated organopolysiloxane (A-1b) has a viscosity of 0.03 Pa·s and is expressed by the following formula:

[0102] Each X represents vinyl, and n is 10 to 20.

[0103] The monovinyl-terminated organopolysiloxane (A-2a) has a viscosity of 0.02 Pa·s and is expressed by the following formula:

[0104] Where X is vinyl and m is 20 to 100.

[0105] The monovinyl-terminated organopolysiloxane (A-2b) has a viscosity of 0.01 Pa·s and is expressed by the following formula:

[0106] Where X is vinyl and m is 10 to 20.

[0107] The crosslinking agent, organohydrogen polysiloxane (B-1), has a viscosity range of 0.01 to 0.1 Pa·s, a Si-H content of 0.05 to 0.5% by weight, and in the examples, a compound of the following formula with a viscosity of 0.02 Pa·s is used:

[0108] Where o is between 20 and 100, and p is between 2 and 20.

[0109] Cubic boron nitride was purchased from Funik (China).

[0110] Aluminum nitride was purchased from Toyo aluminum.

[0111] Nano zinc oxide was purchased from Zochem.

[0112] Cubic BN has a volume average particle size of 50-200 μm ((C-1a: 90 μm), (C-1b: 152 μm), (C-1c: 95 μm), (C-1d: 113 μm), (C-1e: 114 μm)) and a surface oxygen content greater than 5%.

[0113] Aluminum nitride with volume-average particle sizes of 1.2, 5, 20 and 70 μm (C-2a, C-2b, C-2c and C-2d, respectively).

[0114] Nano zinc oxide with a volume average particle size of 0.16 μm (C-3).

[0115] (D-1) is a hydrolyzable organopolysiloxane (II-i) represented by the following formula:

[0116] (Formula II-i)

[0117] (D-2) represents a hydrolyzable polyorganosiloxane represented by a compound of formula (II-ii):

[0118] (Formula II-ii)

[0119] E-1 is selected from 3,3'-thiodipropionate didodecyl ester or 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene, and is used as an additive in formulations.

[0120] F-1 is an inhibitor. Bis(1,1-dimethyl-2-propynoxy)dimethylsilane.

[0121] Example 1: Part A: Weigh polysiloxanes A-1a (1.00 g) and A-2a (1.21 g), hydrolyzable polysiloxane D-1 (1.0 g), and Pt-catalyst G-1 (a 18% by weight solution of Pt dimer complex (2% Pt) in a monovinyl-terminated organopolysiloxane (viscosity 0.02 Pa·s)) (0.286 g) in a plastic container and mix at 2000 rpm for 30 seconds using a Thinky mixer. Gradually add thermally conductive fillers C-1a (45.0 g), C-2a (15.0 g), C-2b (10.0 g), C-2c (20.75 g), and C-3 (5.75 g) to the mixture, mixing all materials together at 2000 rpm for 30 seconds at each step using a Thinky mixer. After each 30-second mixing, manually mix the formulation for 2 minutes using a wide-bladed spatula. The mixture was further mixed in a Thinky mixer at 2000 rpm for 30 seconds. After mixing, the formulation was degassed at room temperature to remove any trapped air. The total weight of the formulation was 100 g.

[0122] Part B: Weigh polysiloxanes A-1a (1.00 g) and A-2a (1.18 g), hydrolyzable polysiloxane D-1 (1.0 g), crosslinking agent B-1 (hydrogen-functionalized organopolysiloxane) (0.12 g), and inhibitor F-1 (bis(1,1-dimethyl-2-propynoxy)dimethylsilane) (a 1.5 wt% solution in hydrogen-functionalized organopolysiloxane (viscosity 0.02 Pa·s)) (0.2 g) in a plastic container and mix at 2000 rpm for 30 seconds using a Thinky mixer. Gradually add thermally conductive fillers C-1a (45.0 g), C-2a (15.0 g), C-2b (10.0 g), C-2c (20.75 g), and C-3 (5.75 g) to the mixture, mixing at 2000 rpm for 30 seconds using a Thinky mixer at each step. Mix all ingredients together at 30 rpm for 30 seconds. After each 30-second mixing, manually mix the formulation for 2 minutes using a wide-bladed spatula. Further mix the mixture in a Thinky mixer at 2000 rpm for 30 seconds. After mixing, degas the formulation at room temperature to remove any trapped air. The total weight of the formulation is 100 g.

[0123] Example 2 was prepared in the same manner as Example 1, wherein...

