WO2023190439A1 - 二液硬化型組成物セット、硬化物及び電子機器 - Google Patents

二液硬化型組成物セット、硬化物及び電子機器 Download PDF

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WO2023190439A1
WO2023190439A1 PCT/JP2023/012376 JP2023012376W WO2023190439A1 WO 2023190439 A1 WO2023190439 A1 WO 2023190439A1 JP 2023012376 W JP2023012376 W JP 2023012376W WO 2023190439 A1 WO2023190439 A1 WO 2023190439A1
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weight
agent
copolymer
curable composition
modified organopolysiloxane
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PCT/JP2023/012376
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English (en)
French (fr)
Japanese (ja)
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正雄 小野塚
朋之 金井
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デンカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks

Definitions

  • the present invention relates to a two-component curable composition set, a cured product, and an electronic device.
  • heat-generating electronic components such as the CPU (central processing unit) of personal computers
  • the amount of heat generated by these electronic components per unit area has become extremely large.
  • the amount of heat they produce is about 20 times that of an iron.
  • Metal heat sinks and casings are used for cooling, but when heat-generating electronic components and heat sinks are brought into direct contact, air exists microscopically at the interface, which impedes heat conduction. It may become. Therefore, in order to efficiently transfer heat, a heat-generating electronic component and a heat sink or the like are sometimes placed with a thermally conductive material interposed therebetween.
  • the thermally conductive material used is, for example, a thermally conductive grease prepared by adding thermally conductive powder to room temperature curing liquid silicone rubber.
  • Room temperature curable liquid silicone rubbers are mainly classified into one-component types and two-component types, and the two-component types are further divided into condensation reaction types and addition reaction types.
  • Two-component type thermally conductive grease containing liquid silicone rubber is used as a two-component curable composition set containing two types of compositions having different compositions.
  • Patent Document 1 discloses that an addition reaction silicone rubber composition containing an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, a platinum catalyst, and an adhesion promoter is less susceptible to curing inhibitors. It is described that it has excellent adhesive properties.
  • a two-component curable composition set is used by mixing two types of compositions and then applying the mixture to a predetermined area, and the mixture is cured over time.
  • the coating is applied to a vertical surface, or if the coated member is placed vertically even if the coating is applied to a horizontal surface, it may be difficult to cure before curing occurs. There is a problem in that the composition mixed with the liquid drips down.
  • pump-out the phenomenon of pumping out
  • the present invention has been made in view of the above problems, and provides a two-component curable composition set that has low viscosity and has excellent drip-off resistance and pump-out resistance, and the two-component curable composition set. It is an object of the present invention to provide a cured product obtained from a curable composition set and an electronic device equipped with the cured product.
  • the present inventors have found that when the first and second parts are mixed in equal volumes, the loss tangent tan ⁇ of the mixture is within a certain amount of time.
  • the present inventors have discovered that a two-component curable composition set that falls within a predetermined range can solve the above problems, and have completed the present invention.
  • a second agent comprising a copolymer A2, a vinyl-modified organopolysiloxane B2, a thermally conductive filler C2, and a hydrosilyl-modified organopolysiloxane E2,
  • the copolymer A1 and the copolymer A2 have a (meth)acrylic monomer unit ⁇ having a carboxy group, a (meth)acrylic monomer unit ⁇ having a tertiary amino group, and a siloxane skeleton.
  • a copolymer having a (meth)acrylic monomer unit ⁇ having After mixing the first agent and the second agent in equal volumes, the time required for the loss tangent tan ⁇ to become less than 0.20 as measured by a rotary rheometer at 25° C. and a frequency of 1 Hz is the time required for the mixture to become less than 0.20.
  • the time required for the loss tangent tan ⁇ to become less than 0.20 as measured by a rotary rheometer at 25° C. and a frequency of 1 Hz is the time required for the mixture to become less than 0.20.
  • the vinyl-modified organopolysiloxane B1 and the vinyl-modified organopolysiloxane B2 each independently have an average of 2.0 or more vinyl groups per molecule,
  • the hydrosilyl-modified organopolysiloxane E2 has an average of more than 2.0 hydrosilyl groups per molecule,
  • the hydrosilyl-modified organopolysiloxane E2 includes a hydrosilyl-modified organopolysiloxane E21 having a hydrosilyl group at both ends, and a hydrosilyl-modified organopolysiloxane E22 having a hydrosilyl group in a side chain.
  • the vinyl-modified organopolysiloxane B1 and the vinyl-modified organopolysiloxane B2 each independently contain an organopolysiloxane having a vinyl group at both ends.
  • the number average molecular weight of the monomer unit ⁇ is 1,500 to 50,000, The two-component curable composition set according to any one of [1] to [4].
  • the content of the copolymer A1 in the first agent is 1 to 40 parts by weight based on 100 parts by weight of the vinyl-modified organopolysiloxane B1
  • the content of the copolymer A2 in the second agent is 1 to 40 parts by weight based on a total of 100 parts by weight of the vinyl-modified organopolysiloxane B2 and the hydrosilyl-modified organopolysiloxane E2.
  • the two-component curable composition set according to any one of [1] to [5].
  • the weight average molecular weights of the copolymer A1 and the copolymer A2 are each independently from 20,000 to 150,000, The two-component curable composition set according to any one of [1] to [6].
  • the content of the monomer unit ⁇ is 0.08 to 6.0 parts by weight, The content of the monomer unit ⁇ is 0.02 to 4.0 parts by weight, The content of the monomer unit ⁇ is 90.0 to 99.9 parts by weight, The two-component curable composition set according to any one of [1] to [7].
  • the thermally conductive filler C1 and the thermally conductive filler C2 are each independently selected from the group consisting of boron nitride, aluminum nitride, aluminum oxide, silicon nitride, silicon oxide, magnesium oxide, metallic aluminum, and zinc oxide. more than one type, The two-component curable composition set according to any one of [1] to [8]. [10] 15 hours after the mixing with respect to the storage elastic modulus G 0 ' of a mixture obtained by mixing the first agent and the second agent in equal volumes with a rotary rheometer at 25° C. and a frequency of 1 Hz immediately after the mixing.
  • the ratio G 15 ′/G 0 ′ of storage elastic modulus G 15 ′ measured in the same manner as above is 100 to 1,500.
  • the first agent and the second agent have the following formula: R 1 a R 2 b Si(OR 3 ) 4-(a+b) (R 1 is each independently an alkyl group having 1 to 15 carbon atoms, R 2 is each independently a saturated or unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms, Each R 3 is independently an alkyl group having 1 to 6 carbon atoms, a is 1 to 3, b is 0 to 2, and a+b is 1 to 3.) Does not contain organosilane represented by The two-component curable composition set according to any one of [1] to [10].
  • a two-component curable composition set having low viscosity and excellent drip-off resistance and pump-out resistance, and a cured product obtained from the two-component curable composition set, and An electronic device including the cured product can be provided.
  • this embodiment an embodiment of the present invention (hereinafter referred to as “this embodiment”) will be described in detail.
  • the present invention is not limited to the following embodiments, and various modifications can be made without departing from the gist thereof.
  • Two-component curable composition set The two-component curable composition set of this embodiment is a first composition containing a copolymer A1, a vinyl-modified organopolysiloxane B1, a thermally conductive filler C1, and an addition reaction catalyst D1.
