Addition-curing thermally conductive organopolysiloxane adhesive composition

Abstract

A two-component addition-curing thermal conductive adhesive composition comprising: A) a vinyl-functionalized polysiloxane having at least two vinyl groups per molecule; B) at least one hydrosilylation catalyst; C) at least one condensation catalyst; D) at least one silylhydride-functionalized polysiloxane; E) at least one thermally conductive filler; F) at least one SiH-functionalized silane; and G) at least one Q-branched alkenyl polymer.

Description

[Technical Field]

[0001] (Field of Invention) This disclosure relates to a two-component addition-curing thermally conductive organopolysiloxane adhesive composition.

[0002] (Introduction) Insulating and thermally conductive adhesives are commonly used in the electronics industry because they thermally bond components together and aid in heat dissipation. Silicone-based thermally conductive adhesives offer advantages such as high elasticity and good durability compared to organic adhesives such as epoxy or PU. Silicone-based thermally conductive adhesives can be obtained by compounding a polysiloxane matrix with a thermally conductive but electrically insulating filler. However, one of the key challenges for addition-curing silicone systems is achieving high adhesive strength at lower curing temperatures, such as 70°C for 0.5 hours.

[0003] Addition-curing silicone systems include vinyl-functionalized polysiloxanes and SiH-functionalized polysiloxanes, and can be cured at room temperature or high temperatures catalyzed via a Pt catalyst (system D). Adhesion promoters designed for addition-curing silicone systems typically require high temperatures to build sufficient adhesive strength. Another type of silicone is condensation-curing silicone, which is catalyzed by a condensation catalyst (system F). This can build good adhesion cured at room temperature simply by exposure to moisture.

[0004] Thermally conductive silicone materials have low surface energy, making it difficult to form strong adhesion to most substrates. For addition-curing silicone products, adhesion promoters such as epoxy or acrylic-functionalized silanes are usually required to achieve good adhesion strength at high temperatures (typically >120°C) during curing. To achieve good adhesion strength at lower temperatures (≤70°C), the D+F system technique has been used.

[0005] However, the adhesive strength of thermally conductive addition-curable silicone compositions is generally still not sufficiently good for some applications where PU or epoxy adhesives are commonly used.

[0006] In view of the above, there still remains a certain need for addition-curable thermally conductive adhesive compositions that exhibit good adhesive strength at low temperatures. Summary of the Invention

[0007] After continuous investigation, the present inventors surprisingly found a two-part addition-curable thermally conductive adhesive composition that exhibits good adhesive strength.

[0008] In a first aspect of the present disclosure, the present disclosure provides a two-part addition-curable thermally conductive adhesive composition, which comprises: A) a vinyl-functional polysiloxane having at least two vinyl groups per molecule, B) at least one hydrosilylation catalyst, C) at least one condensation catalyst, D) at least one silyl hydride-functional polysiloxane, E) at least one thermally conductive filler, F) at least one SiH-functional silane, G) at least one Q-branched alkenyl polymer.

[0009] In a second aspect of the present disclosure, the present disclosure provides an article comprising a cured product formed by curing the two-part addition-curable thermally conductive adhesive composition described herein.

[0010] In a third aspect of the present disclosure, the present disclosure provides use of the composition described herein in the preparation of an article.

[0011] It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and are not intended to limit the claimed invention. Mode for Carrying Out the Invention

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. Furthermore, all publications, patent applications, patents, and other references referenced herein are incorporated by reference.

[0013] Where disclosed herein, the terms “composition,” “formulation,” or “mixture” refer to a physical blend of different components obtained by simply mixing different components by physical means.

[0014] In this specification, “and / or” means “and, or alternatively.” All scopes include endpoints unless otherwise indicated.

[0015] "Alkyl" means an acyclic, branched, or unbranched saturated monovalent hydrocarbon group. Alkyls are exemplified by, but are not limited to, Me, Et, Pr (e.g., iso-Pr and / or n-Pr), Bu (e.g., iso-Bu, n-Bu, tert-Bu and / or sec-Bu), pentyl (e.g., iso-pentyl, neo-pentyl and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, as well as branched saturated monovalent hydrocarbon groups with 6 to 12 carbon atoms. Alkyl groups may have 1 to 30, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, and alternatively 1 to 6 carbon atoms.

[0016] "Alkyloxy" means -O-alkyl, and alkyl is as described above.

[0017] "Alkenyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Alkenyls are exemplified by, but are not limited to, vinyl, allyl, methallyl, propenyl, and hexenyl. An alkenyl group may have 2 to 30, 2 to 24, 2 to 20, 2 to 12, 2 to 10, or 2 to 6 carbon atoms.

[0018] "Aryl" refers to a completely unsaturated cyclic hydrocarbon group. Examples of aryls include, but are not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7, or alternatively 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17, or 10 to 14, or 12 to 14 carbon atoms.

[0019] The term “substituted” as used in relation to another group, such as the hydrocarbyl group, means, unless otherwise indicated, that one or more hydrogen atoms in the hydrocarbyl group are replaced by another substituent. Examples of such substituents include, but are not limited to, halogen atoms, such as chlorine, fluorine, bromine, and iodine; halogen-containing groups such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl groups; oxygen atoms; oxygen-containing groups such as (meth)acrylic and carboxyl groups; nitrogen atoms; nitrogen-containing groups such as amines, amino functional groups, amide functional groups, and cyano functional groups; sulfur atoms; and sulfur-containing groups such as mercapto groups.

[0020] The M, D, T, and Q units are generally R u SiO( 4-u) / 2 [In the formula, u is 3, 2, 1, and 0 for M, D, T, and Q, respectively, and R is an independently selected hydrocarbyl group.] M, D, T, and Q represent one (Mono), two (Di), three (Tri), or four (Quad) oxygen atoms covalently bonded to a silicon atom bonded to the rest of the molecular structure.

