Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/14—Solid materials, e.g. powdery or granular
• • 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
• • 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
  • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

• the present invention relates to a two-component curable composition set, a heat conductive cured product, and an electronic device.
• Room temperature curable liquid silicone rubber exhibits stable performance over a wide temperature range, so it is a CPU (central processing unit) for personal computers and batteries for automobiles. It is used for the purpose of improving the reliability of electrical and electronic devices such as LED devices. Specifically, it is used as a sealing material, a sealing material, a potting material, a coating material, and a heat radiating material for each electronic base material.
• Room temperature curing type liquid silicone rubber is mainly classified into one-component type and two-component type, and the two-component type is further divided into condensation reaction type and addition reaction type.
• the condensation reaction type can exhibit excellent adhesiveness to various substrates that come into contact during curing because the composition is cured by the humidity in the air.
• a composition that is cured by dealcohol condensation using a titanium-based condensation reaction catalyst is suitable as a sealing material or coating material for electrical and electronic equipment because it does not generate an unpleasant odor or corrode metals during curing. Is.
• the condensation reaction type is hermetically sealed because it gradually cures from the part that comes into contact with moisture in the air, so it takes a long time for uniform curing, and it generates outgas during curing. There is a problem that it is not suitable for various applications.
• the addition reaction type has a low shrinkage rate due to curing, high uniform reactivity, and does not generate outgas, so it is suitable as a sealing material or heat radiating material for electrical / electronic equipment.
• the addition reaction type requires a platinum catalyst, which is a precious metal, but the platinum catalyst is sensitive to temperature, and there is a problem that the catalytic activity is deactivated by transportation in a high temperature environment. Further, there is a problem that curing failure occurs on the substrate due to curing inhibitory substances such as nitrogen-containing compound, sulfur-containing compound, phosphorus-containing compound, tin-containing compound, sulfur and solder flux, alcohol, water, carboxylic acid and the like.
• condensation reaction type and the addition reaction type each have advantages and disadvantages, and they are used according to the purpose and purpose, and improvement studies to overcome the disadvantages have been reported.
• Patent Document 1 comprises a mixture of an organopolysiloxane containing an alkoxy group and an organopolysiloxane containing a lower alkenyl group, an organopolysiloxane containing a silicon base paper bonded hydrogen atom, an alkoxysilane, and a catalyst for a hydrosilylation reaction.
• a composition that cures uniformly without causing curing inhibition and has excellent adhesiveness is described.
• Patent Document 2 an addition consisting of an organopolysiloxane containing an alkenyl group, an organohydrogenpolysiloxane, a platinum catalyst, and an adhesive-imparting agent is less susceptible to the effects of curing inhibitors and has excellent adhesiveness.
• Reactive silicone rubber compositions have been described.
• Patent Documents 3 and 4 describe, as a silicone-based composition other than the condensation reaction type and the addition reaction type, a resin composition made of a silicone-modified epoxy resin and a silicone compound having a reactive functional group.
• Japanese Unexamined Patent Publication No. 8-269337 Japanese Unexamined Patent Publication No. 2006-22284 Japanese Unexamined Patent Publication No. 10-0177776 Japanese Unexamined Patent Publication No. 55-90554
• the two-component condensation reaction type and the two-component addition reaction type liquid silicone rubber have advantages and disadvantages, respectively, and it has been desired to develop a room temperature curable liquid silicone rubber that overcomes the disadvantages of both.
• the present invention has been made in view of the above problems, and is a two-component curing type composition that does not require moisture for the curing reaction, has high uniform curing property, does not require a platinum catalyst, and is less likely to cause curing inhibition. It is an object of the present invention to provide a set, a cured product or a heat conductive cured product obtained from the two-component curable composition set, and an electronic device provided with the heat conductive cured product.
• a first agent containing an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and a thermally conductive filler B1 It comprises an amino-modified organopolysiloxane A2 having an amino group-containing group and a second agent containing a thermally conductive filler B2.
• the functional group equivalent of the epoxy group in one molecule of the epoxy-modified organopolysiloxane A1 is 100 to 11000 g / mol.
• the functional group equivalent of the amino group in one molecule of the amino-modified organopolysiloxane A2 is 100 to 8000 g / mol.
