Composition set for use in thermally conductive silicone composition

Abstract

Provided is new technical means capable of obtaining a thermally conductive silicone composition or a cured product thereof having good adhesion properties even when a plastic material or the like is present on an adherend. A composition set for use in a thermally conductive silicone composition, includes a first composition and a second composition. Herein, the first composition includes (A) a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal, (D) an addition reaction catalyst, and (E) a thermally conductive filler, and the second composition includes (A) a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal, (B) a diorganohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and having no cyclic group, (C) an organohydrogensiloxane having a ratio (Si(Cy) / Si(H)) of the number of silicon atoms to which a cyclic group is bonded to the number of silicon atoms to which a hydrogen atom is bonded of 0.15 or more, and (E) a thermally conductive filler. The content of the component (E) in the thermally conductive silicone composition is (50) parts by mass or more relative to (100) parts by mass of the thermally conductive silicone composition.

Description

[0001] WA12447S 1

[0002] COMPOSITION SET FOR USE IN THERMALLY CONDUCTIVE SILICONE COMPOSITION

[0003] Technical Field

[0004]

[0001] The present invention relates to a composition set for use in a thermally conductive silicone composition.

[0005] Background Art

[0006]

[0002] Heat generation during operation and performance deterioration caused thereby are widely known as common problems in electronic component packages, power modules, battery packs, and the like. Various heat dissipation means have been used as measures for solving these problems. As such heat dissipation means, a method of bringing a heat generating body into contact with a cooling member has been generally adopted. There has been interested in realizing more efficient heat dissipation, and various techniques that involve filling a gap that may exist between a heat generating body and a cooling member by using a material having thermal conductivity are being considered.

[0007]

[0003] For example, PTL 1 has proposed a technique for using a thermally conductive silicone composition having a specific chemical composition or a cured product thereof.

[0008] Citation List

[0009] Patent Literature

[0010]

[0004] PTL 1: Japanese Patent Application Laid-Open No. 2023-074699

[0011] Summary of Invention

[0012] Technical Problem

[0013]

[0005] In recent years, for example, in a battery pack used in electric autonomous vehicles, a battery cell is covered with a plastic material or the like in some cases for the purpose of imparting strength or the like thereto.

[0014]

[0006] Inventors of the present invention have examined the problems and discovered that conventional thermallyWA12447S 2

[0015] conductive silicone compositions or cured products thereof have insufficient adhesion properties for adhering to plastic materials and the like ( for example, polyethylene terephthalate (PET) ). Therefore, there is a problem that, when plastic materials and the like are present on an adherend to which the thermally conductive silicone composition or the cured product thereof adheres, an air gap may be generated between the composition or cured product thereof and the adherend by expansion and / or contraction of the heat generating body, potentially reducing the heat dissipation efficiency.

[0016]

[0007] Accordingly, one obj ect of the present invention is to provide new technical means capable of obtaining a thermally conductive silicone composition or a cured product thereof having good adhesion properties even when a plastic material or the like is present on an adherend.

[0017] Solution to Problem

[0018]

[0008] The inventors of the present invention have found that good adhesion properties to plastic materials and the like can be imparted to a thermally conductive silicone composition or a cured product thereof by blending a specific organohydrogensiloxane. The present invention has been achieved based on such knowledge.

[0019]

[0009] According to one aspect of the present invention, there is provided a composition set for use in a thermally conductive silicone composition, the set including a first composition and a second composition. Herein,

[0020] the first composition includes:

[0021] a component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;

[0022] a component (D) that is an addition reaction catalyst; and

[0023] a component (E) that is a thermally conductiveWA12447S 3

[0024] filler,

[0025] the second composition includes:

[0026] the component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;

[0027] a component (B) that is a diorganohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and having no cyclic group;

[0028] a component (C) that is an organohydrogensiloxane having a ratio (Si(Cy) / Si(H)) of the number of silicon atoms to which a cyclic group is bonded to the number of silicon atoms to which a hydrogen atom is bonded of 0.15 or more; and the component (E) that is a thermally conductive filler, and

[0029] the content of the component (E) in the thermally conductive silicone composition is 50 parts by mass or more relative to 100 parts by mass of the thermally conductive silicone composition.

[0030] Advantageous Effects of Invention

[0031]

[0010] With the present invention, it is possible to provide a thermally conductive silicone composition or a cured product thereof that can have good adhesion properties even when a plastic material or the like is present on an adherend. Description Of Embodiments

[0032]

[0011] Compositions Set:

[0033] According to an embodiment of the present invention, there is provided a composition set for use in a thermally conductive silicone composition, the set including a first composition and a second composition. Herein,

[0034] the first composition includes:

[0035] a component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;WA12447S 4

[0036] a component (D) that is an addition reaction catalyst; and

[0037] a component (E) that is a thermally conductive filler,

[0038] the second composition includes:

[0039] a component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;

[0040] a component (B) that is a diorganohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and having no cyclic group;

[0041] a component (C) that is an organohydrogensiloxane having a ratio (Si(Cy) / Si(H)) of the number of silicon atoms to which a cyclic group is bonded to the number of silicon atoms to which a hydrogen atom is bonded of 0.15 or more; and a component (E) that is a thermally conductive filler, and

[0042] the content of the component (E) in the thermally conductive silicone composition is 50 parts by mass or more relative to 100 parts by mass of the thermally conductive silicone composition.

[0043] The composition set of the present invention will be described in detail below.

[0044]

[0012] First composition:

[0045] According to an embodiment of the present invention, the composition set of the present invention is configured to include the first composition. The first composition will be described in detail below.

[0046]

[0013] Component (A):

[0047] According to an embodiment of the present invention, the first composition is configured to include a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal (also referred toWA12447S 5

[0048] as the "component (A) " ). The component (A) may be a main agent in the thermally conductive silicone composition.

[0049]

[0014] The component (A) preferably has a Vi (vinyl group) at a molecular chain terminal (more preferably at both molecule chain terminals) from the viewpoint of conferring moderate hardness to the resulting cured product. The component (A) may have an OH group at a molecular chain terminal.

[0050]

[0015] According to an embodiment of the present invention, the component (A) has, on average, at least 2, preferably 2 to 50, and more preferably 2 to 20 alkenyl groups bonded to silicon atoms within one molecule.

[0051]

[0016] According to an embodiment of the present invention, the component (A) has an alkenyl group only at a molecular chain terminal. The component (A) having an alkenyl group only at the molecular chain terminal is advantageous from the viewpoint that it would be less entangled with other molecules and be able to exhibit good reactivity.

[0052]

[0017] The component (A) may have, for example, a linear structure, a partially branched linear structure, a branched structure, a cyclic structure, or a partially branched cyclic structure. The structure of the molecular chain terminal of the component (A) is not particularly limited, and may be an organosiloxy group, a silanol group or the like, or combinations thereof. The molecular chain of the component (A) usually contains a diorganosiloxane repeating unit as a main unit, but may contain a silanol group or the like in part of a side chain. The component (A) may be a polymer composed of a single type of siloxane unit or a copolymer composed of two or more types of siloxane units. From the viewpoint of obtaining a cured product having uniform physical properties with little curing unevenness, it is preferable that the component (A) be a component that has a substantially linear structure. It is more preferable that the component (A) include a componentWA12447S 6

[0053] that contains a linear chain structure in which the molecular chain is mainly composed of a diorganosiloxane repeating unit (preferably a dialkylsiloxane unit, more preferably a dimethylsiloxane unit) and of which both terminals of the molecular chain are blocked with a triorganosiloxy group (preferably an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group) or an alkenyl group). From the viewpoint of obtaining a cured product having appropriate hardness, it is particularly preferable that the component (A) include a component that contains a linear diorganopolysiloxane having a vinyl group at both terminals of the molecular chain.

[0054]

[0018] The component (A) may use a component having any viscosity as long as the obj ect of the present invention can be achieved. From the viewpoint of obtaining a thermally conductive silicone composition having appropriate fluidity, the component (A) may include a component that has a viscosity of 10 to 7,000 mPa·s, preferably 30 to 5,000 mPa·s, and more preferably 50 to 2,500 mPa·s. It is conceivable that when the viscosity falls within the above-described range, an appropriate fluidity of the thermally conductive silicone composition is obtained and that as a result the ej ectability of the thermally conductive silicone composition becomes high, enhancing the manufacturability. In addition, when the viscosity falls within the above-described range, it is conceivable that flexibility of the cured product of the thermally conductive silicone composition can be enhanced. The viscosity in the present invention refers to a value measured by a rotational viscometer ( ISO3219) at 25°C. Hereinafter, viscosities of other components in the present invention refer to values produced by the same measurement method.

[0055]

[0019] The component (A) may use a component that has any degree of polymerization as long as the obj ect of the presentWA12447S 7

[0056] invention can be achieved. The component (A) may include a component having a degree of polymerization of 40 to 300 from the viewpoint that the resulting thermally conductive silicone composition would be able to have moderate fluidity.

[0057]

[0020] According to an embodiment of the present invention, the component (A) includes a component having an average composition represented by the following formula ( I ):

[0058] R1aSiO(4-a) / 2… (I)

[0059] (in the formula,

[0060] R1is an unsubstituted or substituted monovalent hydrocarbon group, which can be the same across all units or vary from unit to unit, that has 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms); and

[0061] a is 1.7 to 2.1 (preferably 1.8 to 2.5, more preferably 1.95 to 2.05),

[0062] provided that the component contains at least one alkenyl group at a molecular chain terminal).

[0063]

[0021] According to an embodiment of the present invention, two or more of the unsubstituted or substituted monovalent hydrocarbon groups that are represented by the aforementioned R1and have 1 to 18 carbon atoms are selected from alkenyl groups such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group, and a cyclohexenyl group. Groups other than these groups are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, other than alkenyl groups. Specifically, the aforementioned R1is selected from the group consisting of an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; a cycloalkylWA12447S 8

[0064] group such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group; and a halogen-substituted or cyano-substituted alkyl group in which a part or all of hydrogen atoms in the above-described monovalent hydrocarbon groups have been substituted with a halogen atom, a cyano group, or the like, such as a chloromethyl group, a 2-bromoethyl group, a 3, 3, 3-trif luoropropyl group, a 3-chloropropyl group, and a cyanoethyl group.