  • copolymer A1 and copolymer A2 is a (meth)acrylic monomer unit ⁇ having a carboxy group, a (meth)acrylic monomer unit ⁇ having a tertiary amino group, and a (meth)acrylic monomer having a siloxane skeleton. It is a copolymer having the unit ⁇ , and after mixing the first part and the second part in equal volumes, the loss tangent tan ⁇ of the mixture measured with a rotary rheometer at 25 ° C. and a frequency of 1 Hz is less than 0.20. The time required for this to occur is within 24 hours from mixing.
  • the first agent includes copolymer A1, vinyl-modified organopolysiloxane B1, thermally conductive filler C1, and addition reaction catalyst D1, and may further include other components as necessary. good.
  • Copolymer A1 consists of a (meth)acrylic monomer unit ⁇ having a carboxy group, a (meth)acrylic monomer unit ⁇ having a tertiary amino group, and a (meth)acrylic monomer unit having a siloxane skeleton. It has a monomer unit ⁇ .
  • the dispersibility of the thermally conductive filler C1 can be improved, and the viscosity of the first agent can be lowered.
  • the curing speed when mixing the first part and the second part can be set within a suitable range, and the drip-off resistance and/or pump-out resistance of the two-component curable composition set can be further improved.
  • the drip-off resistance and/or pump-out resistance of a two-part curable composition set refers to the mixture obtained by mixing the first part and second part of the two-part curable composition set, and the cured product thereof. , meaning that it is less likely to cause dripping and/or pump-out.
  • the content of copolymer A1 is preferably 1 to 40 parts by weight (inclusive of both extremes), based on 100 parts by weight of vinyl-modified organopolysiloxane B1. ), more preferably 2 to 30 parts by weight, still more preferably 3 to 20 parts by weight, even more preferably 5 to 15 parts by weight.
  • the content of the copolymer A1 is within the above range, the dispersibility of the thermally conductive filler C1 is further improved, and the viscosity of the first agent tends to be further reduced.
  • the weight average molecular weight of copolymer A1 is preferably 20,000 to 150,000, more preferably 30,000 to 120,000, and even more preferably 40,000 to 100,000. When the weight average molecular weight of the copolymer A1 is within the above range, the dispersibility of the thermally conductive filler C1 tends to be further improved, and the viscosity of the first agent tends to be further reduced.
  • the weight average molecular weight can be determined by GPC (gel permeation chromatography).
  • copolymer A1 refers to a monomer having a polymerizable unsaturated bond before polymerization
  • “monomer unit” refers to a repeating unit that forms part of the copolymer after polymerization. It refers to a unit derived from a specific monomer.
  • (meth)acrylic includes acrylic and methacryl
  • (meth)acrylic monomer includes (meth)acrylate and (meth)acrylamide.
  • (meth)acrylic monomer unit ⁇ " and the like are also simply referred to as “monomer unit ⁇ " and the like.
  • monomer units ⁇ , monomer units ⁇ , and monomer units ⁇ may be included randomly or in blocks.
  • at least monomer unit ⁇ and monomer unit ⁇ are preferably contained as a random copolymer.
  • the monomer unit ⁇ further has an electron-withdrawing group bonded to the carboxy group.
  • an electron-withdrawing group is not particularly limited as long as it has the effect of stabilizing the negative charge on the carboxy group.
  • the monomer unit ⁇ may be a unit derived from an acrylic monomer containing an electron-withdrawing substituent such as a halogen element on the carbon atom at the ⁇ -position of the carboxy group.
  • the monomer unit ⁇ has no electron-donating group bonded to the carboxy group or has a group with low electron-donating property.
  • an electron-donating group is not particularly limited as long as it has the effect of destabilizing the negative charge on the carboxy group.
  • the monomer unit ⁇ may be a unit derived from an acrylic monomer that does not contain a substituent of an electron-donating group such as a methyl group on the carbon atom at the ⁇ -position of the carboxy group. By including such a monomer unit, the dispersibility of the thermally conductive filler C1 tends to be further improved.
  • Such (meth)acrylic monomers are not particularly limited, but include, for example, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, and the like. Among these, acrylic acid and 2-methacryloyloxyethylsuccinic acid are preferred, and acrylic acid is more preferred.
  • acrylic acid and 2-methacryloyloxyethylsuccinic acid are preferred, and acrylic acid is more preferred.
  • the monomer units ⁇ may be used alone or in combination of two or more types.
  • the content of the monomer unit ⁇ is, for example, 0.05 to 20 parts by weight with respect to the total of 100 parts by weight of the monomer unit ⁇ , monomer unit ⁇ , and monomer unit ⁇ , and is preferably The amount is 0.08 to 6.0 parts by weight, more preferably 0.1 to 5.0 parts by weight, even more preferably 0.3 to 4.0 parts by weight, and even more preferably 0.5 to 4.0 parts by weight. It is 3.0 parts by weight.
  • the content of the monomer unit ⁇ may be 0.7 parts by weight or more, or 2.0 parts by weight or less within the above range.
  • the content of the monomer unit ⁇ is within the above range, the dispersibility of the thermally conductive filler C1 tends to be further improved, and the viscosity of the first agent tends to be further reduced. Moreover, there is a tendency that the curing rate when the first part and the second part are mixed can be set in a more suitable range.
  • (meth)acrylic monomer unit ⁇ having a tertiary amino group The monomer unit ⁇ is a repeating unit having a tertiary amino group.
  • the monomer unit ⁇ further has an electron-donating group bonded to the carbon atom adjacent to the nitrogen atom in the tertiary amino group.
  • an electron-donating group is not particularly limited as long as it has the effect of stabilizing the positive charge on the tertiary amino group.
  • the monomer unit ⁇ may be, for example, a unit derived from an acrylic monomer containing an electron-donating substituent such as a methyl group at the carbon atom at the ⁇ -position of a tertiary amino group.
  • the monomer unit ⁇ does not have an electron-withdrawing group bonded to the carbon atom adjacent to the nitrogen atom in the tertiary amino group, or has a group with low electron-withdrawing property.
  • Such an electron-withdrawing group is not particularly limited as long as it has the effect of destabilizing the positive charge on the tertiary amino group.
  • the monomer unit ⁇ may be, for example, a unit derived from an acrylic monomer that does not contain a substituent of an electron-withdrawing group such as a carboxy group on the carbon atom at the ⁇ -position of the tertiary amino group.
  • Such (meth)acrylic monomers are not particularly limited, but examples include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. Can be mentioned. Among these, dimethylaminoethyl methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate are preferred, and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred. is more preferable.
  • the affinity for the thermally conductive filler C1 tends to be further improved, and the dispersibility of the thermally conductive filler C1 tends to be further improved.
  • the monomer units ⁇ may be used alone or in combination of two or more.
  • the content of monomer unit ⁇ is, for example, 0.02 to 4.0 parts by weight with respect to 100 parts by weight of the total of monomer unit ⁇ , monomer unit ⁇ , and monomer unit ⁇ , Preferably it is 0.05 to 4.0 parts by weight, more preferably 0.07 to 3.0 parts by weight, even more preferably 0.08 to 2.0 parts by weight, and even more preferably 0.08 to 2.0 parts by weight. It is 1 to 1.0 parts by weight.