[0021] Two-component addition-curing thermal conductive adhesive composition, A) A vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, B) At least one hydrosilylation catalyst, C) At least one type of condensation catalyst, D) At least one silylhydride-functionalized polysiloxane, E) At least one type of thermally conductive filler, F) At least one SiH-functionalized silane, G) comprising at least one Q-branched alkenyl polymer.

[0022] Composition components A) Vinyl-functionalized polysiloxane having at least two vinyl groups per molecule A vinyl-functionalized polysiloxane A) having at least two vinyl groups per molecule can be a linear polysiloxane having the following molecular structure (I): R x Vi (3-x) SiO-(R2SiO) d -SiR y Vi (3-y) (I) In the formula, R is independently selected in each occurrence from alkyl groups having 1 to 8 carbon atoms (preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl) and aryl groups having 6 to 14 carbon atoms (preferably phenyl or naphthyl), Vi is a vinyl group (-CH=CH2), x and y represent the average number of terminal R groups at each end of the linear polysiloxane, each of x and y is independently selected from a number in the range of 0 to 2, preferably 1 to 2, and preferably x=y, (3-x) and (3-y) represent the average number of terminal Vi groups on each end of the linear polysiloxane, and d is the average number of (R2SiO) groups in the linear polysiloxane, typically 10 or more, preferably 50 or more, and simultaneously 1000 or less, preferably 500 or less. Ideally, R is methyl in each occurrence, and at the same time, it is generally desirable that x and y are both 2.

[0023] Generally, the content of A) vinyl-functionalized polysiloxane having two vinyl groups per molecule used herein is 3% by weight or more, preferably 4% by weight or more, more preferably 5% by weight or more, most preferably 6% by weight or more, based on the total weight of the adhesive composition, and at the same time 30% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less, most preferably 15% by weight or less.

[0024] B) Hydrosilylation catalyst The hydrosilylation catalyst B) may comprise any substance capable of promoting a hydrosilylation reaction. Suitable hydrosilylation catalysts are known in the art and are commercially available. Component B) may comprise a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium or iridium metal, an organometallic compound thereof, or a combination thereof. Preference is given to platinum compounds such as chloroplatinic acid, reaction products of chloroplatinic acid and alcohols, platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-ketone complexes, and platinum-phosphine complexes; rhodium compounds such as rhodium-phosphine complexes and rhodium-sulfide complexes; and palladium compounds such as palladium-phosphine complexes, more preferred are platinum compounds, and particularly preferred are platinum-vinylsiloxane complexes.

[0025] The hydrosilylation catalyst B) is exemplified by fine platinum metal powder, platinum black, platinum dichloride, platinum tetrachloride; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid hexahydrate; and complexes of the above compounds, for example, platinum complexes of olefins, platinum complexes of carbonyls, platinum complexes of alkenylsiloxanes such as 1,3-divinyltetramethyldisiloxane, platinum complexes of low molecular weight organopolysiloxanes such as 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane, complexes of chloroplatinic acid and β-diketones, complexes of chloroplatinic acid and olefins, and complexes of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane.

[0026] The hydrosilylation catalyst B) may also be a rhodium compound, for example, represented by the formula: RhX3[(R 4 )2S]3;(R 5 3P)2Rh(CO)X,(R 5 3P)2Rh(CO)H,Rh2X2Y4,H f Rh g (En) h Cl i , or Rh[O(CO)R] 3-j (OH) jIt may be expressed as follows (wherein X represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y represents a methyl group, an ethyl group, or a similar alkyl group, CO, C8H) 14 Or 0.5C8H 12 Represents R 4 R represents a methyl, ethyl, propyl, or similar alkyl group; cyclopentyl, cyclohexyl, or similar cycloalkyl group; or phenyl, tolyl, xylyl, or similar aryl group. 5 (where is a methyl group, ethyl group, or similar alkyl group; phenyl, tolyl, xylyl, or similar aryl group; methoxy, ethoxy, or similar alkoxy group; "En" is ethylene, propylene, butene, hexene, or similar olefin; "f" is 0 or 1; "g" is 1 or 2; "h" is an integer from 1 to 4; "i" is 2, 3, or 4; and "j" is 0 or 1). More specifically, rhodium compounds include RhCl(Ph3P)3, RhCl3[S(C4H9)2]3, [Rh(O2CCH3)2]2, Rh(OCCH3)3, and Rh2(C8H 15 These are O2)4, Rh(C5H7O2)3, Rh(C5H7O2)(CO)2, and Rh(CO)[Ph3P](C5H7O2).

[0027] The hydrosilylation catalyst B) may also be an iridium-based catalyst represented by the following formulas: Ir(OOCCH3)3, Ir(C5H7O2)3, [Ir(Z)(En)2]2, or [Ir(Z)(Dien)]2 (wherein "Z" represents a chlorine atom, a bromine atom, an iodine atom, or a methoxy group, an ethoxy group, or a similar alkoxy group; "En" represents ethylene, propylene, butene, hexene, or a similar olefin; and "Dien" represents cyclooctadiene)tetrakis(triphenyl). Component (F) may also be a mixture of palladium, palladium black, and triphenylphosphine.

[0028] The hydrosilylation catalyst B) can be a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex.

[0029] The amount used is a catalytic amount and can be appropriately selected according to the desired curing conditions. Generally, the catalyst content used herein is 0.01% or more, and based on the total weight of the adhesive composition, it is a maximum of 1.0% by weight, preferably a maximum of 0.5% by weight, and more preferably a maximum of 0.25% by weight.