[0065]

[0022] According to an embodiment of the present invention, two or more of R1are preferably selected from the group consisting of a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-l-propenyl group, a 2-methylallyl group, and a 2-butenyl group, and a vinyl group is particularly preferred. As R1other than the alkenyl group, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred. In addition, it is preferable that 70 mol% or more of the entire R1s be a methyl group in consideration of physical properties and economic efficiency of the cured product, and usually, it is preferable that 80 mol% or more of the entire R1s be a methyl group.

[0066]

[0023] Specific examples of the molecular structure of the component (A) include a dimethylpolysiloxane with both molecular chain terminals blocked with a dimethylvinylsiloxy group, a dimethylsiloxane-methylphenylsiloxane copolymer with both molecular chain terminals blocked with a dimethylvinylsiloxy group, a dimethylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked with a dimethylvinylsiloxy group, a

[0067] dime thyl s il oxane -methyl vinyl si 1 oxane -me thylphyenyl siloxane copolymer with both molecular chain terminals blocked with aWA12447S 9

[0068] dimethylvinylsiloxy group, a dimethylsiloxane-methylvinylsiloxane copolymer with both molecular chain terminals blocked with a trimethylsiloxy group, an organopolysiloxane composed of a siloxane unit represented by the formula: (CH3)2ViSiO1 / 2, a siloxane unit represented by the formula: (CH3)3SiO1 / 2, and a siloxane unit represented by the formula: SiO4 / 2(Vi in the formula represents a vinyl group), an organopolysiloxane in which part or all of the methyl groups in the above-mentioned organopolysiloxanes are substituted by an alkyl group such as an ethyl group or a propyl group, an aryl group such as a phenyl group or a tolyl group, and a halogenated alkyl group such as a 3, 3, 3-trif luoropropyl group, and mixtures of two or more of these organopolysiloxanes. From the viewpoint of enhancing elongation at the time of breakage of the cured product due to increased molecular chain length, a linear diorganopolysiloxane with a vinyl group at both molecular chain terminals is preferable.

[0069]

[0024] According to an embodiment of the present invention, 1.0 to 9.0 parts by mass of the component (A) may be an alkenyl group-containing diorganopolysiloxane having at least one silanol group at a molecular chain terminal.

[0070]

[0025] These diorganopolysiloxanes may be commercially available or prepared by methods known to those skilled in the art.

[0071]

[0026] The content of the component (A) is not particularly limited as long as the obj ect of the present invention can be achieved. The content of the component (A) may be, for example, 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, based on 100 parts by mass of the first composition.

[0072] Alternatively, the content of the component (A) may be, for example, 0.3 to 40 parts by mass, preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass, based on 100WA12447S 10

[0073] parts by mass of the thermally conductive silicone composition or its cured product. Note that the content of the component (A) based on the thermally conductive silicone composition or its cured product refers to the total amount of the component (A) contained in the first composition and the component (A) contained in the second composition, which will be described later.

[0074]

[0027] As the component (A), one type thereof may be used solely, or two or more types of components that differ in terms of viscosity, average composition or other properties may be used in combination.

[0075]

[0028] Component (D):

[0076] According to an embodiment of the present invention, the first composition is configured to include an addition reaction catalyst (also referred to as the "component (D) " in the present invention). The component (D) is not particularly limited as long as it can promote an addition curing reaction between an alkenyl group bonded to a silicon atom in the component (A) and a hydrogen atom bonded to a silicon atom in the component (B), which will be described later.

[0077]

[0029] Examples of the component (D) include not only a platinum group element (platinum, rhodium, palladium, osmium, iridium, ruthenium, etc. ), a compound containing a platinum group element (e. g., a platinum halide, a platinum-olef in complex, a platinum-alcohol complex, a platinum-alcoholate complex, a platinum-vinylsiloxane complex, dicyclopentadieneplatinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride), and those in which these catalysts are supported on optional supports (e. g., activated carbon, aluminum oxide, silicon oxide), but also a hydrosilylated iron catalyst (an iron-carbonyl complex catalyst, an iron catalyst having a cyclopentadienyl group as a ligand, an iron catalyst having a terpyridine ligand or having a terpyridine ligand and a bis-trimethylsilylmethylWA12447S 11

[0078] group, an iron catalyst having a bis-iminopyridine ligand, an iron catalyst having a bis-iminoquinoline ligand, an iron catalyst having an aryl group as a ligand, an iron catalyst having a cyclic or acyclic olefin group having an unsaturated group, an iron catalyst having a cyclic or acyclic olefin group having an unsaturated group, and the like), a hydrosilylated cobalt catalyst, a vanadium catalyst, a ruthenium catalyst, an iridium catalyst, a samarium catalyst, a nickel catalyst, and a manganese catalyst. These catalysts may be used solely or two or more types thereof may be used in any combination.

[0079]

[0030] According to an embodiment of the present invention, the component (D) is preferably a platinum group element, a compound containing a platinum group element, or a compound in which any of these catalyst is supported on an optional support, and more preferably a platinum element, a compound containing a platinum element, or a compound in which any of these catalysts is supported on an optional support.

[0080]

[0031] The content of the component (D) is not particularly limited as long as the obj ect of the present invention can be achieved, and can be appropriately adjusted by those skilled in the art in accordance with the desired application, curing temperature, curing time, and the like. The content of the component (D) may be, for example, 0.001 to 5 parts by mass, preferably 0.01 to 3 parts by mass, and more preferably 0.03 to 1 part by mass, based on 100 parts by mass of the first composition. Alternatively, the content of the component (D) may be, for example, 0.0005 to 2.5 parts by mass, preferably 0.005 to 1.5 parts by mass, and more preferably 0.015 to 0.5 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition or a cured product thereof.

[0081]

[0032] Component (E):

[0082] According to an embodiment of the present invention, theWA12447S 12

[0083] first composition is configured to include a thermally conductive filler (also referred to as the "component (E) " in the present invention). The component (E) is not particularly limited as long as it is a filler having thermal conductivity.

[0084]

[0033] Examples of the component (E) include a metal oxide such as aluminum oxide, zinc oxide, magnesium oxide, titanium oxide, and silicon oxide, and beryllium oxide; a metal hydroxide such as aluminum hydroxide and magnesium hydroxide; a nitride such as aluminum nitride, silicon nitride, and boron nitride; a carbide such as boron carbide, titanium carbide, and silicon carbide; graphite; a metal such as aluminum, copper, nickel, and silver; and those in which at least part of the surface thereof is coated with a hydrocarbon compound or the like. These compounds may be used solely or two or more types thereof may be used in any combination.

[0085]

[0034] The component (E) preferably includes a metal oxide, a metal hydroxide or a nitride from the viewpoint that the component can impart electrical insulation to the resulting thermally conductive silicone composition or its cured product, more preferably includes at least one selected from the group consisting of aluminum hydroxide, boron nitride, aluminum nitride, zinc oxide, aluminum oxide, magnesium oxide, and magnesium hydroxide, and still more preferably includes at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, and zinc oxide.

[0086]

[0035] The component (E) preferably includes at least one selected from the group consisting of aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, zinc oxide, aluminum nitride and boron nitride, from the viewpoint that the component would have good compatibility with the component (A) and / or the component (B), which will be described later, that the component can be industrially selected in a wide range of particle sizes, that the component is readilyWA12447S 13

[0087] available from a resource standpoint, the component is available at a low cost, and / or that the resulting thermally conductive silicone composition or its cured product can exhibit good adhesion and / or elongation under vibration conditions. More preferably, the component (E) includes at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, and zinc oxide.

[0088]

[0036] The component (E) may use a component of any shape as long as it does not hinder the achievement of the obj ect of the present invention. The shape of the component (E) may be, for example, spherical, amorphous, fine powder, fibrous, scale-like or the like. The shape of the component (E) is preferably spherical from the viewpoint that the obtained thermally conductive silicone composition or its cured product can be allowed to contain a sufficient amount of the component (E) so that a favorable thermal conductivity can be imparted to the thermally conductive silicone composition or its cured product. Here, the spherical shape is not only a true spherical shape but also a rounded shape.

[0089]

[0037] The average particle diameter of the component (E) is not particularly limited, but may be, for example, 0.05 to 150 μm, preferably 0.1 to 80 μm, and more preferably 0.5 to 80 μm. The average particle diameter of the component (E) in the present invention refers to a D50 value (or median diameter), which is the 50th percentile particle diameter in a volumebased cumulative particle size distribution measured by a laser diffraction particle size measuring device.

[0090]

[0038] The component (E) may use a component that has a thermal conductivity of 10 W / m·K or more from the viewpoint that a good thermal conductivity would be imparted to the obtained thermally conductive silicone composition or its cured product. According to an embodiment of the present invention, the thermal conductivity of the component (E) refers to the thermal conductivity measured by the methodWA12447S 14

[0091] described in Examples of the present invention.

[0092]

[0039] According to an embodiment of the present invention, the content of the component (E) is 50 parts by mass or more based on 100 parts by mass of the thermally conductive silicone composition (or its cured product).

[0093] According to an embodiment of the present invention, the content of the component (E) may be 50 to 95 parts by mass, preferably 65 to 95 parts by mass, and more preferably 75 to 95 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition (or its cured product). Note that the content of the component (E) based on the thermally conductive silicone composition or its cured product refers to the total amount of the component (E) contained in the first composition and the component (E) contained in the second composition, which will be described later. According to an embodiment of the present invention, the content of the component (E) may be, for example, 50 to 95 parts by mass, preferably 65 to 95 parts by mass, and more preferably 75 to 95 parts by mass, based on 100 parts by mass of the first composition.

[0094]

[0040] According to an embodiment of the present invention, the content of the component (E) is an amount of which the component (E) can impart desired thermal conductivity ( for example, 2.0 W / m·K or more) to the resulting thermally conductive silicone composition or its cured product.