• the amino-modified organopolysiloxane A2 in the second agent has hydroxyl group-containing groups at both ends.
• the thermally conductive filler B1 and the thermally conductive filler B2 exhibit a thermal conductivity of 10 W / m ⁇ K or more, such as aluminum oxide, aluminum nitride, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metallic aluminum, and oxidation. Containing at least one selected from the group consisting of magnesium, copper, silver and diamond, The two-component curable composition set according to any one of [1] to [4].
• the two-component curable composition set according to any one of [1] to [5].
• the thermal conductivity of the mixture of the first agent and the second agent after curing, measured according to ASTM D5470, is 1.0 W / mk or more.
• [11] The electronic component, the cured product according to [10], and the housing for accommodating the electronic component and the cured product are provided. The electronic component and the housing are in contact with each other via the cured product. Electronics.
• a two-component curing type composition set that does not require moisture for the curing reaction, has high uniform curing property, does not require a platinum catalyst, and is less likely to cause curing inhibition, and the two-component curing type composition. It is possible to provide a cured product or a heat conductive cured product obtained from a set, and an electronic device provided with the heat conductive cured product.
• the present embodiment an embodiment of the present invention (hereinafter, referred to as “the present 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.
• the two-component curable composition set includes an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group, a first agent containing a thermally conductive filler B1, and an amino-modified organopoly having an amino group-containing group. It comprises a second agent containing siloxane A2 and a thermally conductive filler B2.
• the conventional two-component curable silicone composition utilizes a condensation reaction or an addition reaction.
• the condensation reaction using an organopolysiloxane having a hydroxyl group, an alkoxy group, or the like requires moisture for curing, generates a reaction by-product (outgas), and has a high shrinkage rate.
• an addition reaction using an organopolysiloxane having a vinyl group and an organopolysiloxane having a hydrosilyl group an addition reaction catalyst such as a platinum catalyst has an excellent shrinkage rate, does not generate outgas, and does not require moisture. It is necessary, and there is a problem that curing inhibition occurs depending on the coexisting compound.
• an addition reaction catalyst such as a platinum catalyst is not required. It is possible to provide a two-component curing type composition set which does not cause curing inhibition, does not require moisture for curing, and does not generate outgas.
• both the first agent and the second agent have an organopolysiloxane having a vinyl group at least at the terminal or side chain and an organopolysiloxane having a hydrosilyl group at least at the terminal or side chain. It is preferable that it does not contain polysiloxane.
• the first agent contains an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and a thermally conductive filler B1, and optionally contains additives such as polydimethylsiloxane C, organosilane D, and a colorant E. But it may be.
• Epoxy-modified organopolysiloxane A1 The epoxy-modified organopolysiloxane A1 of the present embodiment has a substituent (epoxy group-containing group) having an epoxy group at the terminal or side chain.
• An organopolysiloxane having an epoxy group is a substituent in which at least a part of R of the Si—R moiety (where R is a substituted or unsubstituted monovalent hydrocarbon group) in the organopolysiloxane molecule has an epoxy group. Is what.
• the epoxy group-containing group is not particularly limited, and examples thereof include an aliphatic epoxy group represented by the following formula (a11) and an alicyclic epoxy group represented by the following formula (a12).
• an aliphatic epoxy group such as a glycidyl group is preferable from the viewpoint of curing reactivity
• an alicyclic epoxy group such as an ethylcyclohexene oxide group is preferable from the viewpoint of increasing the glass transition point of the obtained cured product.
• the epoxy-modified organopolysiloxane A1 may have both an aliphatic epoxy group and an alicyclic epoxy group.
• R 1 represents an alkyl group having 1 to 6 carbon atoms.
• the epoxy-modified organopolysiloxane A1 may have any of a linear structure, a branched structure, and a cyclic structure, and may be a combination of a linear structure and a cyclic structure or a combination of a branched structure and a cyclic structure. It may have a structure. Among these, a linear structure is preferable from the viewpoint of handleability as a liquid, and a branched structure is preferable from the viewpoint of mechanical properties of the obtained cured product.
• the bonding position of the epoxy group-containing group in the epoxy-modified organopolysiloxane A1 is not particularly limited, and may be a terminal or a side chain, or may be a terminal and a side chain.