  • the content of the monomer unit ⁇ may be 0.3 parts by weight or more, or 0.8 parts by weight or less within the above range. When the content of the monomer unit ⁇ is within the above range, the dispersibility of the thermally conductive filler C1 tends to be further improved, and the viscosity of the first agent tends to be further reduced.
  • (meth)acrylic monomer unit ⁇ having a siloxane skeleton The monomer unit ⁇ is a repeating unit having a siloxane skeleton.
  • the affinity or compatibility between copolymer A1 and vinyl-modified organopolysiloxane B1 increases, and the viscosity of the first agent further decreases.
  • the copolymer A1 since the copolymer A1 has the monomer unit ⁇ , it is possible to suppress the addition reaction catalyst D1 from reacting with the monomer unit ⁇ and being deactivated. This allows the curing speed when mixing the first and second parts to be within a suitable range, further improving the drip-off resistance and/or pump-out resistance of the two-component curable composition set. be able to.
  • Examples of the siloxane skeleton in the monomer unit ⁇ include organopolysiloxane skeletons such as dialkylpolysiloxane, diphenylpolysiloxane, and alkylphenylpolysiloxane.
  • the alkyl contained in the siloxane skeleton is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.
  • the phenyl group that the siloxane skeleton has is not particularly limited, but examples include phenyl groups and phenyl groups having substituents, and specific examples include phenyl groups and benzyl groups.
  • Examples of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Such (meth)acrylic monomers are not particularly limited, but include, for example, (meth)acrylic acid polysiloxanes in which the terminals of the siloxane skeleton are modified with (meth)acrylic acid as described above. Specific examples include ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane.
  • the monomer units ⁇ may be used alone or in combination of two or more.
  • the number average molecular weight of the monomer unit ⁇ is preferably 1,500 to 50,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
  • the number average molecular weight of the monomer unit ⁇ is 1,500 or more, the deactivation of the addition reaction catalyst D1 is further suppressed, and the drip-off resistance and/or pump-out resistance of the two-component curable composition set is improved. There is a tendency for this to further improve.
  • the number average molecular weight of the monomer unit ⁇ is 50,000 or less, the viscosity of the first agent tends to be further reduced.
  • the number average molecular weight of the monomer unit ⁇ can be determined by GPC (gel permeation chromatography).
  • the content of the monomer unit ⁇ is, for example, 70.0 to 99.9 parts by weight with respect to the total of 100 parts by weight of the monomer unit ⁇ , monomer unit ⁇ , and monomer unit ⁇ , Preferably it is 80.0 to 99.5 parts by weight, preferably 90.0 to 99.0 parts by weight, more preferably 93.0 to 98.8 parts by weight, still more preferably 96.0 to 98.8 parts by weight. It is 98.7 parts by weight.
  • the content of the monomer unit ⁇ is within the above range, the dispersibility of the thermally conductive filler C1 tends to be further improved, and the viscosity of the first agent tends to be further reduced. Furthermore, the drip-off resistance and/or pump-out resistance of the two-component curable composition set tends to be further improved.
  • the total content of monomer units ⁇ , monomer units ⁇ , and monomer units ⁇ in copolymer A1 is preferably 90% by weight or more based on the total amount of copolymer A1, It is more preferably 95% by weight or more, still more preferably 99% by weight or more, and even more preferably 100% by weight.
  • the upper limit of the total content of monomer units ⁇ , monomer units ⁇ , and monomer units ⁇ is not particularly limited, and is, for example, 100% by weight, 99% by weight, 98% by weight, or 95% by weight. It's good.
  • the method for manufacturing copolymer A1 is not particularly limited, and any known polymerization method for (meth)acrylic monomers can be used. Examples of polymerization methods include radical polymerization and anionic polymerization. Among these, radical polymerization is preferred.
  • Thermal polymerization initiators used in radical polymerization are not particularly limited, but include, for example, azo compounds such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, and di-tert-butyl peroxide. Examples include things.
  • the photopolymerization initiator used in radical polymerization is not particularly limited, but includes benzoin derivatives.
  • known polymerization initiators used in living radical polymerization such as ATRP and RAFT can also be used.
  • the polymerization conditions are not particularly limited and can be adjusted as appropriate depending on the initiator used, the boiling point of the solvent, and other types of monomers.
  • the order of adding the monomers is not particularly limited, but for example, when synthesizing a random copolymer, the monomers may be mixed to start polymerization, or when synthesizing a block copolymer, the monomers may be mixed to start polymerization.
  • the monomers may be sequentially added to the polymerization system.
  • Organopolysiloxane B1 Vinyl-modified organopolysiloxane B1 (hereinafter also simply referred to as "organopolysiloxane B1") is an organopolysiloxane having at least one vinyl group. Organopolysiloxane B1 may have a vinyl group in a side chain and/or at a terminal. Such an organopolysiloxane has a structural unit represented by the following formula (b1-1) or a terminal structure represented by the formula (b1-2). Organopolysiloxane B1 includes, for example, at least one of a structural unit represented by formula (b1-1) and a terminal structure represented by formula (b1-2), and a structural unit represented by formula (b1-3). It may have.
  • R is any monovalent hydrocarbon group that may have a substituent. That is, in organopolysiloxane B1, any monovalent hydrocarbon group that may have a substituent is bonded to the side chain of the siloxane skeleton.
  • Examples of such monovalent hydrocarbon groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl.
  • Alkyl groups such as groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, and 2-phenylpropyl group groups; and groups having substituents in these groups.
  • Examples of the substituent that the above-mentioned monovalent hydrocarbon group has include a halogen atom, particularly a fluorine atom or a chlorine atom.
  • Organopolysiloxane B1 is contained in the first agent singly or in combination of two or more.
  • the number of vinyl groups in organopolysiloxane B1 contained in the first agent is preferably 2.0 or more per molecule on average. That is, when the first agent contains one type of organopolysiloxane B1, it is preferable that the organopolysiloxane has two or more vinyl groups per molecule.
  • the arithmetic average of the number of vinyl groups in each organopolysiloxane is 2.0 or more.
  • the crosslinking density can be adjusted, and the curing speed when mixing the first and second agents can be set within a more suitable range. tends to be possible. As a result, there is a tendency that the drip-off resistance and/or pump-out resistance of the two-component curable composition set can be further improved.
  • the upper limit of the number of vinyl groups in organopolysiloxane B1 is not particularly limited, and may be, for example, 4.0, 3.0, or 2.5 on average per molecule.
  • the average number of vinyl groups per molecule of organopolysiloxane B1 may be 2.0.
  • the average number of vinyl groups per molecule of organopolysiloxane B1 may be measured by NMR. Specifically, the measurement may be performed using, for example, ECP-300NMR manufactured by JEOL, and dissolving organopolysiloxane B1 in heavy chloroform as a heavy solvent. The average number of vinyl groups per molecule can be calculated by dividing the measurement results obtained in this manner by the average molecular weight of organopolysiloxane B1.
  • the organopolysiloxane B1 contains at least an organopolysiloxane having vinyl groups at both ends.
  • an organopolysiloxane having vinyl groups at both ends.
  • the crosslinking density can be adjusted, and the curing rate when the first and second parts are mixed tends to be within a more suitable range.
  • the drip-off resistance and/or pump-out resistance of the two-component curable composition set can be further improved.