[0124] Part A: Polysiloxanes A-1a (1.0 g) and A-2a (1.21 g), hydrolyzable polysiloxane D-1 (1.0 g), Pt-catalyst G-1 (18 wt% solution of Pt dimer complex (2 wt% Pt) in a monovinyl-terminated organopolysiloxane (viscosity 0.02 Pa·s)) (0.286 g) were mixed with thermally conductive fillers C-1b (45.0 g), C-2a (15.0 g), C-2b (10.0 g), C-2c (20.75 g), and C-3 (5.75 g). The total weight of the preparation was 100 g.

[0125] Part B: Polysiloxanes A-1a (1.0 g) and A-2a (1.18 g), hydrolyzable polysiloxane D-1 (1.0 g), crosslinking agent B-1 (hydrogen-functionalized organopolysiloxane) (0.20 g), inhibitor F-1 (bis(1,1-dimethyl-2-propynoxy)dimethylsilane) (a 1.5 wt% solution in hydrogen-functionalized organopolysiloxane (viscosity 0.02 Pa·s)) (0.2 g) was mixed with thermally conductive fillers C-1b (45.0 g), C-2a (15.0 g), C-2b (10.0 g), C-2c (20.75 g), and C-3 (5.75 g). The total weight of the preparation was 100 g.

[0126] Synthesis of pre-cured gels or crosslinked polysiloxanes: Vinyl-terminated PDMS (500 g, MW ~17280 g / mol, vinyl MEQ ~0.115) was added to a dual planetary mixer at room temperature along with a Pt catalyst (2 wt% Karstedt catalyst, 10 ppm Pt) and an inhibitor (Surfynol® 61, 200 ppm), and allowed to mix at 20 rpm for 30 minutes at room temperature. Silicone hydride (55.4 g, MW ~40802, hydride MEQ ~0.1586) was added to the reaction mixture at 50°C, and mixing was continued at 20 rpm for an additional 1 hour. While continuing mixing at the same rate at 50°C, a vacuum was applied for 60 minutes to remove the inhibitor and form a gel network. The reaction temperature was then increased to 90°C and continued until all hydride was consumed and a gel formed.

[0127] Example 3: Weigh polysiloxane A-1a (1.75 g), crosslinked polysiloxane X-1 (1.0 g), and hydrolyzed polysiloxane D-1 (1.5 g) into a plastic container and mix using a Thinky mixer at 2000 rpm for 30 seconds. Gradually add thermally conductive fillers C-1c (48.5 g), C-2a (15.0 g), C-2b (5.0 g), C-2c (20.95 g), and C-3 (6.0 g) to the mixture, mixing all materials together at 2000 rpm for 30 seconds at each step using a Thinky mixer. After each 30-second mixing, manually mix the formulation for 2 minutes using a wide-bladed spatula. Further mix the mixture in a Thinky mixer at 2000 rpm for 30 seconds. After mixing, degas the formulation at room temperature to remove any trapped air. The total weight of the formulation is 100 g.

[0128] Example 4 was prepared in the same manner as Example 3, wherein polysiloxane A-1a (1.75 g), crosslinked polysiloxane (1.0 g), hydrolyzed polysiloxane D-1 (1.5 g), and thermally conductive fillers C-1a (48.5 g), C-2a (15.0 g), C-2b (5.0 g), C-2c (20.95 g), and C-3 (6.0 g) were mixed. The total weight of the formulation was 100 g.

[0129] Example 5 was prepared in the same manner as Example 3, wherein polysiloxane A-1a (1.75 g), crosslinked polysiloxane (1.0 g), hydrolyzed polysiloxane D-1 (1.5 g) were mixed with thermally conductive fillers C-1d (48.5 g), C-2a (15.0 g), C-2b (5.0 g), C-2c (20.95 g), and C-3 (6.0 g). The total weight of the formulation was 100 g.

[0130] Example 6 was prepared in the same manner as Example 3, wherein polysiloxane A-1a (1.75 g), crosslinked polysiloxane (1.0 g), hydrolyzed polysiloxane D-1 (1.5 g), and thermally conductive fillers C-1e (48.5 g), C-2a (15.0 g), C-2b (5.0 g), C-2c (20.95 g), and C-3 (6.0 g) were mixed. The total weight of the formulation was 100 g.