• the epoxy-modified organopolysiloxane A1 has, for example, a structural unit represented by the following general formula (a1-1) or (a1-2).
• the epoxy-modified organopolysiloxane A1 has, for example, a terminal structure represented by the following general formula (a1-3) (where n is 1 or more). ..
• examples of the structural unit to which the epoxy group-containing group is not bonded include a structural unit represented by the following general formula (a1-4).
• the structural unit of the epoxy-modified organopolysiloxane A1 is not limited to the following, and for example, when it has a branched structure, it may have a branched structural unit, or when it has a cyclic structure. Does not have to have a terminal structure.
• X independently represents an epoxy group-containing group
• R 2 independently represents a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or a polyether group.
• n indicates an integer from 0 to 3.
• the substituted or unsubstituted hydrocarbon group represented by R2 is not particularly limited, and for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and the like.
• Alkyl groups such as decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, trill group, xylyl group and naphthyl group; benzyl group, 2-phenylethyl group and 2-phenylpropyl Aralkyl groups such as groups; examples thereof include alkyl halide groups such as chloromethyl group, 3,3,3-trifluoropropyl group and 3-chloropropyl group.
• the polyether group represented by R 2 is not particularly limited, but for example, a polyethylene glycol group (-(C 2 H 4 O) l -CH 2 H 5 ,-(C 2 H 4 O) l -CH. 2 H 4 OH), polypropylene glycol group (-(C 3 H 6 O) l -CH 3 H 7 ,-(C 3 H 6 O) l -CH 3 H 6 OH), polyethylene glycol-polypropylene glycol copolymer group Can be mentioned.
• l represents an integer of 2 to 1000.
• an organopolysiloxane having a linear structure having an epoxy group-containing group in the side chain is preferable.
• the functional group equivalent of the epoxy group of the epoxy-modified organopolysiloxane A1 is preferably 100 to 11000 g / mol, more preferably 200 to 6000 g / mol, and further preferably 250 to 5000 g / mol.
• the functional group equivalent of the epoxy group is within the above range, the reactivity between the first agent and the second agent tends to be further improved, and the uniform reactivity tends to be further improved.
• the viscosity of the epoxy-modified organopolysiloxane A1 at 25 ° C. is preferably 5 to 15000 mm 2 / s, more preferably 5 to 12000 mm 2 / s, and even more preferably 5 to 10000 mm 2 / s.
• the handleability as a two-component curing type composition set tends to be further improved.
• the thermally conductive filler B1 is, for example, a filler having a thermal conductivity of 10 W / m ⁇ K or more.
• the heat conductive filler B1 is not particularly limited, and for example, aluminum oxide (hereinafter, also referred to as “alumina”), aluminum nitride, silica, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, and metallic aluminum. , Magnesium oxide, diamond, carbon, indium, gallium, copper, silver, iron, nickel, gold, tin, metallic silicon and the like.
• heat conductive filler B1 it is preferable to contain at least one selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metallic aluminum, magnesium oxide, copper, silver and diamond, and alumina. Is more preferable.
• a heat conductive filler B1 By using such a heat conductive filler B1, the filling property tends to be improved, and the thermal conductivity of the obtained cured product tends to be further improved.
• These heat conductive fillers B1 may be used alone or in combination of two or more.
• the average particle size of the heat conductive filler B1 is preferably 0.1 to 120 ⁇ m, more preferably 0.1 to 60 ⁇ m. When the average particle size of the heat conductive filler B1 is within the above range, the fluidity, dispersibility, and filling property tend to be further improved.
• the thermally conductive filler B1 may be used by mixing fillers having different average particle sizes.
• a heat conductive filler (B1-1) having an average particle size of 40 to 50 ⁇ m and a heat conductive filler (B1-2) having an average particle size of 1 to 10 ⁇ m in combination the content of the heat conductive filler (B1-1) is preferably 40 to 80% by mass, more preferably 50 to 70% by mass, based on the total amount of the heat conductive filler B1.
• the content of the heat conductive filler (B1-1) is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, based on the total amount of the heat conductive filler B1.
• the average particle size in this embodiment means D50 (median diameter).
• the content of the heat conductive filler B1 is preferably 400 to 3000 parts by weight, more preferably 600 to 2800 parts by weight, still more preferably, based on 100 parts by weight of the epoxy-modified organopolysiloxane A1. Is 700 to 2600 parts by weight.
