JP7629935B2 - Two-component curing composition set, thermally conductive cured product, and electronic device - Google Patents
Two-component curing composition set, thermally conductive cured product, and electronic device Download PDFInfo
- Publication number
- JP7629935B2 JP7629935B2 JP2022555438A JP2022555438A JP7629935B2 JP 7629935 B2 JP7629935 B2 JP 7629935B2 JP 2022555438 A JP2022555438 A JP 2022555438A JP 2022555438 A JP2022555438 A JP 2022555438A JP 7629935 B2 JP7629935 B2 JP 7629935B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- thermally conductive
- epoxy
- agent
- modified organopolysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 54
- 229920001296 polysiloxane Polymers 0.000 claims description 112
- 239000003795 chemical substances by application Substances 0.000 claims description 68
- 239000011231 conductive filler Substances 0.000 claims description 49
- 125000003277 amino group Chemical group 0.000 claims description 36
- 125000003700 epoxy group Chemical group 0.000 claims description 31
- 125000000524 functional group Chemical group 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 230000017525 heat dissipation Effects 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 description 50
- -1 polydimethylsiloxane Polymers 0.000 description 25
- 239000002245 particle Substances 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 238000007259 addition reaction Methods 0.000 description 14
- 230000009257 reactivity Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 150000001282 organosilanes Chemical class 0.000 description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 239000013523 DOWSIL™ Substances 0.000 description 9
- 229920013731 Dowsil Polymers 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000010943 off-gassing Methods 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- KFUUFPBQCHRNNT-UHFFFAOYSA-N 6-ethyl-7-oxabicyclo[4.1.0]heptane Chemical group C1CCCC2OC21CC KFUUFPBQCHRNNT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000570 polyether Chemical group 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZKVLEFBKBNUQHK-UHFFFAOYSA-N helium;molecular nitrogen;molecular oxygen Chemical compound [He].N#N.O=O ZKVLEFBKBNUQHK-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、二液硬化型組成物セット、熱伝導性硬化物及び電子機器に関する。 The present invention relates to a two-component curing composition set, a thermally conductive cured product, and an electronic device.
室温硬化型の液状シリコーンゴムは、広い温度範囲で安定した性能を発揮することから、パソコンのＣＰＵ（中央処理装置）や自動車のバッテリー。ＬＥＤデバイス等、電気・電子機器の信頼性を向上させる目的で使用される。具体的には各電子基材の封止材やシール材、ポッティング材、コーティング材、放熱材として使用されている。 Room temperature curing liquid silicone rubber exhibits stable performance over a wide temperature range, and is therefore used to improve the reliability of electrical and electronic equipment, such as computer CPUs (central processing units), car batteries, and LED devices. Specifically, it is used as an encapsulant, sealing material, potting material, coating material, and heat dissipation material for various electronic substrates.
室温硬化型の液状シリコーンゴムは、主に一液タイプと二液タイプに分類され、二液タイプはさらに縮合反応型と付加反応型に分けられる。Room temperature curing liquid silicone rubber is mainly classified into one-component and two-component types, and the two-component type is further divided into condensation reaction type and addition reaction type.
縮合反応型は、空気中の湿気により組成物が硬化することで、硬化途上で接触する各種基材に対して優れた接着性を発揮することができる。特に、チタン系の縮合反応用触媒により脱アルコール縮合して硬化する組成物は、硬化時に不快臭の発生や金属類の腐食がないことから、電気・電子機器等のシール材やコーティング材として好適である。Condensation reaction types are cured by the moisture in the air, and can exhibit excellent adhesion to various substrates that they come into contact with during the curing process. In particular, compositions that cure by dealcoholization condensation using a titanium-based condensation reaction catalyst do not emit unpleasant odors or corrode metals during curing, making them ideal as sealing or coating materials for electrical and electronic devices.
一方、縮合反応型は、空気中の湿気と接触する部分から徐々に硬化するために、均一硬化するためには長い時間が必要であり、また、硬化途上でアウトガスを発生させることから、密閉される用途には適さないという問題がある。On the other hand, condensation reaction types cure gradually from the parts that come into contact with moisture in the air, so they require a long time to cure uniformly, and they also generate outgassing during the curing process, making them unsuitable for sealed applications.