[0131] Example 7 was prepared in the same manner as Example 3, wherein polysiloxane A-1a (1.75 g), crosslinked polysiloxane (1.0 g), hydrolyzed polysiloxane D-1 (1.5 g), and thermally conductive fillers C-1b (48.5 g), C-2a (15.0 g), C-2b (5.0 g), C-2c (20.95 g), and C-3 (6.0 g) were mixed. The total weight of the formulation was 100 g.

[0132] As shown in Table 2 and Figure 1 As shown, compositions containing a mixture of thermal conductivity enhancers and CBN exhibit better thermal conductivity and stability.

[0133] Ultra-high thermal conductivity two-part addition-curing thermal composition: Table 1

[0134] TIA2101GF is a commercial two-part silicone formulation manufactured by Momentive Performance Materials.

[0135] Two-part addition-curable thermopolymer compositions were prepared with different filler percentages and achieved ultra-high thermal conductivity (>16 W / mK) accompanied by good dispensability (>13 g / min). They were cured at 70°C for 1 hour by mixing part-A and part-B in a 1:1 ratio. The H / Vi ratio of the cured samples ranged from 0.4 to 1.0.

[0136] As can be seen from Table 2, Examples 3, 4, 5, 6 and 7 show thermal conductivity >14 W / mK, accompanied by less hardness accumulation at high temperatures of 150°C during aging.

[0137] Ultra-high thermal conductivity pre-cured gel composition: Table 2

[0138] Precured thermogel formulations based on cubic boron nitride and other fillers were designed, and they provide very high thermal conductivity in the range of 12-16 W / mK (Table 2). Even with hard fillers such as AlN and cubic boron nitride, and high filler loading in the thermal composition, these thermogel formulations exhibit very good thermal stability at very high temperatures. These thermogel formulations show very little hardness accumulation at 150°C. For example, Examples 3, 4, 5, and 7 show very little hardness accumulation (Shore E) even after aging at 150°C for up to 1000 hours.

[0139] Figure 1 The cumulative hardness data (Shore E) of the thermal composition of pre-cured silicone gel CBN based on part 1 after aging at 150°C are shown (Examples 3-7).

[0140] The embodiments of the invention have been described above. It is certainly impossible to describe every conceivable combination of components or methods for the purposes of describing the invention, but those skilled in the art will recognize that many further combinations and arrangements of the invention are possible. Therefore, the invention is intended to cover all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, to the extent used in the specific embodiments or claims, such a term is intended to be inclusive in a manner similar to the term "comprising," as illustrated when "comprising" is used as a transitional word in the claims.

[0141] The foregoing description defines various non-limiting embodiments of the thermogel composition. Modifications will be conceived by those skilled in the art, as well as those capable of making and using the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter set forth in the claims.

[0142] Other embodiments of the present invention are provided below.

[0143] Embodiment 1: A composition comprising: (A) An organopolysiloxane, wherein the organopolysiloxane comprises (i) Alkenyl-functionalized diorganopolysiloxanes of formula (Ia) M 1 a M 2 b D 1c D 2 d T 1 e T 2 f Q g (Ia) in: M 1 = R 1 R 2 R 3 SiO 1 / 2 M 2 = R 4 R 5 R 6 SiO 1 / 2 D 1 = R 7 R 8 SiO 2 / 2 D 2 = R 9 R 10 SiO 2 / 2 T 1 = R 11 SiO 3 / 2 T 2 = R 12 SiO 3 / 2 Q = SiO 4 / 2 Where R 2 R 3 R 4 R 5 R 6 R 8 R 9 R 10 R 12 Each is independently selected from aliphatic, aromatic, and fluorinated monovalent hydrocarbons, or alkoxy groups, having 1 to 60 carbon atoms; R 1 R 7 R 11 Each is independently selected from aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms and containing at least one terminal olefinic bond; and The subscripts a, b, c, d, e, f, and g are zero or positive integers subject to the following restrictions: 1 ≤ a + b + c + d + e + f + g ≤ 6000, and a + c + e ≥ 1; and (ii) Hydrogen-functionalized organopolysiloxanes of formula (Ib) M 1 a' M 2 b' D 1 c' D 2 d' T 1 e' T 2 f' Q g' (1b) in: M 1 = R 13 R 14 R 15 SiO 1 / 2 M 2 = R 16 R 17 R 18 SiO 1 / 2 D 1 = R 19 R 20 SiO 2 / 2 D 2 = R 21 R 22 SiO 2 / 2 T 1 = R 23 SiO 3 / 2 T 2 = R 24 SiO 3 / 2 Q = SiO 4 / 2 Where R 14 R 15 R 16 R 17 R 18 R 20 R 21 R 22 R 24 Aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms; R 13 R 19 R 23 It is hydrogen; The subscripts a', b', c', d', e', f', and g' are zero or positive integers subject to the following restrictions: 1 ≤ a'+b'+c'+d'+e'+f'+g' ≤ 6000, and a'+c'+e' ≥ 1; The condition is that when a'+c'+e'=1, then a+c+e>1, and when a+c+e=1, then a'+c'+e'>1; Or the cross-linked products of (i) and (ii), and (B) A thermal conductivity enhancer comprising a first thermal conductivity enhancer having a particle size in the range of 50 to 200 μm; a second thermal conductivity enhancer having a particle size in the range of 0.5 to 120 μm; and a third thermal conductivity enhancer having a particle size in the range of 0.01 to 15 μm.