• the content of the heat conductive filler is 400 parts by weight or more with respect to the content of 100 parts by weight of the epoxy-modified organopolysiloxane A1
• the thermal conductivity of the obtained cured product becomes better and 3000 parts by weight. If it is the following, the decrease in fluidity can be suppressed more effectively and the coatability can be ensured.
• Polydimethylsiloxane C Polydimethylsiloxane C can be added to adjust the viscosity of the first agent and the hardness of the resulting cured product.
• the viscosity of the polydimethylsiloxane is not particularly limited, and a plurality of types of polydimethylsiloxane having different viscosities may be used in combination.
• the content of polydimethylsiloxane C is preferably 0 to 80 parts by weight with respect to 100 parts by weight of the total of the epoxy-modified organopolysiloxane A1 and polydimethylsiloxane.
• Organosilane D can be added to adjust the wettability of the thermally conductive filler B1 and the epoxy-modified organopolysiloxane A1.
• the organosilane is not particularly limited, but for example, an organosilane represented by the following general formula (d) is preferably used.
• R 3 independently represents an alkyl group having 1 to 15 carbon atoms
• R 4 independently represents an unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms.
• R 5 independently represent an alkyl group having 1 to 6 carbon atoms
• a is an integer of 1 to 3
• b is an integer of 0 to 2
• a + b is an integer of 1 to 3. .
• the alkyl group having 1 to 15 carbon atoms represented by R 3 is not particularly limited, and is, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a nonyl group, a decyl group, a dodecyl group, or a tetradecyl. Examples thereof include a group, a 3,3,3-trifluoropropyl group, a 2- (perfluorobutyl) ethyl group, a 2- (perfluorooctyl) ethyl group and the like. Of these, R 3 is preferably an alkyl group having 6 to 12 carbon atoms.
• the unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms shown by R4 is not particularly limited, but is not particularly limited, and is, for example, an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a trill group; 2 Examples thereof include an aralkyl group such as a phenylethyl group and a 2-methyl-2-phenylethyl group; and a halogenated hydrocarbon group such as a p-chlorophenyl group.
• the alkyl group having 1 to 6 carbon atoms indicated by R 5 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Of these, R5 is preferably a methyl group or an ethyl group.
• A is an integer of 1 to 3, preferably 1.
• b is an integer of 0 to 2, preferably 0.
• a + b is an integer of 1 to 3, preferably 1.
• the content of the organosilane D is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the epoxy-modified organopolysiloxane A1. Is. When the content of organosilane D is within the above range, the wettability can be effectively improved.
• the colorant E is not particularly limited, and examples thereof include any pigment.
• the content of the colorant E is not particularly limited, and is preferably 0.05 to 0.2 parts by weight with respect to a total of 100 parts by weight of the first agent and the second agent described later.
• the second agent contains an amino-modified organopolysiloxane A2 having an amino group-containing group and a thermally conductive filler B2, and may contain additives such as polydimethylsiloxane C, organosilane D, and a colorant E, if necessary. good.
• the amino-modified organopolysiloxane A2 of the present embodiment has a substituent (amino group-containing group) having an amino group at the terminal or side chain.
• An organopolysiloxane having an amino group is a substituent in which at least a part of R of the Si—R moiety (where R is a substituted or unsubstituted monovalent hydrocarbon group) in the organopolysiloxane molecule has an amino group. Is what.
• the amino group-containing group is not particularly limited, and examples thereof include an amino group represented by the following formula (a21). Such an amino group-containing group may be a primary amino group or a secondary amino group, and among these, a primary amino group in which R6 is a hydrogen atom is preferable.
• R 6 indicates a hydrogen atom or an alkyl group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with an amino group
• R 7 indicates an alkyl group having 1 to 6 carbon atoms.
• R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with an amino group.
• the amino group represented by the formula (a21) has a primary amino group at the terminal such as a 3-aminopropyl group.
• the amino group represented by the formula (a21) has a secondary amino group.
• the amino group represented by the formula (a21) is a primary amino group such as an aminoethylaminopropyl group. It may be a group having a secondary amino group, a group having a plurality of primary amino groups, or a group having a plurality of secondary amino groups.