[0095]

[0041] Component (G):

[0096] According to an embodiment of the present invention, the first composition may include a condensation catalyst (also referred to as the "component (G) " in the present invention). The component (G) included in the first composition is advantageous from the viewpoint that the resulting thermally conductive silicone composition could be cured more efficiently.WA12447S 15

[0097]

[0042] The component (G) is not particularly limited as long as it can cure the resulting thermally conductive silicone composition more efficiently. Examples thereof include compounds containing metal elements such as magnesium, aluminum (e. g., trivalent aluminum), titanium, chromium, iron (e. g., trivalent iron), cobalt (e. g., trivalent cobalt), nickel, copper, zinc (e. g., divalent zinc), zirconium (e. g., tetravalent zirconium), tungsten, bismuth (e. g., trivalent bismuth), and the like. Examples of the compounds include organic acid salts of octylic acid, lauric acid, stearic acid and the like; alkoxides such as propoxide and butoxide; catechol; crown ether; polycarboxylic acid; hydroxy acid; a diketone such as ethylacetoacetate; a chelate compound such as a keto acid; and an alkoxide. These compounds may be used solely or two or more types thereof may be used in any combination.

[0098]

[0043] More specific examples of the component (G) include:

[0099] an alkoxy group-containing titanium compound such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraaryloxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-s-butoxide, titanium tetra-t-butoxide, titanium tetra-n-pentyloxide, titanium tetracyclopentyloxide, titanium tetrahexyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetraoctyloxide, titanium tetrakis (2-ethylhexyloxide), titanium tetradecyloxide, titanium tetradodecyloxide, titanium tetrastearyloxide, titanium tetrabutoxide dimer, titanium tetrakis ( 8-hydroxyoctyloxide), titanium diisopropoxide bis (2-ethyl-1, 3-hexanediolato), titanium bis (2-ethylhexyloxy) bis (2-ethyl-1, 3-hexanediolato), titanium tetrakis (2-methoxyethoxide ), titanium tetrakis (2-ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxideWA12447S 16

[0100] dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium butoxide triisopropoxide, titanium dibutoxide diisopropoxide, and titanium tetraphenoxide;

[0101] a titanium chelate compound such as titanium dimethoxybis (ethylacetoacetate), titanium

[0102] dimethoxybis ( acetylacetonate ), titanium

[0103] diethoxybis (ethylacetoacetate), titanium

[0104] diethoxybis (acetylacetonate), titanium

[0105] diisopropoxybis (ethylacetoacetate), titanium diisopropoxybis (methylacetoacetate), titanium diisopropoxybis ( t-butylacetoacetate ), titanium diisopropoxybis (methyl-3-oxo-4, 4-dimethylhexanoate), titanium diisopropoxybis (acetylacetonate), titanium di-n-butoxybis (ethylacetoacetate), titanium di-n-butoxybis (acetylacetonate), titanium

[0106] diisobutoxybis (acetylacetonate), titanium di-t-butoxybis (ethylacetoacetate), titanium di-t-butoxybis (acetylacetonate), titanium

[0107] tetrakis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium bis ( trimethylsiloxy )

[0108] bis (ethylacetoacetate), and titanium bis (trimethylsiloxy) bis (acetylacetonate);

[0109] an alkoxy group-containing zirconium compound such as zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraaryloxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-s-butoxide, zirconium tetra-t-butoxide, zirconium tetra-n-pentyloxide, zirconium tetracyclopentyloxide, zirconium tetracyclohexyloxide, zirconium tetracyclohexyloxide, zirconium tetrabenzyloxide, zirconium tetraoctyloxide, zirconium tetrakis (2-ethylhexyloxide ), zirconium tetradecyloxide, zirconium tetradodecyloxide, zirconium tetrastearyloxide, zirconiumWA12447S 17

[0110] tetrakis (2-methoxyethoxide), zirconium tetrakis (2-ethoxyethoxide ), zirconium butoxide trimethoxide, zirconium dibutoxide dimethoxide, zirconium butoxide triethoxide, zirconium dibutoxide diethoxide, and zirconium butoxide triisopropoxide;

[0111] a zirconium chelate compound such as zirconium tetra ( acetylacetonate ), zirconium

[0112] dimethoxybis (ethylacetoacetate), zirconium

[0113] dimethoxybis (acetylacetonate), zirconium

[0114] diethoxybis (ethylacetoacetate), zirconium

[0115] diethoxybis (acetylacetonate), zirconium

[0116] diethoxybis (ethylacetoacetate), zirconium diisopropoxybis (ethylacetoacetate), zirconium triisopropoxy ( ethylacetoacetate ), zirconium tri-n-butoxy ( ethylacetoacetate ), zirconium

[0117] diisopropoxybis (methylacetoacetate), zirconium diisopropoxybis ( t-butylacetoacetate ), zirconium diisopropoxybis (acetylacetonate), zirconium di-n-butoxybis (ethylacetoacetate), zirconium di-n-butoxybis (acetylacetonate), zirconium

[0118] diisobutoxybis (ethylacetoacetate), zirconium diisobutoxybis (acetylacetonate), zirconium di-t-butoxybis (ethylacetoacetate), zirconium di-t-butoxybis (acetylacetonate), zirconium

[0119] isopropoxytris (ethylacetoacetate), zirconium-n-butoxytris (ethylacetoacetate), zirconium

[0120] tetrakis (ethylacetoacetate), and zirconium

[0121] tetrakis (acetylacetonate);

[0122] an alkoxy group-containing aluminum compound such as aluminum trimethoxide, aluminum triethoxide, aluminum triaryloxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, aluminum tri-n-pentyloxide, aluminumWA12447S 18

[0123] tricyclopentyloxide, aluminum tridecyloxide, aluminum tridodecyloxide, aluminum tristearyloxide, aluminum tris (2-methoxyethoxide ), aluminum tris (2-ethoxyethoxide), aluminum butoxide dimethoxide, aluminum methoxide dibutoxide, aluminum butoxide diethoxide, aluminum ethoxide dibutoxide, aluminum butoxide diisopropoxide, aluminum isopropoxide dibutoxide, and aluminum triphenoxide; and

[0124] an aluminum chelate compound such as aluminum methoxybis (ethylacetoacetate), aluminum

[0125] methoxybis ( acetylacetonate ), aluminum

[0126] ethoxybis (ethylacetoacetate), aluminum

[0127] ethoxybis (acetylacetonate), aluminum

[0128] isopropoxybis (ethylacetoacetate), aluminum

[0129] isopropoxybis (methylacetoacetate), aluminum isopropoxybis (t-butylacetoacetate ), aluminum dimethoxide (ethylacetoacetate), aluminum dimethoxy (acetylacetonate), aluminum diethoxy (ethylacetoacetate), aluminum diethoxy (acetylacetonate), aluminum diisopropoxy (ethylacetoacetate), aluminum diisopropoxy (methylacetate), aluminum diisopropoxy (t-butylacetoacetate), aluminum diisopropoxy (methylacetoacetate ), aluminum isopropoxybis (acetylacetonate), aluminum-n-butoxybis (ethylacetoacetate), aluminum-n-butoxybis (acetylacetonate), aluminum

[0130] isobutoxybis (ethylacetoacetate), aluminum

[0131] isobutoxybis (acetylacetonate), aluminum-t-butoxybis (ethylacetoacetate), aluminum-t-butoxybis (acetylacetonate), aluminum-2-ethylhexoxybis (ethylacetoacetate), aluminum

[0132] tris (ethylacetoacetate), aluminum tris (acetylacetonate), and aluminum (acetylacetonate) bis (ethylacetoacetate). These compounds may be used solely or two or more types thereof may be used in any combination.

[0133]

[0044] The component (G) preferably contains at least one compound selected from the group consisting of a titaniumWA12447S 19

[0134] chelate compound and a zirconium chelate compound (preferably contains a titanium chelate compound, more preferably titanium diisopropoxybis (ethylacetoacetate) ) from the viewpoint that a good balance between reactivity and stability would be obtained. Although the present invention is not bound by any particular theory, the titanium chelate compound has a structure in which two alkoxy groups are bonded to and two chelate ligands are coordinated to titanium, and a combination of the alkoxy groups having high reactivity and the chelate having low reactivity is formed, so that a good balance between reactivity and stability can be obtained.

[0135]

[0045] The content of the component (G) is not particularly limited as long as the obj ect of the present invention can be achieved. The content of the component (G) may be, for example, 0.001 to 5 parts by mass, preferably 0.01 to 3 parts by mass, and more preferably 0.03 to 1 part by mass, based on 100 parts by mass of the first composition. Alternatively, the content of the component (G) may be, for example, 0.0005 to 2.5 parts by mass, preferably 0.005 to 1.5 parts by mass, and more preferably 0.015 to 0.5 part by mass, based on 100 parts by mass of the thermally conductive silicone composition or a cured product thereof.

[0136]

[0046] Other components:

[0137] According to an embodiment of the present invention, the first composition may contain not only the components (A), (D) and (E) and the optional component (G) described above, but also other components (also referred to as the "component (H) " in the present invention), such as a silane coupling agent, a crosslinking agent, an adhesion aid, a pigment, a dye, a curing inhibitor, a heat-resistant imparting agent, a flame retardant, an antistatic agent, an electroconductivity imparting agent, an air-tightness improver, a radiation shielding agent, an electromagnetic shielding agent, a preservative, a stabilizer, an organic solvent, a plasticizer,WA12447S 20

[0138] a fungicide, and the like, as needed. The component (H) may be used solely or two or more types thereof may be used in any combination.

[0139]

[0047] Examples of the silane coupling agent include, but are not particularly limited to, octyltrimethoxysilane, octyl triethoxysilane, de cyl trimethoxysilane,

[0140] de cyl triethoxysilane, dodecyl trimethoxysilane, dodecyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryl oxypropyl trimethoxysilane, 3-acryl oxypropyl trimethoxysilane, 3 -aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used solely or two or more types thereof may be used in any combination.

[0141]

[0048] When a silane coupling agent is used, the content of the silane coupling agent may be, for example, 0.001 to 3 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the first composition. Alternatively, the content of the silane coupling agent may be, for example, 0.001 to 3 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product.