[0030] C) Condensation catalyst The condensation catalyst is a component that promotes the condensation reaction of the composition according to the present invention, thereby imparting primary curability to the composition according to the present invention at a temperature range of 70°C or less, preferably 60°C or less, and more preferably between room temperature (25°C) and 50°C. Examples of such condensation catalysts include organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, tin octene, dibutyltin dioctate, tin laurate, dimethyltin dineodecanoate, and stanas octoate; tetra(isopropoxy)titanium, tetra(n-butoxy)titanium, tetra(t-butoxy)titanium, di(isopropoxy)bis(ethylacetoacetate)titanium (also called diisopropoxy di(ethoxyacetoacetyl)titanium), and di(isopropoxy)bis(methyl Examples include organotitanium compounds such as acetacetate titanium, di(isopropoxy)bis(acetylacetonate) titanium, tetrabutyl titanate, tetrapropyl titanate, and dibutoxybis(ethylacetate); acidic compounds such as hydrochloric acid, sulfuric acid, and dodecylbenzenesulfonic acid; alkali compounds such as ammonia and sodium hydroxide; and amine compounds such as 1,8-diazabicyclo[5.4.0]undecene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0031] The amount used is a catalytic amount and can be appropriately selected according to the desired curing conditions. Generally, the catalyst content used herein is 0.01% or more, and based on the total weight of the adhesive composition, it is a maximum of 1.0% by weight, preferably a maximum of 0.5% by weight, and more preferably a maximum of 0.25% by weight.

[0032] D) Silylhydride functional polysiloxane Silyl hydride-functionalized polysiloxanes have at least two silyl hydride groups on average per molecule. To avoid misunderstanding, a silyl hydride group is a SiH group. Silyl hydride-functionalized polysiloxanes are sometimes called crosslinking agents in compositions. Preferably, D) the silyl hydride-functionalized polysiloxane is a linear polysiloxane having the following general molecular structure: R' 3-h H h SiO-(HRSiO) a -(R2SiO) b -SiH h’ R' 3-h’ (II) In the formula, R and R' are, independently in each appearance, an alkyl having 1 to 8 carbon atoms (preferably an alkyl having 1 to 6 carbon atoms, more preferably an alkyl having 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tert-butyl), an alkyloxy having 1 to 8 carbon atoms (preferably an alkoxy having 1 to 6 carbon atoms, more preferably an alkoxy having 1 to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy or tert-butoxy), and selected from aryl groups having 6 to 14 carbon atoms (preferably phenyl or naphthyl), where H is hydrogen, the subscripts h and h' refer to the average number of terminal hydrogens at each end of the molecule and have a value of 0, 1, 2, or 3 (preferably 0, 1, or 2, more preferably 0 or 1, most preferably 1), the subscript a is the average number of (HRSiO) groups per molecule, the subscript b is the average number of (R2SiO) groups per molecule, the subscripts a and b are between 0 and 1000, provided that a and b are not both 0, and the sum of a, h and h' is at least 1, preferably at least 2. Preferably, the silyl hydride-functionalized polysiloxane is a trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer or a hydride-terminated polydimethylsiloxane.

[0033] Generally, the content of silyl hydride-functionalized polysiloxane used herein is 0.05% by weight or more, preferably 0.10% by weight or more, more preferably 0.15% by weight or more, most preferably 0.20% by weight or more, based on the total weight of the adhesive composition, while simultaneously being 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less, most preferably 0.6% by weight or less.

[0034] E) Thermally conductive filler Examples of thermally conductive fillers include, but are not limited to, Al2O3, AlN, BN, SiC, and ZnO, as well as other fillers such as TiO2, SiO2, Fe2O3, Fe3O4, finely ground quartz, chalk, talc, diatomaceous earth, zeolite, conductive fillers, Ag, carbon black, graphite, metal oxides, functional nanoparticles, and hollow beads. These fillers may be made hydrophobic by treatment with, for example, organosilanes and / or organosiloxanes, stearic acid, or other agents.

[0035] The shape of the thermal conductive filler particles is not particularly limited, but if they are circular or spherical particles, it is possible to prevent the viscosity from increasing to an undesirable level due to a high concentration of thermal conductive filler in the composition. The average particle size of the thermal conductive filler will depend on various factors, such as the type of thermal conductive filler selected for component E), the exact amount added to the curable composition, and the thickness of the joint of the device in which the cured product of the composition is used. In some specific cases, the thermal conductive filler may have an average particle size in the range of 0.1 micrometers to 80 micrometers, or 0.1 micrometers to 50 micrometers, or 0.1 micrometers to 10 micrometers.

[0036] Alternatively, the thermally conductive filler is independently one or more particles selected from the group consisting of aluminum, copper, silver, carbon nanotubes, carbon fibers, graphene, graphite, silicon nitride, aluminum nitride, diamond, silicon carbide, silica, alumina, aluminum trihydrate, zinc oxide, beryllium oxide, and magnesium oxide. Preferably, the thermally conductive filler is one or more particles selected from the group consisting of silica, alumina, aluminum trihydrate, and zinc oxide. More preferably, the thermally conductive filler is a combination of particles of silica, alumina, and zinc oxide, or a combination of particles of silica and aluminum trihydrate. More preferably, the thermally conductive filler is a combination of particles of spherical Al2O3 having a particle size of 20 to 60 μm, disordered Al2O3 having a particle size of 1 to 10 μm, ZnO having a particle size of 0.05 to 0.20 μm, and SiO2, or the thermally conductive filler is a combination of particles of aluminum trihydrate having a particle size of 15 to 35 μm, aluminum trihydrate having a particle size of 0.5 to 2 μm, and SiO2.

[0037] The amount used can be appropriately selected depending on the desired application. Generally, the content of the thermally conductive filler used herein is 60% by weight or more, 65% by weight or more, 70% by weight or more, based on the total weight of the adhesive composition, and at the same time 95% by weight or less, preferably 90% by weight or less, and more preferably 88% by weight or less.

[0038] F) SiH functional silane SiH-functionalized silanes are also referred to as adhesion promoter AP components in this disclosure.

[0039] F)SiH functionalized silane has the following structure: HR 1 R 2 Si [OSiK 3 R 4 ] n -X-Si(OR 5 )3(II) In the formula, n is an integer from 1 to 10, preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 2, and X is a bonding group selected from the group consisting of C2 to C6 alkylenes (more preferably C2 to C4 alkylenes) and O, and R 1 Each of ~R5 is independently a C1-C6 alkyl group, preferably a C1-C4 alkyl group, more preferably a methyl or ethyl group.