• the amino-modified organopolysiloxane A2 may have any of a linear structure, a branched structure, and a cyclic structure, and may be a combination of a linear structure and a cyclic structure or a combination of a branched structure and a cyclic structure. It may have a structure. Among these, a linear structure is preferable from the viewpoint of handleability as a liquid, and a branched structure is preferable from the viewpoint of mechanical properties of the obtained cured product.
• the bonding position of the amino group-containing group in the amino-modified organopolysiloxane A2 is not particularly limited, and may be a terminal or a side chain, or may be a terminal and a side chain.
• the amino-modified organopolysiloxane A2 has, for example, a structural unit represented by the following general formula (a2-1) or (a2-2).
• the amino group-containing group is contained at the terminal, the amino-modified organopolysiloxane A2 has, for example, a terminal structure represented by the following general formula (a2-3) (provided that m is 1 or more). ..
• examples of the structural unit to which the amino group-containing group is not bonded include a structural unit represented by the following general formula (a2-4).
• the structural unit of the amino-modified organopolysiloxane A2 is not limited to the following, and for example, when it has a branched structure, it may have a branched structural unit, or when it has a cyclic structure. Does not have to have a terminal structure.
• Y independently represents an amino group-containing group
• R 8 independently represents a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms
• m is 0 to 3. Indicates an integer of.
• the substituted or unsubstituted hydrocarbon group represented by R8 is not particularly limited, and for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and the like.
• Alkyl groups such as decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, trill group, xylyl group and naphthyl group; benzyl group, 2-phenylethyl group and 2-phenylpropyl Aralkyl groups such as groups; examples thereof include alkyl halide groups such as chloromethyl group, 3,3,3-trifluoropropyl group and 3-chloropropyl group.
• the amino-modified organopolysiloxane A2 is an organopolysiloxane having a linear structure having an amino group-containing group at the terminal or side chain, or having a hydroxyl group at the terminal and having an amino group-containing group in the side chain.
• Organopolysiloxanes with a linear structure are preferred.
• the functional group equivalent of the amino group of the amino-modified organopolysiloxane A2 is preferably 100 to 8000 g / mol, more preferably 200 to 6000 g / mol, more preferably 300 to 4000 g / mol, and even more preferably. Is 300 to 2000 g / mol.
• the functional group equivalent of the amino group is within the above range, the reactivity between the first agent and the second agent tends to be further improved, and the uniform reactivity tends to be further improved.
• the viscosity of the amino-modified organopolysiloxane A2 at 25 ° C. is preferably 5 to 2000 mm 2 / s, more preferably 5 to 1750 mm 2 / s, and even more preferably 5 to 1500 mm 2 / s.
• the handleability as a two-component curing type composition set tends to be further improved.
• the amino-modified organopolysiloxane A2 further has a hydroxyl group-containing group in which a hydroxyl group is bonded to a silicon atom.
• the bonding position of the hydroxyl group-containing group is not particularly limited, and may be a terminal or a side chain, or may be a terminal and a side chain.
• amino-modified organopolysiloxane A2 having a linear structure having an amino group-containing group at both ends is preferable.
• the heat conductive filler B2 is, for example, a filler having a thermal conductivity of 10 W / m ⁇ K or more, and examples thereof include the same ones as the heat conductive filler B1. Among these, it is preferable to contain at least one selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metallic aluminum, magnesium oxide, copper, silver and diamond.
• the filling property tends to be improved, and the thermal conductivity of the obtained cured product tends to be further improved.
• These thermally conductive fillers B2 may be used alone or in combination of two or more.
• the average particle size and the content of the heat conductive filler B2 can be the same as those of the heat conductive filler B1, and the description regarding the heat conductive filler B1 is applied by replacing it with the heat conductive filler B2. be able to.
• the types and contents of the polydimethylsiloxane C, the organosilane D, and the colorant E that can be contained in the second agent are the same as those of the first agent described above, and the description regarding these in the first agent is the second. Since it can be read and applied as related to a drug, a duplicate description is omitted here.
• the heat conductive filler, polydimethylsiloxane, organosilane, and colorant as the second agent and the heat conductive filler, polydimethylsiloxane, organosilane, and colorant as the first agent are of the same type. It may be different.