  • the organopolysiloxane B1 contains at least polydimethylsiloxane having vinyl groups at both ends.
  • the viscosity of organopolysiloxane B1 at 25° C. is preferably 30 to 500 mPa ⁇ s, more preferably 50 to 400 mPa ⁇ s, and even more preferably 70 to 300 mPa ⁇ s.
  • the viscosity of organopolysiloxane B1 is 500 mPa ⁇ s or less, the viscosity of the first agent tends to decrease further.
  • the viscosity of organopolysiloxane B1 is 30 mPa ⁇ s or more, mechanical strength such as shear displacement and elongation at break in a cured product, which will be described later, tends to be further improved.
  • the viscosity of the organopolysiloxane at 25°C can be measured using a digital viscometer "DV-1" manufactured by BROOKFIELD.
  • DV-1 digital viscometer
  • rotor no Using the RV spindle set, rotor no.
  • the rotor Using a container that can accommodate the rotor and fill the organopolysiloxane up to the reference line, the rotor is immersed in the organopolysiloxane, and the viscosity is measured at 25° C. and a rotation speed of 10 rpm.
  • vinyl-modified organopolysiloxane B1 undergoes an addition reaction with hydrosilyl-modified organopolysiloxane E2 contained in the second agent in the presence of addition reaction catalyst D1.
  • addition reaction catalyst D1 By appropriately adjusting the number of vinyl groups and the number of hydrosilyl groups of vinyl-modified organopolysiloxane B1 and hydrosilyl-modified organopolysiloxane E2, and the viscosity, the viscosity of the first and second parts and the mixing of the first and second parts are adjusted.
  • the curing speed can be controlled.
  • the content of vinyl-modified organopolysiloxane B1 is preferably 60 to 99% by weight, more preferably 70 to 98% by weight, based on the total of components other than the thermally conductive filler C1 of the first part, More preferably, it is 80 to 95% by weight.
  • Thermal conductive filler C1 The thermally conductive filler C1 is a filler that has thermal conductivity.
  • the thermal conductivity of the thermally conductive filler C1 is not particularly limited, but is, for example, 10 W/m ⁇ K or more, 20 W/m ⁇ K or more, or 30 W/m ⁇ K or more.
  • the upper limit of the thermal conductivity of the thermally conductive filler C1 is not particularly limited, and may be, for example, 400 W/m ⁇ K or 300 W/m ⁇ K.
  • thermally conductive filler C1 is not particularly limited, but includes, for example, aluminum oxide (hereinafter also referred to as "alumina"), aluminum nitride, silica, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, and metal.
  • alumina aluminum oxide
  • aluminum nitride aluminum nitride
  • silica aluminum nitride
  • boron nitride silicon nitride
  • zinc oxide aluminum hydroxide
  • metal examples include aluminum, magnesium oxide, diamond, carbon, indium, gallium, copper, silver, iron, nickel, gold, tin, and metallic silicon.
  • the first agent contains one or more types selected from the group consisting of boron nitride, aluminum nitride, aluminum oxide, silicon nitride, silicon oxide, magnesium oxide, metal aluminum, and zinc oxide as the thermally conductive filler C1. It is preferable that it contains one or more selected from the group consisting of aluminum oxide, magnesium oxide, aluminum nitride, and metal aluminum, and it is even more preferable that it contains aluminum oxide. This is because the thermally conductive filler has high thermal conductivity, high insulation properties, and is inexpensive.
  • the thermally conductive filler C1 may be used alone or in combination of two or more.
  • the average particle size of the thermally conductive filler C1 is preferably 0.05 to 120 ⁇ m, more preferably 0.1 to 70 ⁇ m. When the average particle size of the thermally conductive filler C1 is within the above range, the fluidity of the first agent and the dispersibility and filling properties of the thermally conductive filler C1 tend to be further improved.
  • the thermally conductive filler C1 may be a mixture of fillers having different average particle diameters.
  • a thermally conductive filler (C1-1) having an average particle size of 30 to 100 ⁇ m, a thermally conductive filler (C1-2) having an average particle size of 1.5 to 25 ⁇ m, and an average particle size It is preferable to use a combination of two or more types of thermally conductive filler (C1-3) having a diameter of 0.05 to 1.0 ⁇ m, and at least the thermally conductive filler (C1-1) and the thermally conductive filler (C1-3) are used in combination. It is more preferable to use 2), and it is even more preferable to use all of the thermally conductive filler (C1-1), the thermally conductive filler (C1-2), and the thermally conductive filler (C1-3).
  • the average particle size of the thermally conductive filler can be measured using, for example, "Laser Diffraction Particle Size Distribution Analyzer SALD-20" (trade name) manufactured by Shimadzu Corporation.
  • the evaluation sample is prepared, for example, by adding 50 ml of pure water and 5 g of the thermally conductive filler powder to be measured into a glass beaker, stirring with a spatula, and then performing dispersion treatment with an ultrasonic cleaner for 10 minutes. do. Thereafter, the solution of the thermally conductive filler powder subjected to the dispersion treatment is added drop by drop to the sampler section of the apparatus using a dropper, and the measurement is performed when the absorbance becomes stable.
  • the particle size distribution is calculated from data on the light intensity distribution of diffraction/scattering holes by particles detected by a sensor.
  • the average particle size is determined by multiplying the measured particle size value by the relative particle amount (difference %) and dividing by the total relative particle amount (100%). Note that the average particle size is the average diameter of particles, and can be determined as a cumulative weight average value D50 (median diameter). Note that D50 is the particle diameter with the highest appearance rate.
  • the content of the thermally conductive filler (C1-1) is preferably 30 to 70% by weight, more preferably 40 to 60% by weight, based on the total amount of the thermally conductive filler C1.
  • the content of the thermally conductive filler (C1-2) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on the total amount of the thermally conductive filler C1.
  • the content of the thermally conductive filler (C1-3) is preferably 5 to 30% by weight, more preferably 10 to 20% by weight, based on the total amount of the thermally conductive filler C1.
  • the thermally conductive filler C1 By using the thermally conductive filler C1 as described above, the fluidity of the first agent and the dispersibility and filling properties of the thermally conductive filler C1 tend to be further improved.
  • the average particle diameter in this specification shall mean D50 (median diameter).
  • the content of the thermally conductive filler C1 is preferably 400 to 3000 parts by weight, more preferably 600 to 2800 parts by weight, and even more preferably The amount is 700 to 2,600 parts by weight.
  • the content of the thermally conductive filler C1 is 400 parts by weight or more, the thermal conductivity of the obtained cured product tends to be further improved, and when it is 3000 parts by weight or less, the viscosity of the first agent is further reduced. There is a tendency.
  • the addition reaction catalyst D1 is not particularly limited as long as it catalyzes the addition reaction between the vinyl-modified organopolysiloxane B1 and the hydrosilyl-modified organopolysiloxane E2.
  • Examples of the addition reaction catalyst D1 include platinum compound catalysts, rhodium compound catalysts, palladium compound catalysts, and the like. Among these, platinum compound catalysts are preferred.
  • the platinum compound catalyst is not particularly limited, but includes, for example, simple platinum, platinum compounds, and platinum-supported inorganic powder.
  • the platinum compound include, but are not limited to, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds, and the like.
  • the platinum-supported inorganic powder is not particularly limited, and examples thereof include platinum-supported alumina powder, platinum-supported silica powder, and platinum-supported carbon powder.