[0040] Generally, the SiH-functionalized silane content used herein is 0.05% by weight or more, preferably 0.08% by weight or more, more preferably 0.1% by weight or more, most preferably 0.12% by weight or more, based on the total weight of the adhesive composition, and at the same time 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, most preferably 0.4% by weight or less.

[0041] G)Q Branched alkenyl polymer G)Q Branched alkenyl polymers have the following structure:

[0042] [ka] During the ceremony, R is independently selected in each appearance from substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms (preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl), or substituted or unsubstituted aryl groups having 6 to 14 carbon atoms (preferably phenyl or naphthyl). R' is independently selected in each occurrence from R and a terminally unsaturated alkenyl (preferably a terminally unsaturated vinyl) having 2 to 6 carbon atoms. The average value of each subscript n1 to n4 is greater than 0 and independently selected from the range of 10 to 200, preferably 20 to 180, more preferably 50 to 170, even more preferably 100 to 160, and most preferably 120 to 155. However, at least one R' is a terminally unsaturated alkenyl (preferably a terminally unsaturated vinyl) having 2 to 6 carbon atoms.

[0043] Generally, the content of the Q-branched alkenyl polymer used herein is 0.5% by weight or more, preferably 0.8% by weight or more, more preferably 1.0% by weight or more, most preferably 1.2% by weight or more, based on the total weight of the adhesive composition, and at the same time 10% by weight or less, preferably 8% by weight or less, more preferably 6% by weight or less, most preferably 4% by weight or less.

[0044] I) Other adjuvants The compositions of the present invention may optionally contain (I) other adjuvants. A single compound (I) or a mixture of two or more may be used. These adjuvants (I) include, for example, inhibitors, stabilizers, silanes other than (F), adhesion promoters, antifungal agents, fragrances, rheological additives, moisture scavengers, rust inhibitors, filler treatment agents, antioxidants, light stabilizers, flame retardants, agents for affecting electrical properties, dispersing aids, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, and heat stabilizers. They include adjuvants such as metal carbonates, metal sulfates, metal salts of carboxylic acids, fibers such as glass fibers and plastic fibers, plastic powders, dyes, and pigments.

[0045] Suitable inhibitors include polymethylvinylcyclosiloxanes such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-dodecine-3-ol, methylvinylcyclosiloxane, 1,3,5,7-tetravinyltetramethyltetracyclosiloxane, divinyltetramethyldisiloxane, tetravinyldimethyldisiloxane, trialkylcyanurates, alkyl maleates, organic sulfoxides, organic amines, diamines, phosphanes and phosphites, nitriles, diaziridines, and oximes, acetylene compounds, phosphites, maleates, amines, or alcohols, which can be used to adjust the processing life, starting temperature, and crosslinking rate of the compositions of the present invention to suit the purpose.

[0046] The content of the inhibitor (e.g., methylvinylcyclosiloxane) is 0-1.5% by weight, 0.01%-1.0% by weight, or 0.02%-0.5% by weight, based on the total weight of the adhesive composition.

[0047] F) The content of adhesion promoters other than SiH functional silanes is 0 to 5% by weight based on the total weight of the adhesive composition.

[0048] The pigment content (e.g., iron oxide (Fe2O3)) is 0-10% by weight, based on the total weight of the adhesive composition.

[0049] The content of filler treatment agents (e.g., n-decyltrimethoxysilane; dimethylsiloxane, monodimethylvinylsiloxy-terminated and monotrimethoxysiloxy-terminated) is 0 to 1% by weight based on the total weight of the adhesive composition. The content of moisture scavenging agents (e.g., trimethoxymethylsilane) is 0 to 1% by weight based on the total weight of the adhesive composition.

[0050] composition The composition is a two-component addition-curing type thermal conductive adhesive composition.

[0051] Preferably, A) a vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, B) at least one hydrosilylation catalyst, C) at least one condensation catalyst, E) at least one thermally conductive filler, G) at least one Q-branched alkenyl polymer, and optionally I) other adjuvants (filler treatment agents, etc.) are present in liquid A of the two-component addition-curing thermal conductive adhesive composition, and A) a vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, D) at least one silylhydride-functionalized polysiloxane, E) at least one thermally conductive filler, F) at least one SiH-functionalized silane, G) at least one Q-branched alkenyl polymer, and optionally I) other adjuvants (filler treatment agents, pigments, curing inhibitors, etc.) are present in liquid B of the two-component addition-curing thermal conductive adhesive composition.

[0052] Preferably, the SiH / alkenyl ratio in the composition is greater than 0.7, preferably greater than 1.0. For example, the SiH / alkenyl ratio in the composition can be 1.01 to 1.50, or 1.02 to 1.40.

[0053] Preferably, the composition further comprises one or more or all of the following as components: inhibitors, other adhesion promoters, pigments, filler treatment agents, moisture scavengers, and antioxidants.

[0054] Preferably, A) the amount of vinyl-functionalized polysiloxane having two vinyl groups per molecule is 5 to 30% by weight based on the total weight of the composition, B) the amount of at least one hydrosilylation catalyst is 0.01 to 0.5% by weight based on the total weight of the composition, C) the amount of at least one condensation catalyst is 0.01 to 0.5% by weight based on the total weight of the composition, and D) the amount of at least one silylhydride-functionalized polysiloxane is 0.05 to 10% by weight based on the total weight of the composition.

[0055] The composition does not contain epoxy group-containing coupling agents as adhesion promoters, such as (γ)-glycidylpropylmethyldimethoxysilane.

[0056] manufacturing technology A) a vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, B) at least one hydrosilylation catalyst, C) at least one condensation catalyst, E) at least one thermally conductive filler, G) at least one Q-branched alkenyl polymer, and optionally I) other adjuvants (filler treatment agents, moisture scavengers, etc.) are mixed together to form liquid A of a two-component addition-curing thermally conductive adhesive composition.