• the ratio of the epoxy-modified organopolysiloxane A1 in the first agent and the amino-modified organopolysiloxane A2 in the second agent is the epoxy-modified organopolysiloxane A1 in the first agent. It can be appropriately set according to the content of the epoxy group and the content of the amino group of the amino-modified organopolysiloxane A2 in the second agent.
• Epoxide group content Epoxide-modified organopolysiloxane A1 content / functional group equivalent
• Amino group content Amino-modified organopolysiloxane A2 content / functional group equivalent
• the epoxy group content / amino group content satisfied by the combination of the first agent and the second agent is preferably 70/30 to 10/90, and more preferably 55/45 to 20/80.
• the ratio of the epoxy group content and the amino group content is within the above range, uniform reactivity is improved and a cured product having a sufficiently crosslinked structure can be obtained.
• the thermal conductivity of the mixture of the first agent and the second agent after curing is preferably 1.0 W / mk or more, more preferably 2.0 W / mk or more.
• Such a two-component curing type composition set of the present embodiment can be suitably used as a heat conductive heat dissipation material.
• the cured product according to the present embodiment can be obtained, for example, by mixing the first agent and the second agent in the above-mentioned two-component curing type composition set. More specifically, the cured product (crosslinked cured product) is the epoxy group of the epoxy-modified organopolysiloxane A1 contained in the first agent in the mixture obtained by mixing the first agent and the second agent.
• the above-mentioned cured product is obtained by advancing the addition reaction of the amino-modified organopolysiloxane A2 contained in the two agents with the amino group to form a three-dimensional network structure having a cross-linking bond.
• the cured product of the present embodiment may be formed into a desired shape after mixing the first agent and the second agent. Further, since the cured product according to the present embodiment contains a heat conductive filler, it can be suitably used as a heat conductive heat radiating material.
• a mixer such as a roll mill, a kneader, a Banbury mixer, a line mixer, etc. is used.
• the doctor blade method is preferable as the molding method, but an extrusion method, a press method, a calendar roll method, or the like can be used depending on the viscosity of the resin.
• the reaction conditions in the progress of the addition reaction are not particularly limited, but are usually carried out from room temperature (for example, 25 ° C.) to 150 ° C. for 0.1 to 24 hours.
• the mixing ratio of the first agent and the second agent can be appropriately set according to the type of the first agent and the second agent to be used and the purpose of use.
• the first agent: the second agent 1.5 in terms of volume ratio. : 1.0 to 1.0: 1.5, and may be 1.0: 1.0.
• the electronic device of the present embodiment includes an electronic component, the cured product, and a housing for accommodating the electronic component and the cured product, and the electronic component and the housing are in contact with each other via the cured product.
• the electronic components are not particularly limited, and examples thereof include motors, battery packs, circuit boards sold in in-vehicle power supply systems, power transistors, electronic components that generate heat such as microprocessors, and the like.
• the metal housing is not particularly limited, and examples thereof include a heat sink configured for heat dissipation and heat absorption.
• ⁇ A1 component organopolysiloxane> A1-1: DOWNSIL BY 16-839 Fluid (manufactured by Dow Toray Co., Ltd., trade name), epoxy-modified organopolysiloxane, viscosity at 25 ° C.: 6000 mm 2 / s, functional group equivalent of epoxy group: 3700 g / mol, fat Cyclic type (ethylcyclohexene oxide group), epoxy group bond position: side chain A1-2: DOWNSIL BY 8411 Fluid (manufactured by Dow Toray Co., Ltd., trade name), epoxy-modified organopolysiloxane, viscosity at 25 ° C: 8000 mm 2 / S, Epoxide group functional group equivalent: 3300 g / mol, aliphatic type (glycidyl group), epoxy group bond position: side chain A1-3: DOWNSIL SE 1885A (manufactured by Dow Toray Co., Ltd., trade name)
• ⁇ B1 component thermally conductive filler>
• B1-1 Spherical alumina, average particle size: 45 ⁇ m, DAW45S (manufactured by Denka Co., Ltd., trade name), thermal conductivity 35 W / mK
• B1-2 Spherical alumina, average particle size: 5 ⁇ m, DAW05 (manufactured by Denka Co., Ltd., trade name), thermal conductivity 35 W / mK
• C1 Regino Black # 442 (Regino Color Industry Co., Ltd., product name)
• ⁇ A2 component organopolysiloxane> A2-1: DOWNSIL BY 16-213 (manufactured by Dow Toray Co., Ltd., trade name), amino-modified organopolysiloxane, viscosity at 25 ° C.: 60 mm 2 / s, functional group equivalent of amino group: 2700 g / mol, primary amine (3-Aminopropyl group), Amino group bond position: Side chain A2-2: DOWNSIL BY 16-853U (manufactured by Dow Toray Co., Ltd., trade name), amino-modified organopolysiloxane, viscosity at 25 ° C.