[0142]

[0049] Examples of the crosslinking agent include, but are not particularly limited to, an organopolysiloxane having 10 or more (preferably 15 or more) hydrosilyl groups. These may be used solely or two or more types thereof may be used in any combination.

[0143]

[0050] When a crosslinking agent is used, the content ofWA12447S 21

[0144] the crosslinking agent may be, for example, 0.001 to 3 parts by mass, preferably 0.003 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the first composition. Alternatively, the content of the crosslinking agent may be, for example, 0.0005 to 1.5 parts by mass, preferably 0.0015 to 1 part by mass, and more preferably 0.005 to 0.5 part by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product.

[0145]

[0051] Examples of the pigment include, but are not particularly limited to, titanium oxide, alumina silicate, iron oxide, zinc oxide, calcium carbonate, carbon black, rare earth oxide, chromium oxide, a cobalt pigment, ultramarine blue, cerium silanolate, aluminum oxide, aluminum hydroxide, titanium yellow, carbon black, barium sulfate, and precipitable barium sulfate. These may be used solely or two or more types thereof may be used in any combination. The pigment may be added, for example, to visually distinguish the first composition from the second composition.

[0146]

[0052] According to an embodiment of the present invention, the first composition does not include components (B), (C) and / or (F), which will be described below. According to a preferred embodiment of the present invention, the first composition does not include components (B), (C) and (F), which will be described below.

[0147]

[0053] The first composition may be produced by any method. The conditions in which the first composition is produced (e. g., temperature, time, order of blending each component, and the like) may be appropriately adjusted by those skilled in the art depending on the desired first composition, the thermally conductive silicone composition, the cured product thereof, and the like. For example, the first composition may be produced by mixing the components (A) and (D) and, as necessary, the components (G) and (H),WA12447S 22

[0148] followed by mixing the component (E).

[0149]

[0054] The viscosity of the first composition is not particularly limited, but may be, for example, 10 to 1000 Pa·s, preferably 20 to 500 Pa·s, and more preferably 50 to 200 Pa·s.

[0150]

[0055] Second composition:

[0151] According to an embodiment of the present invention, the composition set of the present invention includes a second composition. The second composition will be described in detail below.

[0152]

[0056] Component (A):

[0153] According to an embodiment of the present invention, the second composition includes a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal (i. e., the component (A) ). The component (A) contained in the second composition may have the same definition and preferred embodiments as those of the component (A) described above for the first composition.

[0154]

[0057] The component (A) contained in the second composition may be the same as or different from the component (A) contained in the first composition.

[0155]

[0058] Component (B):

[0156] According to an embodiment of the present invention, the second composition includes a diorganopolysiloxane (also referred to as the "component (B) " in the present invention) having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and no cyclic group. The component (B) may be included to cure the resulting thermally conductive silicone composition.

[0157]

[0059] The term "cyclic group" in the present invention refers to a group having a cyclic structure such as an alicyclic group, heterocyclic group, aryl group, heteroaryl group and the like, which may be unsubstituted or substituted. The cyclic group may be monocyclic, bicyclic, polycyclic or spiro. Examples of the cyclic groups include, but are notWA12447S 23

[0158] limited to, an alicyclic group such as a cycloalkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group; an aryl group having 6 to 18 ring atoms such as a phenyl group, a naphthyl group, an anthracenyl group, an indenyl group, and an azulenyl group; and a heteroaryl group having 5 to 18 ring atoms such as a pyridinyl group and a thiophenyl group. These groups may be unsubstituted or hydrogen atoms therein may be partially or entirely substituted with a halogen atom, a cyano group, and the like. According to an embodiment of the present invention, the cyclic group described above has at least one double bond within its structure ( for example, unsubstituted or substituted cycloalkenyl group, aryl group, or heteroaryl group).

[0159]

[0060] According to an embodiment of the present invention, the component (B) does not include a component having at least one double bond within its structure as the cyclic group described above. According to an embodiment of the present invention, the component (B) does not contain unsubstituted or substituted aryl and heteroaryl groups as the cyclic group described above. According to an embodiment of the present invention, the component (B) does not contain unsubstituted or substituted aryl groups (preferably an unsubstituted or substituted aryl group having 6 to 18 ring atoms, more preferably an unsubstituted or substituted aryl group having 6 to 10 ring atoms, more preferably an unsubstituted or substituted phenyl group) as the cyclic group described above.

[0160]

[0061] The component (B) may have hydrogen atoms bonded to silicon atoms at a molecular chain terminals, and theWA12447S 24

[0161] molecular chain may also contain hydrogen atoms bonded to silicon atoms. The number of hydrogen atoms bonded to silicon atoms contained in the molecule of the component (B) may be, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2. The component (B) preferably has hydrogen atoms bonded to silicon atoms only at a molecular chain terminals from the viewpoint that the reactivity could increase and / or that the resulting cured product of the thermally conductive silicone composition could become flexible. According to an embodiment of the present invention, the component (B) contains hydrogen atoms bonded to silicon atoms at both the molecular chain terminals (more preferably 1 per molecular chain terminal).

[0162]

[0062] The hydrogen content of the component (B) is not particularly limited, but may be 0.01 to 10.0 mmol / g, preferably 0.03 to 3.0 mmol / g, and more preferably 0.1 to 1.5 mmol / g, from the viewpoint that the resulting cured product of the thermally conductive silicone composition may have good hardness and / or that the resulting cured product of the thermally conductive silicone composition may have good flexibility and / or adhesion.

[0163]

[0063] The component (B) may have, for example, a linear structure, a partially branched linear structure, a branched structure, a cyclic structure, or a partially branched cyclic structure. The structure of the molecular chain terminal of the component (B) is not particularly limited, and may be an organosiloxy group, a silanol group, or a combination thereof. The molecular chain of the component (B) usually contains mainly diorganosiloxane repeating units, but a part of the side chain may be a silanol group or the like. The component (B) may be a polymer composed of a single type of siloxane unit or a copolymer composed of two or more types of siloxane units. It is preferable that the component (B) be a component that has a substantially linear structure from the viewpointWA12447S 25

[0164] that the cured product obtained may have more stable physical properties.

[0165]

[0064] The component (B) may use a component that has any viscosity as long as the obj ect of the present invention can be achieved. The component (B) may include a component that has a viscosity of 10 to 7,000 mPa·s, preferably 10 to 2,500 mPa·s, and more preferably 10 to 500 mPa·s, from the viewpoint of appropriate fluidity of the thermally conductive silicone composition.

[0166]

[0065] According to an embodiment of the present invention, the component (B) includes a component that has an average composition represented by the following formula ( II ):

[0167] R2pHqS i O ( 4 -p-q ) / 2... ( II )

[0168] (in the formula,

[0169] R2is an unsubstituted or substituted monovalent hydrocarbon group, which can be the same across all units or vary from unit to unit, that has 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms);

[0170] p is 0 to 3.0 (preferably 0.7 to 2.1 );

[0171] q is 0.0001 to 3.0 (preferably 0.001 to 1.0); and p + q is 0.5 to 3.0 (preferably 0.8 to 3.0);

[0172] provided that the molecular chain terminal contains a hydrogen atom bonded to at least one silicon atom; and

[0173] R2is not a cyclic group).

[0174]

[0066] The unsubstituted or substituted monovalent hydrocarbon group in the component (B) may be the same as those defined above for the component (A).

[0175]

[0067] According to an embodiment of the present invention, R2can be the same across all units or vary from unit to unit and may be an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutylWA12447S 26

[0176] group, and a tert-butyl group.

[0177]

[0068] According to a preferred embodiment of the present invention, the component (B) may include 1, 1, 3, 3-tetramethyldisiloxane, a methylhydrogencyclopolysiloxane, a methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, tris (dimethylhydrogensiloxy) methylsilane, a dimethylsiloxanemethylhydrogensiloxane copolymer with both molecular chain terminals blocked with a dimethylhydrogensiloxy group, a methylhydrogenpolysiloxane with both molecular chain terminals blocked with a dimethylhydrogensiloxy group, a methylhydrogenpolysiloxane with both molecular chain terminals blocked with a trimethylsiloxy group, a dimethylpolysiloxane with both molecular chain terminals blocked with a dimethylhydrogensiloxy group, a dimethylsiloxanemethylhydrogensiloxane copolymer with both molecular chain terminals blocked with a trimethylsiloxy group, a dimethylsiloxane-methylhydrogensiloxane copolymer with both molecular chain terminals blocked with a dimethylhydrogensiloxy group, a copolymer of H(CH3)2SiO1 / 2and SiO2 units, and a copolymer of H(CH3)2SiO1 / 2, (CH3)3SiO1 / 2and SiO2units.

[0178]

[0069] The content of the component (B) is not particularly limited as long as the obj ect of the present invention can be achieved. The content of the component (B) may be, for example, 0.1 to 25 parts by mass, preferably 0.3 to 20 parts by mass, and more preferably 1 to 15 parts by mass, based on 100 parts by mass of the second composition. Alternatively, the content of the component (B) may be, for example, 0. 05 to 12.5 parts by mass, preferably 0.015 to 10 parts by mass, and more preferably 0.5 to 7.5 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product.

[0179]

[0070] As the component (B), one type thereof may be used solely, or two or more types of components that differ inWA12447S 27

[0180] terms of viscosity, average composition or other properties may be used in combination.

[0181]

[0071] Component (C):

[0182] According to an embodiment of the present invention, the second composition is configured to include an organohydrogensiloxane (also referred to as the "component (C) " in the present invention) in which the ratio

[0183] (Si (Cy) / Si (H) ) of the number of silicon atoms (Si (Cy) ) to which a cyclic group is bonded to the number of silicon atoms (Si (H) ) to which a hydrogen atom is bonded is 0.15 or more. The component (C) may be included in order to impart, to the resulting thermally conductive silicone composition or its cured product, good adhesion properties with respect to the surface of the obj ect to be an adherend ( for example, plastics such as PET) to which the obtained thermally conductive silicone composition or its cured product adheres. Although the present invention is not bound by any particular theory, the component (C) is not highly compatible with other components. Thus, it is considered that when the thermally conductive silicone composition or its cured product described above is brought into contact with the adherend of the obj ect, the component (C) is likely to be locally distributed on the surface ( i. e., the surface that comes into contact with the obj ect), that is, Si (H) remaining in the component (C) is likely to interact with the adherend.