[0144] Embodiment 2: The composition according to Embodiment 1 further comprises a dispersant represented by Formula II.

[0145] in

[0146] R 25 It is an alkoxysilyl group having 1 to 4 carbon atoms; R 26 It is a linear organosilyloxy(III) group: (III) Each R 28 Independently, it is a monovalent hydrocarbon group having 1 to 12 carbon atoms; L is selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms and alkoxysilyl groups having 1 to 4 carbon atoms; and k is an integer from 10 to 500; Each X is independently a divalent hydrocarbon group having 2 to 10 carbon atoms; h and i are each an independent integer of 1 or greater; j is an integer of 0 or greater; h+i+j is an integer of 4 or greater; and Each R 27 Independently selected from hydrogen and monovalent hydrocarbon groups having 1 to 6 carbon atoms; or represented by formula IV.

[0147] Formula IV

[0148] Among them, R 29 Indicates unsubstituted or substituted alkyl, alkenyl or aryl groups, each R 30 Independently representing unsubstituted or substituted alkyl, alkenyl, or aryl groups, R 31 and R 32Each represents the same or different unsubstituted or substituted monovalent hydrocarbon group, each R 33 Each R represents a hydrogen atom independently or an unsubstituted or substituted monovalent hydrocarbon group. 34 Independently represents an unsubstituted or substituted alkyl, alkoxyalkyl, alkenyl or acyl group, and n represents an integer from 2 to 20.

[0149] Embodiment 3: The composition according to Embodiment 1, wherein the organopolysiloxane contains an H / Vi ratio greater than 0.4.

[0150] Embodiment 4: The composition according to Embodiment 2, wherein the dispersant is a compound represented by the following formula: .

[0151] Embodiment 5: The composition according to Embodiment 4, wherein the dispersant comprises two or more hydrolyzable organopolysiloxane compounds of formula (II).

[0152] Embodiment 6: The composition according to Embodiment 4, wherein the dispersant comprises a first hydrolyzable organopolysiloxane represented by Formula (II) and having a k value in the range of 10 to 50, and a second hydrolyzable organopolysiloxane represented by Formula (II) and having a k value in the range of 100 to 500.

[0153] Embodiment 7: A composition according to any one of Embodiments 1 to 6, wherein the composition contains the first thermal conductivity enhancer in an amount of 15% to 50% by weight, based on the total weight of the composition.

[0154] Embodiment 8: The composition according to Embodiment 7, wherein the first thermal conductivity enhancer is cubic boron nitride.

[0155] Embodiment 9: The composition according to Embodiment 8, wherein cubic boron nitride has a surface oxygen content of greater than 5%.

[0156] Embodiment 10: The composition according to Embodiments 1 to 6, wherein the second thermal conductivity enhancer is alumina, boron nitride, cubic boron nitride, and aluminum nitride.

[0157] Embodiment 11: The composition according to Embodiment 10, wherein the composition contains the second thermal conductivity enhancer in an amount of 20% to 50% by weight, based on the total weight of the composition.

[0158] Embodiment 12: The composition according to Embodiment 10 or 11, wherein the second thermal conductivity enhancer is present with a first average particle size in the range of 0.5 to less than 1.5 μm, a second average particle size in the range of 1.5 μm to less than 10 μm, and a third average particle size in the range of 10 μm to 120 μm.