  • addition reaction catalyst D1 may be used alone or in combination of two or more. Further, when preparing the first agent, addition reaction catalyst D1 may be blended alone, or may be mixed in advance with other components such as vinyl-modified organopolysiloxane B1 or other organopolysiloxanes. May be blended.
  • the content of the addition reaction catalyst D1 is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the vinyl-modified organopolysiloxane B1. More preferably, it is 1 to 10 parts by weight.
  • the first part may contain additives such as a coloring agent and a reaction retarder, if necessary.
  • the content of the colorant is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the total amount of the first agent.
  • the reaction retarder is not particularly limited as long as it is a component that retards the reaction when the first part and the second part are mixed, but examples thereof include alkenyl alcohols, among which 1-ethynyl-1-cyclohexanol is used. preferable.
  • the content of the reaction retarder is preferably 0.1 to 20 parts by weight, more preferably The amount is 0.5 to 10 parts by weight.
  • the reaction retarder may not be included in the first part but only in the second part.
  • the first agent has the following formula: R 1 a R 2 b Si(OR 3 ) 4-(a+b) (R 1 is each independently an alkyl group having 1 to 15 carbon atoms, R 2 is each independently a saturated or unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms, Each R 3 is independently an alkyl group having 1 to 6 carbon atoms, a is 1 to 3, b is 0 to 2, and a+b is 1 to 3.) It is preferable that the organosilane represented by is not included.
  • Such organosilane has been conventionally used to improve the wettability of thermally conductive fillers, but it is not included in the first agent in the two-component curable composition set of this embodiment. Preferably not. According to such an embodiment, the viscosity of the first agent tends to be further reduced compared to the case where the organosilane as described above is included. The reason for this is not necessarily clear, but when the first agent contains an organosilane, the copolymer A1 and the organosilane compete as components that improve the wettability of the thermally conductive filler. It is conceivable that the effect of
  • R 1 in the above formula is not particularly limited, and examples thereof include a methyl group, ethyl group, propyl group, hexyl group, nonyl group, decyl group, dodecyl group, and tetradecyl group.
  • R 1 is preferably an alkyl group having 6 to 12 carbon atoms.
  • R2 in the above formula is not particularly limited, but includes, for example, alkyl groups such as methyl, ethyl, propyl, hexyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl and allyl groups; alkenyl groups such as phenyl groups, tolyl groups; aralkyl groups such as 2-phenylethyl groups and 2-methyl-2-phenylethyl groups; 3,3,3-trifluoropropyl groups, 2-( Examples include halogenated hydrocarbon groups such as perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, and p-chlorophenyl group.
  • alkyl groups such as methyl, ethyl, propyl, hexyl, and octyl
  • cycloalkyl groups such as cyclopentyl and cyclohe
  • R 3 in the above formula is not particularly limited, but is, for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group, preferably a methyl group. Or it is an ethyl group.
  • a is an integer from 1 to 3, preferably 1.
  • b is an integer of 0 to 2, preferably 0.
  • a+b is an integer from 1 to 3, preferably 1.
  • the content of the organosilane in the first agent is preferably 1 part by weight or less, more preferably 0.1 part by weight or less, based on 100 parts by weight of the thermally conductive filler C1. It is preferably 0.01 part by weight or less, particularly preferably 0 part by weight (ie, does not contain organosilane). When the content of organosilane is within the above range, the wettability of the thermally conductive filler tends to be effectively improved.
  • the viscosity of the first agent at 25° C. and a shear rate of 10 s ⁇ 1 is preferably 20 to 160 Pa ⁇ s, more preferably 50 to 150 Pa ⁇ s, and still more preferably 70 to 140 Pa ⁇ s.
  • the viscosity is 20 Pa ⁇ s or more, there is a tendency that the dripping resistance and/or pump-out resistance of the two-component curable composition set can be further improved.
  • the viscosity is 160 Pa ⁇ s or less, the handling properties are excellent, and the coating properties of the liquid mixture obtained by mixing the first agent and the second agent tend to be improved.
  • the viscosity of the first agent and the second agent described later at 25° C. and a shear rate of 10 s ⁇ 1 can be measured using a rotary rheometer “HANKE MARS III” manufactured by Thermo Fisher Scientific. More specifically, the measurement can be performed using a parallel plate with a diameter of 35 mm ⁇ , a gap of 0.5 mm, a temperature of 25° C., and a shear rate of 10 s ⁇ 1 .
  • Second Part contains copolymer A2, vinyl-modified organopolysiloxane B2, thermally conductive filler C2, and hydrosilyl-modified organopolysiloxane E2, and may contain other components as necessary. You can stay there.
  • Copolymer A2 Details such as specific examples and preferred embodiments of copolymer A2 are the same as those for copolymer A1 contained in the first agent, and redundant explanation will be omitted. Copolymer A1 contained in the first agent and copolymer A2 contained in the second agent may be the same or different.
  • the content of copolymer A2 is preferably 1 to 40 parts by weight, more preferably 2 parts by weight, based on a total of 100 parts by weight of vinyl-modified organopolysiloxane B2 and hydrosilyl-modified organopolysiloxane E2. 30 parts by weight, more preferably 3 to 20 parts by weight, even more preferably 5 to 15 parts by weight.
  • the content of the copolymer A2 is within the above range, the dispersibility of the thermally conductive filler C2 tends to be further improved, and the viscosity of the second agent tends to be further reduced.
  • Vinyl modified organopolysiloxane B2 Details such as specific examples and preferred embodiments of the vinyl-modified organopolysiloxane B2 are the same as those of the vinyl-modified organopolysiloxane B1 contained in the first agent, and redundant explanations will be omitted.
  • the vinyl-modified organopolysiloxane B1 contained in the first part and the vinyl-modified organopolysiloxane B2 contained in the second part may be the same or different.
  • the content of vinyl-modified organopolysiloxane B2 is preferably 40 to 98 parts by weight, more preferably is 45 to 95 parts by weight, more preferably 50 to 93 parts by weight.
  • the curing rate when the first part and the second part are mixed tends to be within a more suitable range.
  • the content of vinyl-modified organopolysiloxane B2 may be 90 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less within the above range.
  • Thermal conductive filler C2 Details such as specific examples and preferred embodiments of the thermally conductive filler C2 are the same as those of the thermally conductive filler C1 included in the first agent, and redundant explanation will be omitted.
  • the thermally conductive filler C1 contained in the first part and the thermally conductive filler C2 contained in the second part may be the same or different.
  • the content of the thermally conductive filler C2 is preferably 400 to 3000 parts by weight, more preferably 600 to 2800 parts by weight, based on a total of 100 parts by weight of vinyl-modified organopolysiloxane B2 and hydrosilyl-modified organopolysiloxane E2. and more preferably 700 to 2,600 parts by weight.
  • the content of the thermally conductive filler C2 is 400 parts by weight or more, the thermal conductivity of the obtained cured product tends to be further improved, and when it is 3000 parts by weight or less, the viscosity of the second agent is further reduced. There is a tendency.