[0184]

[0072] The ratio (Si (Cy) / Si (H) ) of the number of silicon atoms (Si (Cy) ) to which a cyclic group is bonded to the number of silicon atoms (Si (H) ) to which a hydrogen atom is bonded in the component (C) is preferably 0.4 or less, from the viewpoint that the obtained thermally conductive silicone composition or its cured product can exhibit better displacement characteristics. According to an embodiment of the present invention, the ratio of Si (Cy) / Si (H) in the component (C) may fall within a range of 0.15 to 0.4,WA12447S 28

[0185] preferably 0.2 to 0.4, and more preferably 0.25 to 0.4.

[0186]

[0073] The number of silicon atoms, to which a hydrogen atom is bonded, contained in the component (C) is not particularly limited as long as the Si (Cy) / Si (H) falls within the above-mentioned range.

[0187]

[0074] The number of cyclic groups contained in the component (C) is not particularly limited as long as the Si (Cy) / Si (H) falls within the above-mentioned range.

[0188]

[0075] According to an embodiment of the present invention, Si (Cy) in the component (C) may be present at a molecular chain terminal, in the molecular side chain, or in both. Although the present invention is not bound by any particular theory, it is considered that Si (Cy) in the component (C) may contribute to better adhesion properties to an adherend. From this viewpoint, Si (Cy) in the component (C) may preferably be present in the molecular side chain, and is more preferably present only in the molecular side chain.

[0189]

[0076] According to an embodiment of the present invention, Si (H) in the component (C) may be present at a molecular chain terminal, in the molecular side chain, or in both. Although the present invention is not bound by any particular theory, it is considered that Si (H) present at a molecular chain terminal has higher addition reactivity than Si (H) present in a molecular side chain and is more likely to be consumed in a crosslinking reaction. In addition, it is considered that Si (H) remaining without being consumed in the crosslinking reaction can contribute to better adhesion properties to an adherend. From this viewpoint, Si (H) in the component (C) is preferably present in a molecular side chain, and more preferably is present only in a molecular side chain.

[0190]

[0077] According to an embodiment of the present invention, Si (Cy) in the component (C) is present in a molecular side chain, and Si (H) in component (C) is present in a molecular side chain. According to an embodiment of theWA12447S 29

[0191] present invention, Si (Cy) in the component (C) is present only in a molecular side chain, and Si (H) in the component (C) is present only in a molecular side chain.

[0192]

[0078] According to an embodiment of the present invention, the component (C) includes a component that has at least one double bond in the structure as the cyclic group. According to an embodiment of the present invention, the component (C) contains at least one selected from the group consisting of an aryl group and heteroaryl group as the cyclic group, which may be unsubstituted or substituted. According to an embodiment of the present invention, the component (C) contains, as the cyclic group, an unsubstituted or substituted aryl group (preferably an unsubstituted or substituted aryl group having 6 to 18 ring atoms, more preferably an unsubstituted or substituted aryl group having 6 to 10 ring atoms, and more preferably an unsubstituted or substituted phenyl group). From the viewpoint that the obtained thermally conductive silicone composition or its cured product may have better adhesion properties to an adherend, it is advantageous for the component (C) to contain a cyclic group having at least one double bond in the structure. Although the present invention is not bound by any particular theory, it is considered that when the component (C) contains a cyclic group in the molecule having at least one double bond in the structure and the adherend contains a double bond ( for example, PET, etc. ), the component (C) may exhibit improved adhesion properties due to stacking with the double bond included in the structure of the adherend.

[0193]

[0079] The component (C) may have, for example, a linear structure, a partially branched linear structure, a branched structure, a cyclic structure, or a partially branched cyclic structure. The structure of the molecular chain terminal of the component (C) is not particularly limited, and may be an organosiloxy group, a silanol group or the like, orWA12447S 30

[0194] combinations thereof. The molecular chain of the component (C) usually contains a diorganosiloxane repeating unit as a main unit, but may contain a silanol group or the like in part of a side chain. The component (C) may be a polymer composed of a single type of siloxane unit or a copolymer composed of two or more types of siloxane units. It is preferable that the component (C) be a component that has a substantially linear structure from the viewpoint of easy controllability of the amount of substitution of the cyclic group and / or handling property. Although the present invention is not bound by any particular theory, the component (C) that is a component having a linear structure has a lower compatibility with other components than that having a branched chain structure. Thus, such a component (C) is particularly advantageous from the viewpoint that when the thermally conductive silicone composition or its cured product described above is brought into contact with an adherend of an obj ect, the component (C) is more likely to be locally distributed on the surface ( i. e., the surface that comes into contact with the obj ect), that is, Si (H) remaining in the component (C) is more likely to interact with the adherend. Although the present invention is not bound by any particular theory, the component (C) that has a linear structure is particularly advantageous from the viewpoint that the component (C) has better adhesion properties, when the adherend is a plastic (especially PET), compared to that having a branched chain structure or a cyclic structure.

[0195]

[0080] It is considered that the lower the viscosity of the component (C), the easier the component (C) migrates from the thermally conductive silicone composition to the adherend, so that the thermally conductive silicone composition or its cured product may have higher adhesion properties with respect to the adherend. On the other hand, if the viscosity of the component (C) is too low, it is considered that handlingWA12447S 31

[0196] performance and compatibility problems may occur. In view of the above, the component (C) may include a component that has a viscosity of 1 to 500 mPa-s, preferably 5 to 100 mPa-s, and more preferably 10 to 70 mPa-s.

[0197]

[0081] According to an embodiment of the present invention, the component (C) includes a component having an average composition of the following formula ( III ):

[0198] R3rHsSiO(4-r-s) / 2… (III)

[0199] (in the formula,

[0200] R3is an unsubstituted or substituted monovalent hydrocarbon group, which can be the same across all units or vary from unit to unit, that has 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms);

[0201] r is 0 to 3.0 (preferably 0.7 to 2.1 );

[0202] s is 0.0001 to 3.0 (preferably 0.001 to 1.0); and r + s is 0.5 to 3.0 (preferably 0.8 to 3.0);

[0203] provided that the component contains a hydrogen atom bonded to a silicon atom in the molecule;

[0204] at least a portion of R3is a cyclic group (preferably having at least one double bond in its structure).

[0205]

[0082] According to an embodiment of the present invention, R3that is not a cyclic group can be the same across all units or vary from unit to unit, and may be an unsubstituted or substituted C1-6alkyl group (e. g., methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and tert-butyl).

[0206]

[0083] According to an embodiment of the present invention, R3that is a cyclic group can be the same across all units or vary from unit to unit, and may be at least one selected from the group consisting of an aryl group and a heteroaryl group, which may be unsubstituted or substituted (preferably an unsubstituted or substituted aryl group, more preferably an unsubstituted or substituted aryl group having 6WA12447S 32

[0207] to 18 ring atoms, more preferably an unsubstituted or substituted aryl group having 6 to 10 ring atoms, and still more preferably an unsubstituted or substituted phenyl group).

[0208]

[0084] According to an embodiment of the disclosure, the component (C) includes a component having a structure

[0209]

[0210] (in the formula:

[0211] R3ais an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, which can be the same across all units or vary from unit to unit;

[0212] R3bis a cyclic group, which can be the same across all units or vary from unit to unit (preferably one having at least one double bond in the structure, more preferably an unsubstituted or substituted aryl or heteroaryl group, more preferably an unsubstituted or substituted aryl group having 6 to 18 ring atoms, still more preferably an unsubstituted or substituted aryl group having 6 to 10 ring atoms, and further preferably an unsubstituted or substituted phenyl group);

[0213] x is 1 to 20 (preferably 2 to 10, more preferably 3 to 6);

[0214] y is 1 to 30 (preferably 2 to 20, more preferably 3 to 10);

[0215] z is 1 to 50 (preferably 2 to 40, more preferably 3 to 30); and

[0216] x + y + z is 3 to 200 (preferably 5 to 100, more preferably 10 to 50) ).

[0217]

[0085] According to an embodiment of the presentWA12447S 33

[0218] invention, the component (C) includes a component having a structure represented by the following formula ( III-2):

[0219]

[0220] (in the formula, each substituent is defined as described above).

[0221]

[0086] The content of the component (C) is not particularly limited as long as the obj ect of the present invention can be achieved. The content of the component (C) may be, for example, 0.0001 to 1 part by mass, preferably 0.0003 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass, and still more preferably 0.02 to 0.1 parts by mass, based on 100 parts by mass of the second composition. Alternatively, the content of the component (C) may be, for example, 0.00005 to 0.5 parts by mass, preferably 0.00015 to 0.15 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product. According to an embodiment of the present invention, the content of the component (C) that may fall within the above-mentioned range is advantageous from the viewpoint that a sufficient amount of the component (E) can be included in the second composition, the resulting thermally conductive silicone composition or its cured product (that is, a desired thermal conductivity can be obtained. ). The content of the component (C) is preferably less than 0.06 parts by mass, more preferably 0.0005 to 0.05 parts by mass, and more preferably 0.01 to 0.05 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product, from the viewpoint of imparting good displacementWA12447S 34

[0222] characteristics to the obtained thermally conductive silicone composition or its cured product.

[0223]

[0087] As the component (C), one type thereof may be used solely, or two or more types of components that differ in terms of viscosity, average composition or other properties may be used in combination.

[0224]

[0088] Component (E):

[0225] According to an embodiment of the present invention, the second composition is configured to include a thermally conductive filler (i. e., the component (E) ). The component (E) included in the second composition may have the same definition and preferred embodiments as the component (E) described above for the first composition.

[0226]

[0089] The component (E) included in the second composition may be the same as or different from the component (E) included in the first composition.

[0227]

[0090] Component (F):

[0228] According to an embodiment of the present invention, the second composition may include a curing retarder (herein also referred to as the "component (F) " ). The component (F) may be used to retard the curing speed of the addition reaction.