[0057] A) a vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, D) at least one silylhydride-functionalized polysiloxane, E) at least one thermally conductive filler, F) at least one SiH-functionalized silane, and G) at least one Q-branched alkenyl polymer, along with optionally I) other adjuvants (filler treatment agents, pigments, curing inhibitors, etc.), are mixed together to form liquid B of a two-component addition-curing thermally conductive adhesive composition.

[0058] The present application also provides articles comprising cured products formed by curing the two-component addition-curing thermal conductive adhesive composition described herein. Preferably, the articles are electronic components or electronic devices.

[0059] This application also relates to the use of the compositions of this disclosure in the preparation of articles. Preferably, the articles are electronic components or electronic devices. [Examples]

[0060] Next, some embodiments of the present invention will be described in the following examples. Here, all parts and percentages are given by weight unless otherwise specified.

[0061] The raw materials used in the examples are listed in Table 1 below.

[0062] [Table 1]

[0063] Composition and experimental procedures of CE1-11 samples and IE1-6

[0064] [Table 2]

[0065] [Table 3]

[0066] [Table 4]

[0067] CE1-11 and IE1-6 were prepared using a 4L kneader mixer. Composition of Solution A The VP and QP polymer components and the TA filler treatment agent are filled into a 10 L Turello mixer container and mixed for 5 minutes at 20 revolutions per minute (RPM) under a nitrogen flow of 0.4 cubic meters / hour. The thermally conductive filler components are added and stirring is continued for 15 minutes. The mixture is heated to 120°C under vacuum (approximately 0.1 megapascals) for 1 hour. After cooling to 22°C, the MS, Pt1 catalyst and Ti catalyst components are added and mixed for 15 minutes at 750 RPM under nitrogen purging.

[0068] Composition of Solution B Fill a 10L Turello mixer container with VP and QP polymer components, red pigment, and TA component, and mix at 20 RPM for 5 minutes under a nitrogen flow of 0.4 cubic meters / hour. Add the thermally conductive filler component and continue stirring for 15 minutes. Heat the mixture under vacuum (approximately 0.1 megapascals) to 120°C for 1 hour. Cool to 22°C, add the curing inhibitor, crosslinking agent XL component, and adhesion promoter AP component, and mix at 750 RPM for 15 minutes under nitrogen purging.

[0069] [Table 5]

[0070] [Table 6]

[0071] Adhesion can be a physical or chemical bond between two materials. Substrates with reactive groups available for bonding, such as hydroxyl (OH) or carbonyl (C=O) groups on glass, plastics, and aluminum, amplify this chemical attraction via van der Waals forces or weak hydrogen attraction. As is known, Al has a surface energy of about 45 dynes / cm², which represents the thermodynamic effect of how a liquid "wets" a surface. Silicone, however, has a lower surface energy, and there is a mismatch between Al substrates and silicone matrices. To improve adhesion, adhesion promoters can be used to treat the surface of the substrate.

[0072] There are several types of adhesion promoters to minimize mismatch and increase adhesive strength to the substrate. Adhesion can be increased by using silane adhesion promoters that do not inhibit the Pt catalyst. As is known, silanes can act as adhesion promoters by functionalizing the interface between the polymer matrix and the substrate and are widely used to improve adhesion to metal or glass substrates. Mobility is one important consideration in the selection of silanes. Therefore, if a silane has good mobility, can easily move to the interface, and at the same time has strong interactions with both the silicone composite and the substrate, then the silane should be a candidate idea as an adhesion promoter in this self-adhesive formulation. However, most adhesion promoters require high temperatures to build good adhesive strength.

[0073] Therefore, several functionalized silanes were added to thermally conductive potent formulations and evaluated by testing the improvement in lap shear strength. All lap shear test samples of CE and IE were first cured at 70°C for 30 minutes, and then left at room temperature for a further 7 days. The lap shear strengths were then collected as shown in Table 2.

[0074] From CE1 to CE3, it can be observed that the addition of functionalized silane adhesion promoters does not significantly improve the adhesion strength cured at a lower temperature of 70°C. Functionalized silanes with epoxy groups show a slight improvement when a condensation catalyst is added (CE4). When a gemini-type trioxysyl functionalized silane (i.e., bis(trimethoxysilyl)hexane) is used with a Ti catalyst, the adhesion strength increased to over 1 MPa. When a SiH functionalized silane is used to act as an adhesion promoter, the adhesion strength can reach approximately 2 MPa in the presence of a Ti catalyst. From CE7 to CE9, it can be seen that the combination of SiH and bis(trimethoxysilyl)hexane has good adhesion strength in the presence of a Ti catalyst, and the adhesion strength improves as the SiH / Vi ratio increases from approximately 0.85 to approximately 1.35. Further increases in SiH / Vi to approximately 2.0 do not significantly improve the adhesion strength, as shown from CE10. In CE11, we demonstrate that adhesion improvement still works with different filler systems using SiH-functionalized silanes and Ti catalysts. In CE11, pure ATH filler is used to provide a low-density adhesive of 2 W / mK. However, none of the CE samples provide strong adhesion strengths exceeding 2.5 MPa, even when using both hydrosilylation and condensation catalysts.

[0075] In the IE sample, a Q-branched alkenyl polymer is added to the system. The Q-branched alkenyl polymer has one siloxane branching point ("Q" siloxane unit) and four polysiloxane chains having alkenyl groups (preferably vinyl groups). One, two, three, or even all of the alkenyl groups (preferably vinyl groups) on the four polysiloxane chains can react in situ with the SiH-functionalized silane when solutions A and B are mixed in the presence of Pt and Ti catalysts. The in-situ formation of 1 to 4 trioxysyl functional groups on the Q-siloxane unit may result in stronger interaction with the Al substrate and thus improve the adhesive strength of the composite.