  • Organopolysiloxane E2 Hydrosilyl-modified organopolysiloxane E2 (hereinafter also simply referred to as "organopolysiloxane E2") is an organopolysiloxane having at least one hydrosilyl group. Organopolysiloxane E2 may have a hydrosilyl group in the side chain and/or at the end. Such an organopolysiloxane has a structural unit represented by the following formula (e2-1) or a terminal structure represented by the formula (e2-2). Organopolysiloxane E2 includes, for example, at least one of a structural unit represented by formula (e2-1) and a terminal structure represented by formula (e2-2), and a structural unit represented by formula (e2-3). It may have.
  • R is any monovalent hydrocarbon group which may have a substituent. That is, in organopolysiloxane E2, any monovalent hydrocarbon group that may have a substituent is bonded to the side chain of the siloxane skeleton.
  • Examples of such monovalent hydrocarbon groups include the same monovalent hydrocarbon groups that vinyl-modified organopolysiloxane B1 may have.
  • Organopolysiloxane E2 is contained in the second agent singly or in combination of two or more types.
  • the second agent contains at least a hydrosilyl-modified organopolysiloxane E22 having a hydrosilyl group in a side chain as the organopolysiloxane E2, and a hydrosilyl-modified organopolysiloxane E21 having a hydrosilyl group at both ends; It is more preferable to include organopolysiloxane E22.
  • Organopolysiloxane E21 has at least two hydrosilyl groups at both ends of the organopolysiloxane skeleton. Organopolysiloxane E21 may further have a hydrosilyl group in the side chain. Organopolysiloxane E21 may be an organopolysiloxane having hydrosilyl groups only at both ends.
  • Organopolysiloxane E22 has at least one hydrogen atom in the side chain of the organopolysiloxane skeleton, and the hydrogen atom and silicon atom constitute a hydrosilyl group. Organopolysiloxane E22 may further have hydrosilyl groups at both ends of the organopolysiloxane skeleton.
  • the number of hydrosilyl groups in organopolysiloxane E22 is preferably more than 2.0 on average per molecule, more preferably 2.5 or more on average per molecule, even more preferably on average per molecule. 3.0 or more. Note that the upper limit of the number of hydrosilyl groups in organopolysiloxane E22 is not particularly limited, and may be, for example, 8.0, 6.0, or 5.0 on average per molecule.
  • the number of hydrosilyl groups in the organopolysiloxane E2 contained in the second agent is preferably more than 2.0 on average per molecule, more preferably 2.5 or more on average per molecule. That is, when the second agent contains one type of organopolysiloxane E2, it is preferable that the organopolysiloxane has more than two (that is, three or more) hydrosilyl groups per molecule. When the second agent contains two or more types of organopolysiloxanes E2, the arithmetic average of the number of hydrosilyl groups in each organopolysiloxane is preferably more than 2.0.
  • organopolysiloxane E21 and organopolysiloxane E22 can be controlled separately as described above, by appropriately mixing them and using them, while controlling the viscosity of the second agent, It tends to be possible to control the reactivity with the first agent.
  • the second agent contains organopolysiloxane E22, it forms a network structure when reacting with vinyl-modified organopolysiloxanes B1 and B2, resulting in a cured product with better mechanical strength such as shear displacement and elongation at break. You tend to be able to get it.
  • the average number of hydrosilyl groups per molecule of organopolysiloxane E2 may be measured by NMR. Specifically, the measurement may be performed by dissolving organopolysiloxane E2 in heavy chloroform as a heavy solvent using, for example, ECP-300NMR manufactured by JEOL. The average number of hydrosilyl groups per molecule can be calculated by dividing the measurement results obtained in this manner by the average molecular weight of organopolysiloxane E2.
  • the viscosity of organopolysiloxane E21 at 25° C. is preferably 5 to 100 mPa ⁇ s, more preferably 10 to 80 mPa ⁇ s, and still more preferably 15 to 50 mPa ⁇ s.
  • the viscosity of organopolysiloxane E21 is 100 mPa ⁇ s or less, the viscosity of the second agent tends to decrease further.
  • the viscosity of organopolysiloxane E21 is 5 mPa ⁇ s or more, mechanical strength such as shear displacement and elongation at break in a cured product, which will be described later, tends to be further improved.
  • the viscosity of organopolysiloxane E22 at 25° C. is preferably 1 to 100 mPa ⁇ s, more preferably 2 to 90 mPa ⁇ s, and still more preferably 3 to 80 mPa ⁇ s.
  • the viscosity of organopolysiloxane E22 is 100 mPa ⁇ s or less, the viscosity of the second agent tends to decrease further.
  • the viscosity of organopolysiloxane E22 is 1 mPa ⁇ s or more, mechanical strength such as shear displacement and elongation at break in a cured product, which will be described later, tends to be further improved.
  • the viscosity of organopolysiloxane E22 at 25° C. may be 60 to 80 mPa ⁇ s within the above range.
  • the content of hydrosilyl-modified organopolysiloxane E2 is preferably 2 to 60 parts by weight, more preferably is 5 to 55 parts by weight, more preferably 7 to 50 parts by weight.
  • the curing rate when the first part and the second part are mixed tends to be within a more suitable range.
  • the content of the hydrosilyl-modified organopolysiloxane E2 may be 10 parts by weight or more, 20 parts by weight or more, or 30 parts by weight or more within the above range.
  • the total content of vinyl-modified organopolysiloxane B2 and hydrosilyl-modified organopolysiloxane E2 is preferably 60 to 99% by weight, more preferably is 70 to 98% by weight, more preferably 80 to 95% by weight.
  • reaction retarder F2 is an additive that is optionally added to control the reaction between the hydrosilyl group and the vinylsilyl group.
  • the first part contains the addition reaction catalyst D1 and the second part contains a reaction retarder.
  • the reaction retarder F2 is not particularly limited as long as it is a component that retards the reaction when the first part and the second part are mixed, but examples thereof include alkenyl alcohols, among which 1-ethynyl-1-cyclohexanol is preferred.
  • the curing speed when the first part and the second part are mixed can be set in a suitable range, and the dripping resistance and/or dripping resistance of the two-part curable composition set can be improved. Alternatively, it tends to be possible to further improve pump-out resistance.
  • the content of the reaction retarder F2 is preferably 0.1 to 20 parts by weight based on a total of 100 parts by weight of the vinyl-modified organopolysiloxane B2 and the hydrosilyl-modified organopolysiloxane E2. Parts by weight, more preferably 0.5 to 10 parts by weight.
  • the second agent may contain additives such as colorants, if necessary. Details such as specific examples, preferred embodiments, and content of the colorant are the same as those for the first agent, and redundant explanations will be omitted.
  • the additives contained in the first part and the additives contained in the second part may be the same or different.
  • the second agent has the following formula: R 1 a R 2 b Si(OR 3 ) 4-(a+b) (R 1 is each independently an alkyl group having 1 to 15 carbon atoms, R 2 is each independently a saturated or unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms, Each R 3 is independently an alkyl group having 1 to 6 carbon atoms, a is 1 to 3, b is 0 to 2, and a+b is 1 to 3.) It is preferable that the organosilane represented by is not included. By not containing the organosilane, the viscosity of the second agent tends to be further reduced.
  • organosilane described above are the same as the organosilane that is preferably not included in the first agent. Further, the preferable content of the organosilane in the second part is also the same as that in the first part.
  • the viscosity of the second agent at 25° C. and a shear rate of 10 s ⁇ 1 is preferably 20 to 150 Pa ⁇ s, more preferably 50 to 140 Pa ⁇ s, and even more preferably 70 to 130 Pa ⁇ s.