[0229]

[0091] Examples of the component (F) include, but are not limited to, a phosphorus-containing compound such as triphenylphosphine; a nitrogen-containing compound such as tributylamine, tetramethylethylenediamine, and benzotriazole; a sulfur-containing compound; an acetylenic compound including various "en-yne" systems such as 3-methyl-3-pentene-l-yne and 3. 5-dimethyl-3-hexene-l-yne and an acetylenic alcohol such as 3. 5-dimethyl-l-hexyn-3-ol, 1-ethynyl-l-cyclohexanol, and 2-phenyl-3-butyne-2-ol; a compound containing two or more alkenyl groups; a hydroperoxy compound; a maleic acid derivative and a fumaric acid derivative such as dialkyl, dialkenyl and dialkoxyalkyl fumarates or maleates; and an organopolysiloxane having 5 or more alkenyl groups. These mayWA12447S 35

[0230] be used solely, or two or more types thereof may be used in any combination.

[0231]

[0092] From the viewpoint of imparting good adhesion properties and / or displacement characteristics to the obtained thermally conductive silicone composition or its cured product, the component (F) preferably contains an organopolysiloxane having 5 or more (preferably 7 or more, more preferably 10 or more) alkenyl groups bonded to silicon atoms, and more preferably contains an organopolysiloxane having 5 or more (preferably 7 or more, more preferably 10 or more) alkenyl groups bonded to silicon atoms only in the molecular side chains ( i. e., no alkenyl group at molecular chain terminals ). Furthermore, it is still more preferable that the component (F) is an organopolysiloxane having a viscosity of 1000 mPa-s or lower (preferably 300 mPa-s or lower, more preferably 100 mPa-s or lower) and having 5 or more (preferably 7 or more, more preferably 10 or more) alkenyl groups bonded to silicon atoms only in the molecular side chains.

[0232]

[0093] The content of the component (F) is not particularly limited as long as the obj ect of the present invention can be achieved. The content of the component (F) may be, for example, 0.001 to 6 parts by mass, preferably 0.01 to 3 parts by mass, and more preferably 0.03 to 1.5 parts by mass, based on 100 parts by mass of the second composition. Alternatively, the content of the component (F) may be, for example, 0.0005 to 3 parts by mass, preferably 0.005 to 1.5 parts by mass, and more preferably 0.015 to 0.75 parts by mass, based on 100 parts by mass of the thermally conductive silicone composition or its cured product.

[0233]

[0094] Other components:

[0234] According to an embodiment of the present invention, the second composition may include not only the above-described components (A), (B), (C), and (E) and the optional componentWA12447S 36

[0235] (F), but also other components (i. e., the component (H) ), such as a silane coupling agent, a crosslinking agent, an adhesion aid, a pigment, a dye, a curing inhibitor, a heat resistantimparting agent, a flame retardant, an antistatic agent, a conductivity-imparting agent, an air-tightness improver, a radiation shielding agent, an electromagnetic shielding agent, a preservative, a stabilizer, an organic solvent, a plasticizer, and a fungicides, as needed. These may be used solely, or two or more types thereof may be used in any combination. The component (H) that may be included in the second composition may have the same definition and preferred embodiments as the component (H) described above for the first composition.

[0236]

[0095] According to an embodiment of the present invention, the second composition does not contain the component (D).

[0237]

[0096] The second composition may be produced by any method. The conditions for production of the second composition (e. g., temperature, time, order of blending each component, and the like) may be appropriately adjusted by those skilled in the art depending on the desired second composition, the thermally conductive silicone composition, the cured product thereof, and the like. For example, the second composition may be produced by mixing the components (A), (B) and (C), and, as necessary, the components (F) and (H), followed by mixing the component (E).

[0238]

[0097] The viscosity of the second composition is not particularly limited, but may be, for example, 10 to 1000 Pa-s, preferably 20 to 500 Pa-s, and more preferably 30 to 200 Pa-s.

[0239]

[0098] Method for producing composition set:

[0240] The composition set of the present invention may be produced by filling the first composition and the second composition into separate containers or the like.

[0241]

[0099] The mass ratio of the first composition to theWA12447S 37

[0242] second composition and the like may be adjusted appropriately by those skilled in the art depending on the chemical composition of the first composition and / or the second composition, the mixing ratio of the first composition to the second composition, a desired thermally conductive silicone composition or a cured product thereof, and the like.

[0243]

[0100] According to an embodiment of the present invention, the mass ratio of the first composition to the second composition ( first composition / second composition) in the composition set is 0.1 to 10, preferably 0.3 to 3, and more preferably 0.5 to 2.

[0244]

[0101] Use of compositions set:

[0245] The composition set of the present invention may be used to obtain a thermally conductive silicone composition or a cured product thereof.

[0246]

[0102] According to another embodiment of the present invention, the first composition is provided for the production of a thermally conductive silicone composition or a cured product thereof obtained by mixing the first and second compositions.

[0247]

[0103] According to another embodiment of the present invention, the second composition is provided for the production of a thermally conductive silicone composition or a cured product thereof obtained by mixing the first and second compositions.

[0248]

[0104] Thermally conductive silicone composition / Thermally conductive silicone cured product:

[0249] According to an embodiment of the present invention, a thermally conductive silicone composition is provided that can be obtained by mixing the first and second compositions.

[0250]

[0105] The thermally conductive silicone composition may be produced by mixing the first and second compositions at a desired mixing ratio. The conditions for mixing the first and second compositions (temperature, time, pressure, etc. ) may beWA12447S 38

[0251] appropriately adjusted by those skilled in the art depending on the chemical composition of the first composition and / or the second composition, the mixing ratio of the first composition to the second composition, the desired thermally conductive silicone composition or a cured product thereof, and the like.

[0252]

[0106] The thermally conductive silicone composition may have a viscosity immediately after production ( for example, immediately after mixing the first and second compositions) of 10 to 1000 Pa-s, preferably 20 to 500 Pa-s, and more preferably 30 to 300 Pa-s.

[0253]

[0107] According to an embodiment of the present invention, there is provided a thermally conductive silicone cured product which is a cured product of the thermally conductive silicone composition.

[0254]

[0108] The thermally conductive silicone cured product may be obtained by curing the thermally conductive silicone composition under a desired condition. The conditions for curing the thermally conductive silicone composition may be appropriately adjusted by those skilled in the art depending on the chemical composition of the first composition and / or the second composition, the mixing ratio of the first composition to the second composition, the desired thermally conductive silicone composition or the cured product thereof, and the like.

[0255]

[0109] The thermally conductive silicone composition or the thermally conductive silicone cured product can have good adhesion properties to any adherend. Therefore, the thermally conductive silicone composition or the thermally conductive silicone cured product may be used as gap fillers.

[0256]

[0110] The surface of the adherend may be of any material, such as a metal such as iron, copper, aluminum, magnesium, nickel, titanium, stainless steel, lead, zinc, molybdenum, or alloys thereof; plastics such as PET, polyethylene, polyester,WA12447S 39

[0257] epoxy, polyamide, acrylonitrile-butadiene-styrene (ABS), styrene, polypropylene, polyacetal, acrylic resin, polycarbonate (PC), polybutylene terephthalate (PBT), polyetheretherketone (PEEK), and polymethyl methacrylate (PMMA); silicone; silicon; glass; and a carbon material. These materials may be used solely or two or more types may be used in any combination. The surface of the material (e. g., metal) may be coated by electrodeposition or the like.

[0258]

[0111] The thermally conductive silicone composition and / or the thermally conductive silicone cured product of the present invention can be advantageously used for a plastic material (preferably PET) as a surface of an adherend, from the viewpoint of having good adhesion properties even to a plastic material such as PET.

[0259]

[0112] The composition set, the thermally conductive silicone composition and / or the thermally conductive silicone cured product of the present invention can be advantageously used as gap fillers capable of efficiently transmitting heat caused by a heat generating body to a cooling member. Examples of the heat generating bodies include, but are not particularly limited to, a battery for use in an electric vehicle and an electronic device (a personal computer and a smartphone); an electronic device (e. g., a cell phone, a smartphone, a tablet, a smartwatch, and a computer); various substrates (e. g., a semiconductor package substrate, an electronic circuit substrate, an LED package substrate, a sensor substrate, an imaging device substrate, a liquid crystal substrate, and an organic EL substrate). According to an embodiment of the present invention, the composition set, thermally conductive silicone composition and / or thermally conductive silicone cured product of the present invention are particularly advantageously used as gap fillers for use in batteries for electric vehicles.

[0260]

[0113] The present invention encompasses the following:WA12447S 40

[0261]

[0001] A composition set for use in a thermally conductive silicone composition, the set including a first composition and a second composition, wherein:

[0262] the first composition includes:

[0263] (A) a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;

[0264] (D) an addition reaction catalyst;

[0265] (E) a thermally conductive filler;

[0266] and

[0267] the second composition includes:

[0268] (A) a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;

[0269] (B) a diorganohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and having no cyclic group;

[0270] (C) an organohydrogensiloxane having a ratio

[0271] (Si (Cy) / Si (H) ) of the number of silicon atoms to which a cyclic group is bonded to the number of silicon atoms to which a hydrogen atom is bonded of 0.15 or more; and

[0272] (E) a thermally conductive filler;

[0273] and

[0274] a content of the component (E) in the thermally conductive silicone composition is 50 parts by mass or more relative to 100 parts by mass of the thermally conductive silicone composition.

[0275]

[0002] The composition set as set forth in

[0001] , wherein the cyclic group has at least one double bond in a structure thereof.

[0276] [3] The composition set as set forth in

[0001] or

[0002] , wherein the cyclic group is at least one selected from the group consisting of an unsubstituted or substituted aryl group and an unsubstituted or substituted heteroaryl group.

[0277]

[0004] The composition set as set forth in any of

[0001] to [3], wherein the cyclic group is an unsubstituted or substitutedWA12447S 41

[0278] phenyl group.

[0279] [5] The composition set as set forth in any of

[0001] to

[0004] , wherein a content of the component (C) in the thermally conductive silicone composition is less than 0.06 parts by mass relative to 100 parts by mass of the thermally conductive silicone composition.