[0076] Sample IE1 contains a SiH-functionalized silane adhesion promoter with a Q-branched alkenyl polymer and exhibits good adhesion strength exceeding 2.5 MPa, thus meeting the requirements. Samples IE2-3 contain both SiH and gemini-type trioxysyl-functionalized silane adhesion promoters, differing in the amount of Q-branched alkenyl polymer used. Samples IE4-5 have the same amount of Q-branched alkenyl polymer using a low-density filler ATH, but differ in SiH / VI ratio. The low-density versions of samples IE4-5 exhibit good adhesion strength >3.3 MPa, representing a significant improvement compared to the adhesion strength of sample CE11.

[0077] CE1: An addition-curing, thermally conductive adhesive with a curing strength of 2.0 W / mK containing an epoxy-functionalized silane adhesion promoter. Al2O3 and ZnO were used as thermally conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.09 W / mK and density approximately 2.78 g / cm³). 3 The SiH / Vi ratio was approximately 1.00. Solution B contained 0.4% by weight of a high-temperature adhesion promoter (epoxy-functionalized silane). However, the overlapping shear strength against the Al substrate cured at low temperatures was less than 0.1 MPa. This suggests that the adhesive strength was almost nonexistent.

[0078] Conclusion: Epoxy-functionalized adhesion promoters do not provide the necessary adhesion during low-temperature curing.

[0079] CE2: An addition-curing, thermally conductive adhesive with a viscosity of 2.0 W / mK containing a bis(trimethoxysilyl)hexane adhesion promoter. Al2O3 and ZnO were used as thermally conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.13 W / mK, density approximately 2.80 g / cm³). 3 The SiH / Vi ratio was approximately 1.00. Solution B contained 0.4 wt% bis(trimethoxysilyl)hexane. The overlapping shear strength against the Al substrate cured at low temperature was approximately 0.15 MPa. This indicates the presence of weak adhesion.

[0080] Conclusion: Adhesion promoters containing bis(trimethoxysilyl)hexane can provide weak adhesion to Al substrates cured at low temperatures.

[0081] CE3: An addition-curing thermal conductive adhesive with a temperature of 2.0 W / mK containing a SiH-functionalized silane adhesion promoter. Al2O3 and ZnO were used as thermal conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.10 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.01. Solution B contained 0.4% by weight of a SiH-functionalized silane adhesion promoter. The overlapping shear strength for the Al substrate cured at low temperatures was low, approximately 0.25 MPa.

[0082] Conclusion: Adhesion promoters containing SiH-functionalized silanes do not provide the necessary adhesion during low-temperature curing.

[0083] CE4: An addition-curing thermal conductive adhesive with a temperature of 2.0 W / mK containing epoxy-functionalized silane and a Ti catalyst. Al2O3 and ZnO were used as thermal conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.09 W / mK, density approximately 2.78 g / cm³). 3 The SiH / Vi ratio was approximately 1.01. Solution B contained 0.4 wt% epoxy-functionalized silane adhesion promoter, and solution A contained 0.18 wt% Ti catalyst. The overlapping shear strength for the Al substrate cured at low temperatures remained low, at approximately 0.15 MPa.

[0084] Conclusion: Adhesion promoters with epoxy functionality in conjunction with a Ti catalyst do not provide the necessary adhesion during low-temperature curing.

[0085] CE5: A 2.0 W / mK addition-curing thermal conductive adhesive containing a bis(trimethoxysilyl)hexane adhesion promoter and a Ti catalyst. Al2O3 and ZnO were used as thermal conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.07 W / mK, density approximately 2.78 g / cm³). 3The SiH / Vi ratio was approximately 1.01. Solution B contained 0.4 wt% bis(trimethoxysilyl)hexane adhesion promoter, and solution A contained 0.18 wt% Ti catalyst. The overlapping shear strength for the Al substrate cured at low temperatures increased to 1.12 MPa.

[0086] Conclusion: Adhesion promoters with gemini-type trioxysyl functionality along with condensation catalysts can improve adhesion at low temperatures, but still fail to meet the requirements.

[0087] CE6: A 2.0 W / mK thermally conductive adhesive containing a SiH-functionalized silane adhesion promoter and a Ti catalyst. Al2O3 and ZnO were used as thermally conductive fillers with different particle sizes. The filler content was 86.3% by weight (TC approximately 2.11 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.02. Solution B contained 0.4 wt% SiH-functionalized silane adhesion promoter, and Solution A contained 0.18 wt% Ti catalyst. The overlapping shear strength for the Al substrate cured at low temperatures increased significantly to approximately 1.63 MPa.

[0088] Conclusion: Adhesion promoters with SiH functionality, along with condensation catalysts, can significantly increase adhesion, but some improvement is still needed to meet the adhesion requirements for low-temperature curing.

[0089] CE7: ​​A 2.0 W / mK thermally conductive adhesive containing 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. The filler set is still a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.02 W / mK, density approximately 2.77 g / cm³). 3 The SiH / Vi ratio was approximately 0.85. When using a combination of adhesion promoters, the overlap shear strength at lower temperatures was good, at approximately 0.97 MPa.

[0090] Conclusion: Adhesion promoters with a combination of SiH functionality and gemini-type trioxysyl functionality, along with condensation catalysts, can significantly increase adhesion, but some improvement is still needed to meet the adhesion requirements for low-temperature curing.

[0091] CE8: A 2.0 W / mK thermally conductive adhesive containing 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. The filler set is still a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.11 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.04. When using a combination of adhesion promoters, the overlap shear strength at lower temperatures increased to approximately 1.75 MPa.

[0092] Conclusion: Adhesion promoters having a combination of SiH functionality and gemini-type trioxysyl functionality, along with condensation catalysts, can significantly increase adhesion. Adhesion strength increased at higher SiH / Vi ratios compared to CE7. However, it still cannot meet the requirements for adhesion at low temperatures.

[0093] CE9: A 2.0 W / mK thermally conductive adhesive containing 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. The filler set is still a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.15 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.35. When using a combination of adhesion promoters, the overlap shear strength at lower temperatures increased to approximately 1.94 MPa.