  • the viscosity is 20 Pa ⁇ s or more, there is a tendency that the dripping resistance and/or pump-out resistance of the two-component curable composition set can be further improved.
  • the viscosity is 150 Pa ⁇ s or less, the handling properties are excellent, and the coating properties of the liquid mixture obtained by mixing the first part and the second part tend to be further improved.
  • the rate of progress of curing and the physical strength during curing are expressed by loss tangent tan ⁇ .
  • loss tangent tan ⁇ the loss tangent tan ⁇ of the mixture is measured with a rotary rheometer at 25° C. and a frequency of 1 Hz after mixing equal volumes of the first and second agents, the loss tangent tan ⁇ is less than 0.20. The time required for this to occur is within 24 hours from mixing.
  • the first and second parts in the two-component curable composition set of this embodiment have a loss tangent tan ⁇ of less than 0.20 within 24 hours as described above, that is, a curing reaction occurs at a predetermined rate.
  • the thermally conductive grease obtained using such a two-component curing composition set has a low viscosity, it starts curing before dripping occurs when used vertically, suppressing dripping.
  • pump-out is also suppressed because it cures sufficiently in a short time.
  • the time required for the loss tangent tan ⁇ to become less than 0.20 is preferably within 12 hours, more preferably within 8 hours, and more preferably within 5 hours from mixing. is even more preferable.
  • the lower limit of the time required for the loss tangent tan ⁇ to become less than 0.20 is not particularly limited, but may be 10 minutes or more, or 30 minutes or more.
  • the rate of progress of curing and the physical strength during curing may be expressed by the storage modulus G'.
  • the storage elastic modulus G 0 ' of a mixture obtained by mixing equal volumes of the first agent and the second agent with a rotary rheometer at 25° C. and a frequency of 1 Hz immediately after mixing is 15 hours after mixing.
  • the ratio G 15 ′/G 0 ′ of the storage modulus G 15 ′, which is later measured in the same manner as above, is preferably 100 to 1,500, more preferably 300 to 1,200, and still more preferably 600 to 1,000.
  • the curing rate when the first and second parts are mixed tends to be within a suitable range, and when it is 1,500 or less, the curing rate tends to be within a suitable range.
  • the viscosity of the mixture immediately after mixing the first part and the second part is not too low, and the drip-off resistance and/or pump-out resistance of the two-part curable composition set tends to be improved. .
  • the value of the storage elastic modulus G 15 ' is not particularly limited, but is preferably 100,000 to 1,000,000 Pa, more preferably 200,000 to 900,000 Pa, even more preferably 300,000 to It is 800,000Pa.
  • the value of the storage elastic modulus G 0 ' is not particularly limited, but is preferably 100 to 3,000 Pa, more preferably 300 to 2,000 Pa, and still more preferably 500 to 1,200 Pa.
  • the two-component curable composition set of this embodiment can be suitably used as a thermally conductive heat dissipating material such as thermally conductive grease.
  • the cured product of this embodiment is obtained by mixing the first part and the second part in the above-mentioned two-component curable composition set. More specifically, the cured product (crosslinked cured product) is a mixture obtained by mixing the first agent and the second agent. The above-mentioned cured product is obtained by progressing the addition reaction of E2 with the hydrosilyl group.
  • a cured product having a desired shape can be obtained by molding it into a desired shape before curing.
  • the cured product of this embodiment contains a thermally conductive filler, it can be suitably used as a thermally conductive heat dissipating material.
  • a mixer such as a roll mill, kneader, Banbury mixer, or line mixer is used, for example. More specifically, examples include a method of kneading using a universal mixer, a hybrid mixer, a trimix (manufactured by Inoue Seisakusho), and a static mixer.
  • a doctor blade method is preferred as the molding method, but extrusion methods, press methods, calender roll methods, etc. may also be used depending on the viscosity of the resin.
  • the reaction conditions for the addition reaction are not particularly limited, but it is usually carried out at room temperature (for example, 25°C) to 150°C for 0.1 to 24 hours.
  • the electronic device of this embodiment includes an electronic component, a cured product, and a heat sink, and the electronic component and the heat sink are in contact with each other via the cured product.
  • electronic components include, but are not particularly limited to, electronic components that generate heat, such as motors, battery packs, circuit boards mounted on vehicle power supply systems, power transistors, microprocessors, and the like.
  • the heat sink is not particularly limited, but includes, for example, a casing, particularly a metal casing.
  • ((meth)acrylic monomer ⁇ having a siloxane skeleton) ( ⁇ -1) ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane), “Siraplane FM-0725” manufactured by JNC, number average molecular weight 10,000 ( ⁇ -2) ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane), “Siraplane FM-0721” manufactured by JNC, number average molecular weight 5000 ( ⁇ -3) ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane), “Siraplane FM-0711” manufactured by JNC, number average molecular weight 1000
  • Copolymer 1 was synthesized as follows. First, in an autoclave equipped with a stirrer, 1.5 parts by weight of acrylic acid, 0.5 parts by weight of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and ⁇ -butyl- ⁇ -( 98.0 parts by weight of 3-methacryloxypropyl) polydimethylsiloxane ( ⁇ -1) was added.
  • the polymerization rate based on 100% monomer charge amount was 98% or more when analyzed by gas chromatography. From this, it was estimated that the ratio of each monomer unit in the copolymer was approximately the same as the monomer charge ratio.
  • the weight average molecular weight of the obtained copolymer 1 was determined as a weight average molecular weight in terms of standard polystyrene using GPC (gel permeation chromatography) method.
  • GPC gel permeation chromatography
  • Copolymers 2-11 The composition ratio of (meth)acrylic monomers listed in Table 1 was used, except that the mixing ratio of toluene and isopropyl alcohol was adjusted to control the solubility of the monomer and the weight average molecular weight of the copolymer. , Radical polymerization was performed in the same manner as for Copolymer 1 to obtain Copolymers 2 to 11. The polymerization rates of the obtained copolymers 2 to 11 were all 98% or more, and the ratio of each monomer unit in the copolymers was estimated to be about the same as the monomer charge ratio. Moreover, the weight average molecular weight was also determined in the same manner as above.
  • composition of monomers is shown in weight %.
  • the weight ratio of ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane was calculated based on its number average molecular weight.
  • A1-1 to 1-11 Copolymers 1 to 11 obtained by the above synthesis method (A1-1 to 1-11 correspond to copolymers 1 to 11 in order, respectively.)