[0159] Embodiment 13: The composition according to Embodiment 12, wherein the second thermal conductivity enhancer having the first average particle size is present in an amount of 5% to 25% by weight, based on the total weight of the composition; the second thermal conductivity enhancer having the second average particle size is present in an amount of 3% to 10% by weight, based on the total weight of the composition; and the second thermal conductivity enhancer having the third average particle size is present in an amount of 5% to 25% by weight, based on the total weight of the composition.

[0160] Embodiment 14: The composition according to any one of Embodiments 10 to 13, wherein the second thermal conductivity enhancer is selected from aluminum nitride.

[0161] Embodiment 15: The composition according to any one of Embodiments 1 to 6, wherein the third thermal conductivity enhancer is selected from alumina, zinc oxide, SiC and aluminum nitride.

[0162] Embodiment 16: The composition according to any one of Embodiments 1 to 13, comprising the third thermal conductivity enhancer in an amount of 1% to 10% by weight, based on the total weight of the composition.

[0163] Embodiment 17: The composition according to Embodiment 14, wherein the third thermal conductivity enhancer is ZnO having a particle size in the range of 0.01 to 15 μm.

[0164] Embodiment 18: A device comprising a first substrate, a second substrate, and an interface material bridging an interface between the first and second substrates, wherein the interface material comprises a composition according to any one of Embodiments 1 to 15.

[0165] Embodiment 19: A heat dissipation material comprising the composition according to any one of Embodiments 1 to 15.

[0166] Embodiment 20: A method for dissipating heat from a substrate, the method comprising contacting the substrate with the composition of any one of Embodiments 1 to 15.

[0167] Embodiment 21: A method for preparing a treated substrate, comprising applying the composition of any one of Embodiments 1 to 15 to the surface of the substrate.

[0168] Embodiment 22: A device comprising a treated substrate, wherein the treated substrate comprises a composition according to any one of Embodiments 1 to 15.

Claims

1. A composition comprising: (A) An organopolysiloxane, wherein the organopolysiloxane comprises (i) Alkenyl-functionalized diorganopolysiloxanes of formula (Ia) M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g (Ia) in: M 1 =R 1 R 2 R 3 SiO 1 / 2 M 2 =R 4 R 5 R 6 SiO 1 / 2 D 1 =R 7 R 8 SiO 2 / 2 D 2 =R 9 R 10 SiO 2 / 2 T 1 =R 11 SiO 3 / 2 T 2 =R 12 SiO 3 / 2 Q=SiO 4 / 2 Where R 2 R 3 R 4 R 5 R 6 R 8 R 9 R 10 R 12 Each is independently selected from aliphatic, aromatic, and fluorinated monovalent hydrocarbons, or alkoxy groups, having 1 to 60 carbon atoms; R 1 R 7 R 11 Each is independently selected from aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms and containing at least one terminal olefinic bond; and The subscripts a, b, c, d, e, f, and g are zero or positive integers subject to the following restrictions: 1 ≤ a + b + c + d + e + f + g ≤ 6000, and a + c + e ≥ 1; and (ii) Hydrogen-functionalized organopolysiloxanes of formula (Ib) M 1 a' M 2 b' D 1 c' D 2 d' T 1 e' T 2 f' Q g' (1b) in: M 1 =R 13 R 14 R 15 SiO 1 / 2 M 2 =R 16 R 17 R 18 SiO 1 / 2 D 1 =R 19 R 20 SiO 2 / 2 D 2 =R 21 R 22 SiO 2 / 2 T 1 =R 23 SiO 3 / 2 T 2 =R 24 SiO 3 / 2 Q=SiO 4 / 2 Where R 14 R 15 R 16 R 17 R 18 R 20 R 21 R 22 R 24 Aliphatic, aromatic, or fluorinated monovalent hydrocarbons having 1 to 60 carbon atoms; R 13 R 19 R 23 It is hydrogen; The subscripts a', b', c', d', e', f', and g' are zero or positive integers subject to the following restrictions: 1 ≤ a'+b'+c'+d'+e'+f'+g' ≤ 6000, and a'+c'+e' ≥ 1; The condition is that when a'+c'+e'=1, then a+c+e>1, and when a+c+e=1, then a'+c'+e'>1; Or the cross-linked products of (i) and (ii), and (B) A thermal conductivity enhancer comprising a first thermal conductivity enhancer having a particle size in the range of 50 to 200 μm; a second thermal conductivity enhancer having a particle size in the range of 0.5 to 120 μm; and a third thermal conductivity enhancer having a particle size in the range of 0.01 to 15 μm.