[0094] Conclusion: Adhesion promoters having a combination of SiH functionality and gemini-type trioxysyl functionality, along with condensation catalysts, can significantly increase adhesion. The adhesive strength is higher than that of CE8, and the SiH / Vi ratio is slightly higher than 1.0. However, it still cannot meet the requirements for adhesion at low temperatures.

[0095] CE10: A 2.0 W / mK thermally conductive adhesive containing 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. The filler set is still a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.17 W / mK, density approximately 2.80 g / cm³). 3 The SiH / Vi ratio was approximately 2.04. At higher SiH / Vi ratios, the overlapping shear strength at lower temperatures was approximately 1.67 MPa.

[0096] Conclusion: Adhesion promoters having a combination of SiH functionality and gemini-type trioxysyl functionality, along with condensation catalysts, can significantly increase adhesion. Compared to CE9, further increasing the SiH / Vi ratio did not significantly increase adhesive strength and still could not meet the requirements for adhesion at low temperatures.

[0097] CE11: A low-density version of a thermally conductive adhesive with a density of 2.0 W / mK, containing 0.25 wt% SiH functional silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. The filler set consists of pure ATH of different sizes, with a total filler content of 84.13 wt% (TC approximately 2.03 W / mK, density approximately 1.93 g / cm³). 3 The SiH / Vi ratio was approximately 1.03. The overlapping shear strength at lower temperatures was approximately 1.81 MPa.

[0098] Conclusion: Adhesion promoters having a combination of SiH functionality and gemini-type trioxysyl functionality, along with condensation catalysts, can also exhibit good adhesive strength at low temperatures for different filler systems. In pure ATH filler systems, the D+F system technology can provide an adhesive strength of approximately 2 MPa, but further improvements are needed to meet the requirements for adhesion at low temperatures.

[0099] IE1: A 2.0 W / mK thermally conductive adhesive containing 0.4 wt% SiH-functionalized silane adhesion promoter in solution B and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was packed at 1.5 wt% in both solution A and solution B. The filler set was a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.10 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.05. When using a combination of SiH-functionalized silane and Q-branched alkenyl polymer, the overlapping shear strength at lower temperatures increased to approximately 2.54 MPa.

[0100] Conclusion: By using an adhesion promoter having a combination of SiH-functionalized silane and Q-branched alkenyl polymer, the adhesion strength was increased compared to the adhesion strength of CE6 in the presence of a Ti catalyst (>2.5 MPa). This can meet the requirements for adhesion at low temperatures.

[0101] IE2: A 2.0 W / mK thermally conductive adhesive containing 0.4 wt% SiH functionalization enhancer in solution B and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was packed at 3.5 wt% in both solution A and solution B. The filler set was a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.11 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.39. With increasing Q branched alkenyl polymer filler content and SiH / Vi ratio, the overlapping shear strength at lower temperatures increased to approximately 2.79 MPa.

[0102] Conclusion: By increasing the amount of Q-branched alkenyl polymer filler and the SiH / Vi ratio, the adhesive strength was increased in the presence of a Ti catalyst. This can meet the requirements for adhesion at low temperatures.

[0103] IE3: A 2.0 W / mK thermally conductive adhesive containing 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was packed in 3.5 wt% in solution A and 1.0 wt% in solution B. The filler set was a combination of Al2O3 and ZnO, with a total filler content of 86.3 wt% (TC approximately 2.09 W / mK, density approximately 2.79 g / cm³). 3 The SiH / Vi ratio was approximately 1.37. With increasing Q branched alkenyl polymer filler content and SiH / Vi ratio, the overlapping shear strength at lower temperatures increased to approximately 2.65 MPa.

[0104] Conclusion: The Q branched alkenyl polymer decreased from 3.5% to 1.0% by weight in solution B, and the adhesive strength decreased from 2.79 to 2.65 MPa compared to IE2. This can meet the requirements for adhesion at low temperatures.

[0105] IE4: A low-density version of a thermally conductive adhesive with a density of 2.0 W / mK, comprising 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was filled at 1.5 wt% in both solution A and solution B. The filler set consisted of pure ATH of varying sizes, with a total filler content of 84.13 wt% (TC approximately 2.01 W / mK, density approximately 1.95 g / cm³). 3 The SiH / Vi ratio was approximately 1.03. The overlapping shear strength increased to 2.75 MPa at lower temperatures.

[0106] Conclusion: By using an adhesion promoter in combination with a SiH-functionalized silane and a Q-branched alkenyl polymer, the adhesive strength in the presence of a Ti catalyst was increased compared to the adhesive strength of CE11. This can meet the requirements for adhesion at low temperatures.

[0107] IE5: A low-density version of a thermally conductive adhesive with a density of 2.0 W / mK, comprising 0.25 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was filled at 3.5 wt% in solution A and 2.5 wt% in solution B. The filler set consisted of pure ATH of different sizes, with a total filler content of 84.13 wt% (TC approximately 2.05 W / mK, density approximately 1.95 g / cm³). 3 The SiH / Vi ratio was approximately 1.02. The overlapping shear strength increased to 2.86 MPa at lower temperatures.

[0108] Conclusion: By using an adhesion promoter in combination with a SiH-functionalized silane and a Q-branched alkenyl polymer, the adhesive strength in the presence of a Ti catalyst was increased compared to the adhesive strength of CE11. This can meet the requirements for adhesion at low temperatures.

[0109] IE6: A low-density version of a thermally conductive adhesive with a density of 2.0 W / mK, comprising 0.5 wt% SiH-functionalized silane and 0.15 wt% bis(trimethoxysilyl)hexane adhesion promoter in solution B, and 0.18 wt% Ti catalyst in solution A. Q: Branched alkenyl polymer was filled at 3.5 wt% in solution A and 2.5 wt% in solution B. The filler set consisted of pure ATH of different sizes, with a total filler content of 84.13 wt% (TC approximately 2.02 W / mK, density approximately 1.95 g / cm³). 3 The SiH / Vi ratio was approximately 1.36. The overlapping shear strength increased to 3.01 MPa at lower temperatures.