  • B1 Vinyl-modified organopolysiloxane
  • B1-1 RH-Vi100E (manufactured by Runhe Chemical Industry, trade name), vinyl-modified organopolysiloxane, viscosity at 25°C: 105 mPa ⁇ s, average number of vinyl groups per molecule: 2, linear structure, vinyl Group bonding position: both ends
  • C1-1 Thermal conductive filler
  • C1-1 DAW45S (manufactured by Denka, trade name), spherical alumina, average particle size: 45 ⁇ m, thermal conductivity 35 W/m ⁇ K C1-2: DAW05 (manufactured by Denka, trade name), spherical alumina, average particle size: 5 ⁇ m, thermal conductivity 35 W/m ⁇ K C1-3: ASFP40 (manufactured by Denka, trade name), ultrafine powder alumina, average particle size: 0.4 ⁇ m, thermal conductivity 35 W/m ⁇ K C1-4: DMG60 (manufactured by Denka, trade name), magnesium oxide, average particle size: 60 ⁇ m, thermal conductivity 60 W/m ⁇ K C1-5: AN-HF50LG (manufactured by Yasushi Gosei Co., Ltd., trade name), aluminum nitride, average particle size: 50 ⁇ m, thermal conductivity 170 W/m ⁇ K C1-6: Al-63
  • D1-1 Platinum complex polymethylvinylsiloxane solution (manufactured by Blue Star Silicone Co., Ltd., product name: Silicoreath Catalyst 12070)
  • Second agent The following A2 component to C2 component, E2 component, and F2 component were mixed based on the blending ratio (parts by weight) listed in Table 3 to prepare second agent II-1 to II to 19. did.
  • the components were mixed using a hybrid mixer ARE-310 (manufactured by Shinky Co., Ltd., trade name).
  • A2-1 to 2-11 Copolymers 1 to 11 obtained by the above synthesis method (A2-1 to 2-11 correspond to copolymers 1 to 11 in order, respectively.)
  • B2 Vinyl-modified organopolysiloxane
  • B2-1 RH-Vi100E (manufactured by Runhe Chemical Industry, trade name), vinyl-modified organopolysiloxane, viscosity at 25°C: 105 mPa ⁇ s, average number of vinyl groups per molecule: 2, linear structure, vinyl Group bonding position: both ends
  • C2 Thermal conductive filler
  • C2-1 DAW45S (manufactured by Denka, trade name), spherical alumina, average particle size: 45 ⁇ m, thermal conductivity 35 W/m ⁇ K
  • C2-2 DAW05 (manufactured by Denka, trade name), spherical alumina, average particle size: 5 ⁇ m, thermal conductivity 35 W/m ⁇ K C2-3: ASFP40 (manufactured by Denka, trade name), ultrafine alumina powder, average particle size: 0.4 ⁇ m, thermal conductivity 35 W/m ⁇ K C2-4: DMG60 (manufactured by Denka, trade name), magnesium oxide, average particle size: 60 ⁇ m, thermal conductivity 60 W/m ⁇ K C2-5: AN-HF50LG (manufactured by Yasushi Gosei Co., Ltd., trade name), aluminum nitride, average particle size: 50 ⁇ m, thermal conductivity 170 W/m ⁇ K C2-6: Al-
  • E2 Hydrosilyl-modified organopolysiloxane
  • E2-1 RH-LHC-3 (manufactured by Runhe Chemical Industry, trade name), hydrosilyl-modified organopolysiloxane, viscosity at 25°C: 5 mPa ⁇ s, average number of hydrosilyl groups per molecule: 3 or more, linear Structure, hydrosilyl group bonding position: side chain
  • E2-2 RH-H45 (manufactured by Runhe Chemical Industry, trade name), hydrosilyl-modified organopolysiloxane, viscosity at 25°C: 20 mPa ⁇ s, average number of hydrosilyl groups per molecule: 2 pieces, linear structure, hydrosilyl group bonding position: both ends
  • F2-1 PA90 (manufactured by Elkem, trade name), a mixture of 1-ethynyl-1-cyclohexanol, polyorganosiloxane, and filler
  • the viscosity of the first and second agents at 25° C. and a shear rate of 10 s ⁇ 1 was measured using a rotary rheometer “HANKE MARS III” manufactured by Thermo Fisher Scientific. Specifically, the measurement was performed using a parallel plate with a diameter of 35 mm ⁇ , a gap of 0.5 mm, a temperature of 25° C., and a shear rate of 10 s ⁇ 1 . The results are shown in Table 4.
  • the drip resistance of the thermally conductive grease obtained from the first and second parts was evaluated by the test method shown in FIGS. 1 and 2.
  • shims 11 with a thickness of 2 mm are installed at the four corners of a glass plate 10 of 80 mm x 80 mm, and the first and second agents are mixed in the combinations shown in Table 4 at a volume ratio of 1:1.
  • the mixture 12 obtained by mixing in step 1 was applied in a circular manner approximately at the center of the glass plate 10, and the mixture 12 was sandwiched between glass plates 13 of 80 mm x 80 mm.
  • the amount of the mixture 12 applied was such that the size of the circular shape of the thermally conductive grease formed when the glass plates 10 and 13 were sandwiched was 15 mm ⁇ .
  • Pump-out rate (%) (diameter after thermal shock test - diameter before thermal shock test) / diameter before thermal shock test x 100 ⁇ : Pump-out rate less than 5%. ⁇ : Pump-out rate of 5% or more.
  • a first agent containing copolymer A1, vinyl-modified organopolysiloxane B1, thermally conductive filler C1, and addition reaction catalyst D1, copolymer A2, and vinyl-modified organopolysiloxane B2
  • a second agent containing a thermally conductive filler C2 and a hydrosilyl-modified organopolysiloxane E2 wherein the copolymer A1 and the copolymer A2 are (meth)acrylic monomers having a carboxy group.
  • Comparative Examples 18, 23, and 28 in which either the first part or the second part does not contain a copolymer, and the copolymer contains monomer units ⁇ , monomer units ⁇ , and monomer units In Comparative Examples 15, 16, 19, 20, 24, and 25 that did not contain any of ⁇ , either the first agent or the second agent had a high viscosity.
  • the two-component curable composition set of this embodiment is a thermally conductive cured product, in particular, for thermally bonding a heating element and a heat sink by mixing and curing a first part and a second part. It has industrial applicability as a material.

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PCT/JP2023/012376 2022-03-29 2023-03-28 二液硬化型組成物セット、硬化物及び電子機器 WO2023190439A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003034784A (ja) * 2001-07-24 2003-02-07 Lion Corp 撥水処理剤
JP2016121350A (ja) * 2014-12-24 2016-07-07 東洋インキＳｃホールディングス株式会社 シリカ分散体、および、活性エネルギー線硬化性樹脂組成物
WO2020080256A1 (ja) * 2018-10-15 2020-04-23 デンカ株式会社 二液硬化型組成物セット、熱伝導性硬化物及び電子機器
WO2021246397A1 (ja) * 2020-06-05 2021-12-09 デンカ株式会社 二液硬化型熱伝導性グリース用組成物、熱伝導性グリース、および電子機器
WO2022075306A1 (ja) * 2020-10-05 2022-04-14 デンカ株式会社 熱伝導性樹脂組成物及び電子機器

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003034784A (ja) * 2001-07-24 2003-02-07 Lion Corp 撥水処理剤
JP2016121350A (ja) * 2014-12-24 2016-07-07 東洋インキＳｃホールディングス株式会社 シリカ分散体、および、活性エネルギー線硬化性樹脂組成物
WO2020080256A1 (ja) * 2018-10-15 2020-04-23 デンカ株式会社 二液硬化型組成物セット、熱伝導性硬化物及び電子機器
WO2021246397A1 (ja) * 2020-06-05 2021-12-09 デンカ株式会社 二液硬化型熱伝導性グリース用組成物、熱伝導性グリース、および電子機器
WO2022075306A1 (ja) * 2020-10-05 2022-04-14 デンカ株式会社 熱伝導性樹脂組成物及び電子機器

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