2. The composition according to claim 1, further comprising a dispersant represented by formula II, Formula II in, R 25 It is a group having an alkoxysilyl group having 1 to 4 carbon atoms; R 26 It is a linear organosilyloxy(III) group: (III) Each R 28 Independently, it is a monovalent hydrocarbon group having 1 to 12 carbon atoms; L is selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms and alkoxysilyl groups having 1 to 4 carbon atoms; and k is an integer from 10 to 500; Each X is independently a divalent hydrocarbon group having 2 to 10 carbon atoms; h and i are each an independent integer of 1 or greater; j is an integer of 0 or greater; h+i+j is an integer of 4 or greater; and Each R 27 Independently selected from hydrogen and monovalent hydrocarbon groups having 1 to 6 carbon atoms; or represented by formula IV. Among them, R 29 Indicates unsubstituted or substituted alkyl, alkenyl or aryl groups, each R 30 Independently representing unsubstituted or substituted alkyl, alkenyl, or aryl groups, R 31 and R 32 Each represents the same or different unsubstituted or substituted monovalent hydrocarbon group, each R 33 Each R represents a hydrogen atom independently or an unsubstituted or substituted monovalent hydrocarbon group. 34 Independently represents an unsubstituted or substituted alkyl, alkoxyalkyl, alkenyl or acyl group, and n represents an integer from 2 to 20.

3. The composition according to claim 1, wherein the organopolysiloxane contains an H / Vi ratio greater than 0.

4.

4. The composition according to claim 2, wherein the dispersant is a compound represented by the following formula: 。 5. The composition according to claim 4, wherein the dispersant comprises two or more hydrolyzable organopolysiloxane compounds of formula (II).

6. The composition according to claim 4, wherein the dispersant comprises a first hydrolyzable organopolysiloxane represented by formula (II) and having a k value in the range of 10 to 50, and a second hydrolyzable organopolysiloxane represented by formula (II) and having a k value in the range of 100 to 500.

7. The composition according to any one of claims 1 to 6, wherein the composition comprises the first thermal conductivity enhancer in an amount of 15% to 50% by weight, based on the total weight of the composition.

8. The composition according to claim 7, wherein the first thermal conductivity enhancer is cubic boron nitride.

9. The composition according to claim 8, wherein cubic boron nitride has a surface oxygen content of greater than 5%.

10. The composition according to claims 1 to 6, wherein the second thermal conductivity enhancer is selected from alumina, boron nitride, cubic boron nitride, and aluminum nitride.

11. The composition of claim 10, wherein the composition comprises the second thermal conductivity enhancer in an amount of 20% to 50% by weight, based on the total weight of the composition.

12. The composition according to claim 10 or 11, wherein the second thermal conductivity enhancer is present with a first average particle size in the range of 0.5 to less than 1.5 μm, a second average particle size in the range of 1.5 μm to less than 10 μm, and a third average particle size in the range of 10 μm to 120 μm.

13. The composition of claim 12, wherein the second thermal conductivity enhancer having the first average particle size is present in an amount of 5% to 25% by weight, based on the total weight of the composition; the second thermal conductivity enhancer having the second average particle size is present in an amount of 3% to 10% by weight, based on the total weight of the composition; and the second thermal conductivity enhancer having the third average particle size is present in an amount of 5% to 25% by weight, based on the total weight of the composition.

14. The composition according to claims 10 to 13, wherein the second thermal conductivity enhancer is selected from aluminum nitride.

15. The composition according to claims 1 to 6, wherein the third thermal conductivity enhancer is selected from alumina, zinc oxide, SiC, and aluminum nitride.

16. The composition according to any one of claims 1 to 15, comprising the third thermal conductivity enhancer in an amount of 1% to 10% by weight, based on the total weight of the composition.

17. The composition according to claim 16, wherein the third thermal conductivity enhancer is ZnO having a particle size in the range of 0.01 to 15 μm.

18. A device comprising a first substrate, a second substrate, and an interface material bridging an interface located between the first and second substrates, wherein the interface material comprises a composition according to any one of claims 1 to 17.

19. A heat dissipation material comprising the composition according to any one of claims 1 to 17.

20. A method for dissipating heat from a substrate, the method comprising contacting the substrate with a composition according to any one of claims 1 to 17.

21. A method for preparing a treated substrate, comprising applying the composition according to any one of claims 1 to 17 to the surface of the substrate.

22. A device comprising a treated substrate, wherein the treated substrate comprises the composition according to any one of claims 1 to 15.

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