[0280]

[0006] The composition set as set forth in any of

[0001] to [5], wherein the component (E) includes at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, and zinc oxide.

[0281]

[0007] The composition set as set forth in any of

[0001] to

[0006] , wherein:

[0282] the first composition and / or the second composition further includes (F) a curing retarder; and

[0283] the component (F) includes an organopolysiloxane having 5 or more alkenyl groups bonded to silicon atoms.

[0284]

[0008] The composition set as set forth in

[0007] , wherein the component (F) includes an organopolysiloxane having a viscosity of 100 mPa·s or lower at 25°C and having 10 or more alkenyl groups bonded to silicon atoms only in a molecular side chain.

[0285] [9] The composition set as set forth in any of

[0001] to

[0008] wherein:

[0286] the first composition and / or the second composition includes (G) a condensation catalyst; and

[0287] the component (G) includes at least one selected from the group consisting of a titanium chelate compound and a zirconium chelate compound.

[0288]

[0010] A thermally conductive silicone composition obtained by mixing the first composition with the second composition as defined in any of

[0001] to

[0009] .

[0289]

[0011] A thermally conductive silicone cured product that is a cured product of the thermally conductive silicone composition as set forth in

[0010] .WA12447S 42

[0290] [Examples ]

[0291]

[0114] Hereinafter, the composition set of the present invention will be described in more detail using examples. However, the following examples are not intended to limit the composition set of the present invention in any way. Unless otherwise stated, percentages and ratios described herein are based on mass. Unless otherwise stated, units and measurement methods described herein are in accordance with the Japanese Industrial Standards (JIS).

[0292]

[0115] Raw materials used in Examples described below are shown as follows:

[0293] [Component (A) -l]

[0294] Linear diorganopolysiloxane having one alkenyl group at each terminal (viscosity: 120 mPa·s)

[0295] [Component (A) -2]

[0296] Linear dimethylpolysiloxane having one alkenyl group at each terminal (viscosity: 1,000 mPa·s)

[0297] [Component (B) ]

[0298] Linear diorganopolysiloxane having two hydrogen atoms at both terminals and no phenyl group as a cyclic group (hydrogen content: 0.5 mmol / g, viscosity: 70 mPa·s)

[0299] [Component (C) — 1]

[0300] Organohydrogensiloxane having silicon atoms (Si (Cy) ) to which a phenyl group as a cyclic group (Cy) is bonded and silicon atoms (Si (H) ) to which a hydrogen atom (H) is bonded (Si (Cy) / Si (H) ratio: 0.36)

[0301] [Component (C) -2]

[0302] Organohydrogensiloxane having silicon atoms to which a phenyl group as a cyclic group is bonded and silicon atoms to which a hydrogen atom is bonded (Si (Cy) / Si (H) ratio: 0.25) [Component (C) -3]

[0303] Organohydrogensiloxane having silicon atoms to which a phenyl group as a cyclic group is bonded and silicon atoms to which a hydrogen atom is bonded (Si (Cy) / Si (H) ratio: 0.16)WA12447S 43

[0304] [Component (C) — 4]

[0305] Organohydrogensiloxane having silicon atoms to which a phenyl group as a cyclic group is bonded and silicon atoms to which a hydrogen atom is bonded (Si (Cy) / Si (H) ratio: 0.10) [Component (C) -5]

[0306] Organohydrogensiloxane having no silicon atom to which a phenyl group as a cyclic group is bonded and having silicon atoms to which a hydrogen atom is bonded (Si (Cy) / Si (H) ratio: 0)

[0307] [Component (D) ]

[0308] Platinum-divinyl tetramethyldisiloxane complex [Component (E) — 1]

[0309] Aluminum oxide and aluminum hydroxide (mass ratio of aluminum oxide to aluminum hydroxide = 1: 4 )

[0310] [Component (E) -2]

[0311] Aluminum hydroxide

[0312] [Component (F) -l]

[0313] Diorganosiloxane having 10 or more alkenyl groups only in molecular side chains (viscosity: 50 mPa·s)

[0314] [Component (F) -2]

[0315] Diorganosiloxane having 10 or more alkenyl groups (viscosity: 1,000mPa·s or higher, alkenyl groups present on both side chains and molecular chain terminals)

[0316] [Component (F) -3]

[0317] 1-Ethynylcyclohexanol

[0318] [Component (G) ]

[0319] Titanium diisopropoxybis(ethylacetoacetate)

[0320] [Component (H) -l]

[0321] Silane coupling agent (hexadecyltrimethoxysilane) [Component (H) -2]

[0322] Crosslinking agent (dimethylpolysiloxane having 10 or more hydrogen atoms bonded to silicon atoms)

[0323] [Component (H) -3]

[0324] PigmentWA12447S 44

[0325]

[0116] Production of first composition:

[0326] The components (A), (D), (G), and (H) in respective amounts shown in Table 1 were mixed and kneaded at room temperature for 30 minutes using a planetary mixer. After that, the component (E) in the amount shown in Table 1 was added to the obtained mixture, and the mixture was mixed and kneaded at room temperature for 15 minutes using the planetary mixer, thereby obtaining first composition 1 and 2.

[0327]

[0117] [Table 1 ]

[0328] First Composition

[0329] 1 2 3

[0330] (A)-1 14.20 14.20 9.90

[0331] (D) 0.15 0.15 0.15

[0332] (E)-1 85.10 89.30

[0333] (E)-2 85.10

[0334] (G) 0.15 0.15 0.15

[0335] (H)-1 0.35 0.35 0.45

[0336] (H)-3 0.05 0.05 0.05

[0337]

[0338] Total 100.00 100.00 100.00

[0339] * Unit for each component: part by mass

[0340]

[0118] Production of second composition:

[0341] The components (A), (B), (C), (F), and (H) in respective amounts shown in Table 2 were mixed and kneaded at room temperature for 30 minutes using a planetary mixer. After that, the component (E) in the amount shown in Table 2 was added to the obtained mixture, and the mixture was mixed and kneaded at room temperature for 15 minutes using the planetary mixer to obtain second compositions 1 to 12.Second Composition

[0342] 1 2 3 4 5 6 7 8 9 10 11 12 13 (A)-2 5.05 5.05 5.05 5.05 5.05 4.80 5.05 5.05 5.05 5.05 5.05 5.05 5.05 (B) 8.74 8.77 8.69 8.67 8.74 5.60 8.74 8.74 8.74 8.74 8.74 8.74 8.74 (0-1 0.05 0.02 0.10 0.12 0.05 0.05 — — 0.05 0.05 — — — (0-2 — — — — — — 0.05 — — — — — — (C)-3 — — — — — — — 0.05 — — — — — CO-4 — — — — — — — — — — — 0.05 0.05 CO-5 — — — — — — — — — — 0.05 — — (E-1) 85.18 85.18 85.18 85.18 — 88.78 85.18 85.18 85.18 85.18 85.18 85.18 85.18 (E-2) 85.18

[0343] (F)-1 0.24 0.24 0.24 0.24 0.24 0.14 0.24 0.24 — — 0.24 0.24 0.24 (F)-2 — — — — — — — — 0.24 — — — — (F)-3 — — — — — — — — — 0.24 — — — (H)-1 0.55 0.55 0.55 0.55 0.55 0.60 0.55 0.55 0.55 0.55 0.55 0.55 0.55 (H)-2 0.19 0.19 0.19 0.19 0.19 0.03 0.19 0.19 0.19 0.19 0.19 0.19 0.19

[0344]

[0345] Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 * Unit for each component: part by massWA12447S 46

[0346]

[0120] Examples 1 to 10, Comparative Example 1, Reference Examples 1 to 2: Production of thermally conductive silicone composition:

[0347] The obtained first composition and second composition described above were mixed at a mass ratio of 1:1, stirred for 30 minutes, and degassed by a vacuum pump, thereby obtaining respective thermally conductive silicone compositions. The combinations of the used first composition and second composition and the compositions of the obtained respective thermally conductive silicone compositions are shown in Table 3.

[0348]

[0121] Test Example 1: Tensile shear adhesion stress test Each of the thermally conductive silicone compositions obtained above was sandwiched between a PET resin test piece and a cationic electrodeposition-coated iron test piece so as to have a coating area of 25 mm in length x 25 mm in width and a thickness of 0.8 mm, and cured at a temperature of 23°C for 72 hours, thereby obtaining a test piece for the tensile shear adhesion test. Using the above test piece, a tensile shear adhesion test was conducted in accordance with JIS K6850, and a graph of a stress-strain (S-S) curve was obtained.

[0349] The maximum value of the stress in the obtained S-S curve graph was defined as the tensile shear adhesion stress of the cured product of the thermally conductive silicone composition corresponding to each test piece.

[0350] The results are shown in Table 3.

[0351]

[0122] Test Example 2: Tensile shear adhesion displacement test ]

[0352] Test pieces for the tensile shear adhesion displacement test were obtained by the same method as in Test Example 1. Using the above test piece, a tensile shear adhesion test was conducted in accordance with JIS K6850, and a graph of a S-S curve was obtained.WA12447S 47

[0353] The stroke amount at the point of the maximum stress in the obtained graph of the S-S curve was defined as the tensile shear adhesion displacement of the cured product of the thermally conductive silicone composition corresponding to each test piece.

[0354] The results are shown in Table 3.

[0355]

[0123] Test Example 3: Thermal conductivity test

[0356] Each of the thermally conductive silicone compositions obtained above was poured into a cylindrical press die having a diameter of 30 mm x a height of 6 mm, and cured at 23°C for 24 hours, thereby obtaining a cylindrical cured product. A thermal conductivity of the obtained cured product was measured using an apparatus (TPS-500, manufactured by Kyoto Electronics Manufacturing Co., Ltd. ) capable of measuring by a hot disk method in accordance with ISO 22007-2.

[0357] The results are shown in Table 3.