• ⁇ B2 component thermally conductive filler>
• B2-1 Spherical alumina, average particle size: 45 ⁇ m
• DAW45S manufactured by Denka Co., Ltd., trade name
• B2-2 Spherical alumina, average particle size: 5 ⁇ m
• DAW05 manufactured by Denka Co., Ltd., product name
• the thermal conductivity of the heat conductive cured product was measured by a method compliant with ASTM D5470 using a resin material thermal resistance measuring device manufactured by Hitachi Technology Co., Ltd. Specifically, the mixture obtained by mixing the first agent and the second agent at the volume ratios described in each Example and Comparative Example was prepared into thicknesses of 0.2 mm, 0.5 mm and 1.0 mm, respectively. Molding was performed, and each of the obtained molded products was held at 25 ° C. for 24 hours to proceed with the curing reaction to obtain a thermally conductive cured product. The thermal resistance values of the obtained heat conductive cured products were measured in a measurement area of 10 mm ⁇ 10 mm. The slope of a straight line obtained with the thermal resistance value as the vertical axis and the thickness of the thermally conductive cured product as the horizontal axis was calculated and used as the thermal conductivity of the thermally conductive cured product.
• the average particle size of the thermally conductive filler was measured using "Laser Diffraction Particle Size Distribution Measuring Device SALD-20" (trade name) manufactured by Shimadzu Corporation.
• SALD-20 "Laser Diffraction Particle Size Distribution Measuring Device SALD-20” (trade name) manufactured by Shimadzu Corporation.
• 50 ml of pure water and 5 g of the heat conductive filler powder to be measured were added to a glass beaker, the mixture was stirred with a spatula, and then dispersed with an ultrasonic cleaner for 10 minutes.
• a solution of the heat conductive filler powder subjected to the dispersion treatment was added drop by drop to the sampler part of the apparatus using a dropper, and the measurement was performed when the absorbance became stable.
• the particle size distribution is calculated from the data of the light intensity distribution of the diffraction / scattering holes by the particles detected by the sensor.
• the average particle size is obtained by multiplying the measured particle size value by the relative particle amount (difference%) and dividing by the total relative particle amount (100%).
• the average particle size is the average diameter of the particles, and can be obtained as the cumulative weight average value D50 (or median diameter) which is the maximum value or the peak value. In addition, D50 has the particle diameter having the largest appearance rate.
• the two-component curable composition set of the present invention of Examples 1 to 6 had good mixability and uniform reactivity, and was excellent in storage stability.
• Comparative Example 1 is an addition reaction type two-component curing type composition set using a platinum catalyst, the catalyst was inactivated by high temperature storage and the storage stability was inferior.
• Comparative Example 2 was a mixture of epoxy-modified organopolysiloxane and carbinol-modified organopolysiloxane, but a cured product was not formed and could not be evaluated.
• Comparative Example 3 was a mixture of epoxy-modified organopolysiloxane and carboxyl-modified organopolysiloxane, but a cured product was not formed and could not be evaluated.
• Examples 5 and 6 had better uniform reactivity than Examples 1 and 3 under substantially the same conditions except that the type of the amino-modified organopolysiloxane of the second agent was different.
• Examples 5 and 6 are different from Examples 1 and 3 in that amino-modified organopolysiloxanes modified with OH at both ends are used as the second agent. From this, it was confirmed that the amino-modified organopolysiloxane used is more preferably double-ended OH-modified.
• composition for a two-component curable heat conductive grease of the present invention heats a heat conductive cured product, particularly a heating element and a metal housing, by mixing and curing the first agent and the second agent. It has industrial applicability as a material for thermally conductive grease used by binding to each other.

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• 2021
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