[0110] Conclusion: By using an adhesion promoter in combination with a SiH-functionalized silane and a Q-branched alkenyl polymer, the adhesive strength in the presence of a Ti catalyst was increased compared to the adhesive strength of CE11. This can meet the requirements for adhesion at low temperatures.

[0111] Determination of thermal conductivity Thermal conductivity was tested using a Hot Disk thermal constant analyzer (Hot Disk TPS 2500S).

[0112] Density determination The density was tested according to the ASTM D792 method.

[0113] Determination of lap shear strength Next, overlap shear strength tests were performed according to ASTM D1002 to test the improvement of adhesion by adding different adhesion promoters. Al Q-panels were used as the substrate. Two Al panels were firmly bonded together using samples of different sizes, 25 mm × 10 mm × 1 mm. After the silicone composite was fully cured at 70°C for 0.5 hours, it was left at room temperature for one week, and a pull-off test device (Instron, ID3366Q3995, maximum power: 300 VA) was used to apply a load to the fixture and pull the joint at a constant speed of 5 mm / min until the composite plug detached from the substrate surface. For each test, five replicated samples were used, and the average value was cited. For each example, at least five samples were prepared and tested.

Claims

1. A) A vinyl-functionalized polysiloxane having at least two vinyl groups per molecule, B) At least one hydrosilylation catalyst, C) At least one type of condensation catalyst, D) At least one silylhydride-functionalized polysiloxane, E) At least one type of thermally conductive filler, F) At least one SiH-functionalized silane, G) A two-component addition-curing thermal conductive adhesive composition comprising at least one Q-branched alkenyl polymer.

2. The above F) SiH functional silane has the following structure: H R １ R ２ Si [OSiR ３ R ４ ] ｎ -X-Si(OR ５ ) ３ (II) In the formula, n is an integer from 1 to 10, X is a bonding group selected from the group consisting of C2 to C6 alkylenes and O, and R １ The composition according to claim 1, wherein each of R5 is independently a C1-C6 alkyl group.

3. The branched alkenyl polymer described above (G)Q has the following structure: 【Chemistry 1】 During the ceremony, R is independently selected in each occurrence from a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. R' is independently selected in each occurrence from R and a terminally unsaturated alkenyl having 2 to 6 carbon atoms. The average values ​​of the subscripts n1 to n4 are each greater than 0 and are independently selected within the range of 10 to 200. The composition according to claim 1, wherein at least one R' is a terminally unsaturated alkenyl having 2 to 6 carbon atoms.

4. The vinyl-functionalized polysiloxane A) is a linear polysiloxane having the following molecular structure (I): R ｘ Vi （３－ｘ） SiO-(R ２ SiO) ｄ -SiR ｙ Vi （３－ｙ） (I) In the formula, R is independently selected in each occurrence from alkyl groups having 1 to 8 carbon atoms and aryl groups having 6 to 14 carbon atoms, Vi is a vinyl group (-CH=CH2), x and y represent the average number of terminal R groups on each end of the linear polysiloxane, each of x and y is independently selected from a number in the range of 0 to 2, (3-x) and (3-y) represent the average number of terminal Vi groups on each end of the linear polysiloxane, and d is the (R) in the linear polysiloxane. ２ The composition according to claim 1, wherein the average number of SiO groups is typically 10 or more, and at the same time 1000 or less.

5. The composition according to claim 1, wherein the E) thermally conductive filler is independently particles of a material selected from the group consisting of aluminum, copper, silver, carbon nanotubes, carbon fibers, graphene, graphite, silicon nitride, aluminum nitride, diamond, silicon carbide, silica, alumina, aluminum trihydrate, zinc oxide, beryllium oxide, and magnesium oxide.

6. D) The silyl hydride-functionalized polysiloxane is a linear polysiloxane having the following general molecular structure: R’ ３－ｈ H ｈ SiO-(HRSiO) ａ -(R ２ SiO) ｂ -SiH ｈ’ R’ ３－ｈ’ (II) In the formula, R and R' are independently selected in each instance from alkyl groups having 1 to 8 carbon atoms, alkyloxy groups having 1 to 8 carbon atoms, and aryl groups having 6 to 14 carbon atoms, H is hydrogen, the subscripts h and h' refer to the average number of terminal hydrogens at each end of the molecule and have a value of 0, 1, 2, or 3, the subscript a is the average number of (HRSiO) groups per molecule, and the subscript b is the (R ２ The composition according to claim 1, wherein the average number of SiO groups is such that the subscripts a and b range from 0 to 1000, provided that a and b are not simultaneously 0, and the sum of a, h and h' is at least 1.

7. The composition according to claim 1, wherein the amount of the thermally conductive filler is 60% by weight or more and 95% by weight or less, based on the total weight of the composition.

8. The composition according to claim 1, wherein the SiH / alkenyl ratio is greater than 0.

7.

9. The composition according to claim 1, wherein the composition further comprises one or more or all of the following as components: an inhibitor, another adhesion promoter, a pigment, a filler treatment agent, a moisture scavenger, and an antioxidant.

10. A) The amount of vinyl-functionalized polysiloxane having two vinyl groups per molecule is 5 to 30% by weight based on the total weight of the composition; B) The amount of at least one hydrosilylation catalyst is 0.01 to 0.5% by weight based on the total weight of the composition; C) The amount of at least one condensation catalyst is 0.01 to 0.5% by weight based on the total weight of the composition; D) The amount of at least one silylhydride-functionalized polysiloxane is 0.05 to 10% by weight based on the total weight of the composition, according to claim 1.

11. An article comprising a cured product formed by curing a two-component addition-curing thermal conductive adhesive composition according to any one of claims 1 to 10.

12. The article according to claim 11, wherein the article is an electronic component or electronic device.

13. Use of the composition according to any one of claims 1 to 10 in the preparation of an article.

14. The use according to claim 13, wherein the article is an electronic component or electronic device.

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