[0358]

[0124] Test Example 4: Tensile shear fatigue test

[0359] A test piece for tensile shear adhesion test was obtained by the same method as in Test Example 1. Using the above test piece, a fatigue test was conducted using a fatigue testing machine (Fatigue and endurance tester manufactured by Shimadzu Corporation) at a displacement width of +0.5 mm in the shear direction for 50, 000 times at 1 Hz. After the test, the presence or absence of peeling of the test piece on the bonded surface was visually confirmed and evaluated based on the following criteria:

[0360] A: No peeling occurred (70% or more area was bonded based on visual observation)

[0361] B: Slight peeling occurred ( 10% or more and less than 70% area was bonded based on visual observation)

[0362] C: Peeling occurred (less than 10% area was bonded based on visual observation).

[0363] The results are shown in Table 3.Example

[0364] 1 2 3 4 5 6 7 8 9 10 First Composition 1 1 1 1 2 3 1 1 1 1 Second Composition 1 2 3 4 5 6 7 8 9 10 (A)-1 7.100 7.100 7.100 7.100 7.100 4.950 7.100 7.100 7.100 7.100 (A)-2 2.525 2.525 2.525 2.525 2.525 2.400 2.525 2.525 2.525 2.525 (B) 4.370 4.385 4.345 4.335 4.370 2.800 4.370 4.370 4.370 4.370 (C)-1 0.025 0.010 0.050 0.060 0.025 0.025 - — 0.025 0.025 (C)-2 - — — - — — 0.025 — — - (C)-3 — — — — — — — 0.025 — — (C)-4 — — — - — — - — — - (C)-5 - — — - — — - — — - (D) 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 (E)-1 85.140 85.140 85.140 85.140 — 89.040 85.140 85.140 85.140 85.140 (E)-2 - — — - 85.140 — - — — - (F)-1 0.120 0.120 0.120 0.120 0.120 0.070 0.120 0.120 — - (F)-2 - — — - — — - — 0.120 - (F)-3 - — — - — — - — — 0.120 (G) 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 0.075 (H)-1 0.450 0.450 0.450 0.450 0.450 0.525 0.450 0.450 0.450 0.450 (H)-2 0.095 0.095 0.095 0.095 0.095 0.015 0.095 0.095 0.095 0.095 (H)-3 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Test Example 1 (Unit: Mpa) 0.3 0.2 0.4 0.45 0.28 0.25 0.25 0.15 0.2 0.15 Test Example 2 (Unit:mm) 0.8 0.78 0.4 0.3 0.7 0.5 0.7 0.6 0.4 0.5 Test Example 3 (Unit: W / m-k) 2.20 2.18 2.25 2.24 2.19 3.00 2.25 2.25 2.25 2.20

[0365]

[0366] Test Example 4 A A A B A A A A A A * Unit for each component: part by massWA12447S 49

[0367]

[0126] [Table 3 -2 ]

[0368] Comp. Ex Reference Ex.

[0369] 1 1 2

[0370] First Composition 1 1 1

[0371] Second Composition 11 12 13

[0372] (A)-1 7.100 7.100 7.100

[0373] (A)-2 2.525 2.525 2.525

[0374] (B) 4.370 4.370 4.345

[0375] (C)-1 — — —

[0376] (C)-2 — — —

[0377] (C)-3 — — —

[0378] (C)-4 — 0.025 0.050

[0379] (C)-5 0.025 — —

[0380] (D) 0.075 0.075 0.075

[0381] (E)-1 85.140 85.140 85.140

[0382] (0-2 — — —

[0383] (0-1 0.120 0.120 0.120

[0384] (0-2 — — —

[0385] (C)-3 — — —

[0386] (O 0.075 0.075 0.075

[0387] (H)-1 0.450 0.450 0.450

[0388] (H)-2 0.095 0.095 0.095

[0389] (H)-3 0.025 0.025 0.025

[0390] Total 100.00 100.00 100.00

[0391] Test Example 1 (Unit: Mpa) 0.02 0.1 0.13

[0392] Test Example 2 (Unit:mm) 0.1 0.4 0.3

[0393] Test Example 3 (Unit: W / m k) 2.10 2.20 2.20

[0394]

[0395] Test Example 4 C C C

[0396] * Unit for each component: part by mass

[0397]

[0127] From the results of Test Example 1, each of the cured products of the thermally conductive silicone compositions of Examples 1 to 10 had a tensile shear adhesion stress of 0.15 MPa or more, and therefore it is considered that the cured product has good adhesion properties even to plastics (For example, PET). Therefore, the composition set for use in the thermally conductive silicone composition of the present invention is advantageous from the viewpoint that a thermally conductive silicone composition and / or a cured product thereof having good adhesion properties even toWA12447S 50

[0398] plastics ( for example, PET) can be obtained.

[0399]

[0128] From the results of Test Example 2, each of the cured products of the thermally conductive silicone compositions of Examples 1 to 3 and 5 to 10 had a tensile shear adhesion displacement of 0.4 mm or more, and therefore it is considered that the cured product has better adhesion displacement characteristics. Therefore, the composition set for use in the thermally conductive silicone composition of the present invention is particularly advantageous from the viewpoint that a thermally conductive silicone composition and / or a cured product thereof having good displacement characteristics can be obtained by setting the content of the component (C) in the thermally conductive silicone composition to less than 0.06 parts by mass based on 100 parts by mass of the thermally conductive silicone composition. Note that the cured product of the thermally conductive silicone composition obtained in Example 4 had high hardness. Although the present invention is not bound by any particular theory, it is considered that when the content of the component (C) is properly adjusted (e. g., less than 0.06 parts by mass based on 100 parts by mass of the thermally conductive silicone composition), the obtained thermally conductive silicone composition or its cured product can have not only good adhesion properties but also moderate hardness.

[0400]

[0129] According to the results of Test Example 3, the cured products of the thermally conductive silicone compositions of Examples 1 to 10 had a thermal conductivity of 2.0 W / m·k or more, and thus are considered to have good thermal conductivity. Therefore, the composition set for use in the thermally conductive silicone composition of the present invention is particularly advantageous from the viewpoint of obtaining a thermally conductive silicone composition and / or a cured product thereof having good thermal conductivity.

[0401]

[0130] According to the results of Test Example 4, theWA12447S 51

[0402] cured products of the thermally conductive silicone compositions of Examples 1 to 3 and 5 to 10 did not peel off from the adherend even after the fatigue test was performed. Therefore, the composition set for use in the thermally conductive silicone composition of the present invention is particularly advantageous from the viewpoint of obtaining a thermally conductive silicone composition and / or a cured product thereof having good adhesion properties and / or displacement characteristics for a long period of time (for example, even if the heat generating body serving as an adherend repeats expansion and contraction).

[0403]

[0131] Although the present invention is not bound by any particular theory, it is considered that, due to the presence of the cyclic group contained in the molecule of the component (C), hydrogen atoms bonded to silicon atoms contained in the molecule of the component (C) and / or component (B) partially remain after curing, and as a result, the remaining hydrogen atoms interact (for example, hydrogen bonding) with the surface of the adherend, thereby exhibiting good adhesion properties.

[0404]

[0132] Furthermore, according to the results of Test Examples 1 and 2, when a diorganosiloxane having 10 or more alkenyl groups only in a molecular side chain was used as the component (F) — 1, it exhibited better adhesion properties and / or displacement characteristics.

[0405] It is considered that use of an organosiloxane having 5 or more (preferably 10 or more) alkenyl groups in the molecule (i.e., no alkenyl group at molecular chain terminals) as an addition reaction retarder can control the addition reaction speed and adjust the usable time before curing. Although the present invention is not bound by any particular theory, it is considered that the use of a polyorganosiloxane having a low viscosity and an alkenyl group only in the molecular side chain as a retarder allows curing to proceed withoutWA12447S 52

[0406] interfering with the chain extension between polymers and prevents high crosslinking density. Therefore, the obtained thermally conductive silicone composition or its cured product is considered to exhibit better tensile elongation and / or adhesion displacement characteristics.

Claims

WA12447S 53Claims

1. A composition set for use in a thermally conductive silicone composition, the set including a first composition and a second composition, wherein:the first composition includes:a component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;a component (D) that is an addition reaction catalyst;a component (E) that is a thermally conductive filler;andthe second composition includes:the component (A) that is a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal;a component (B) that is a diorganohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom at a molecular chain terminal and having no cyclic group;a component (C) that is an organohydrogensiloxane having a ratio (Si(Cy) / Si(H)) of the number of silicon atoms to which a cyclic group is bonded to the number of silicon atoms to which a hydrogen atom is bonded of 0.15 or more; and the component (E) that is a thermally conductive filler;anda content of the component (E) in the thermally conductive silicone composition is 50 parts by mass or more relative to 100 parts by mass of the thermally conductive silicone composition.WA12447S 54

2. The composition set according to claim 1, wherein the cyclic group has at least one double bond in a structure thereof.

3. The composition set according to claim 1, wherein the cyclic group is at least one selected from the group consisting of an unsubstituted or substituted aryl group and an unsubstituted or substituted heteroaryl group.

4. The composition set according to claim 1, wherein the cyclic group is an unsubstituted or substituted phenyl group.

5. The composition set according to claim 1, wherein a content of the component (C) in the thermally conductive silicone composition is less than 0.06 parts by mass relative to 100 parts by mass of the thermally conductive silicone composition.

6. The composition set according to claim 1, wherein the component (E) includes at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, and zinc oxide.

7. The composition set according to claim 1, wherein:the first composition and / or the second composition further includes (F) a curing retarder; andthe component (F) includes an organopolysiloxane having 5 or more alkenyl groups bonded to silicon atoms.

8. The composition set according to claim 7, wherein the component (F) includes an organopolysiloxane having a viscosity of 100 mPa·s or lower at 25°C and having 10 or more alkenyl groups bonded to silicon atoms only in a molecularWA12447S 55side chain.

9. The composition set according to claim 1, wherein:the first composition and / or the second composition includes (G) a condensation catalyst; andthe component (G) includes at least one selected from the group consisting of a titanium chelate compound and a zirconium chelate compound.

10. A thermally conductive silicone composition obtained by mixing the first composition with the second composition according to any one of claims 1 to 9.

11. A thermally conductive silicone cured product that is a cured product of the thermally conductive silicone composition according to claim 10.

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