付加反応型は、硬化による収縮率が低く、均一反応性が高く、また、アウトガスが発生しないことから、電気・電子機器等の封止材や放熱材として好適である。 The addition reaction type has a low shrinkage rate due to curing, high uniform reactivity, and does not generate outgassing, making it ideal as a sealing material or heat dissipation material for electrical and electronic devices.
一方、付加反応型は、貴金属である白金触媒が必要であるが、白金触媒は温度に敏感であり、高温環境下での輸送により触媒活性が失活する問題がある。また、基材上に窒素含有化合物、硫黄含有化合物、リン含有化合物、スズ含有化合物、硫黄、ハンダフラックス等の硬化阻害物質やアルコール、水、カルボン酸などにより硬化不良を生じるという問題がある。On the other hand, the addition reaction type requires a platinum catalyst, which is a precious metal, but platinum catalysts are sensitive to temperature, and there is a problem that their catalytic activity is lost when transported in a high-temperature environment. There is also a problem that poor curing occurs due to the presence of curing inhibitors such as nitrogen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, tin-containing compounds, sulfur, solder flux, etc. on the substrate, as well as alcohol, water, carboxylic acids, etc.
上記のとおり、縮合反応型と付加反応型には、それぞれに長所と短所があり、用途や目的によって使い分がなされ、また、短所を克服する改良検討が報告されている。As mentioned above, condensation reaction and addition reaction types each have their own advantages and disadvantages, and are used depending on the application and purpose. Improvements to overcome the disadvantages have also been reported.
例えば、特許文献１では、アルコキシ基を含有するオルガノポリシロキサンと低級アルケニル基を含有するオルガノポリシロキサンの混合物、ケイ素原紙結合水素原子を含有するオルガノポリシロキサン、アルコキシシラン、ヒドロシリル化反応用触媒からなる組成物により、硬化阻害を生じることなく均一に硬化し、優れた接着性を有する組成物が記載されている。For example, Patent Document 1 describes a composition that cures uniformly without cure inhibition and has excellent adhesive properties, the composition comprising a mixture of an organopolysiloxane containing an alkoxy group and an organopolysiloxane containing a lower alkenyl group, an organopolysiloxane containing silicon-bonded hydrogen atoms, an alkoxysilane, and a catalyst for a hydrosilylation reaction.
特許文献２では、アルケニル基を含有するオルガノポリシロキサンと、オルガノハイドロジェンポリシロキサン、白金触媒、接着性付与剤からなる組成物により、硬化阻害物質の影響を受けにくく、優れた接着性を有する付加反応型シリコーンゴム組成物が記載されている。Patent Document 2 describes an addition reaction type silicone rubber composition that is less susceptible to the effects of cure inhibitors and has excellent adhesive properties, due to the composition consisting of an organopolysiloxane containing alkenyl groups, an organohydrogenpolysiloxane, a platinum catalyst, and an adhesion promoter.
また、特許文献３、４では、上記縮合反応型や付加反応型以外のシリコーン系組成物として、シリコーン変性エポキシ樹脂と反応性官能基を有するシリコーン化合物による樹脂組成物が記載されている。Furthermore, Patent Documents 3 and 4 describe resin compositions made from silicone-modified epoxy resins and silicone compounds having reactive functional groups as silicone-based compositions other than the above-mentioned condensation reaction type and addition reaction type.
二液縮合反応型と二液付加反応型の液状シリコーンゴムは、上記のとおり、それぞれに長所と短所があり、両者の短所を克服した室温硬化型の液状シリコーンゴムの開発が望まれていた。As mentioned above, two-component condensation reaction type and two-component addition reaction type liquid silicone rubbers each have their own advantages and disadvantages, and there was a need to develop a room-temperature curing liquid silicone rubber that overcomes the disadvantages of both.
本発明は、上記問題点に鑑みてなされたものであり、硬化反応に湿気が不要で、均一硬化性が高く、また、白金触媒を必要とせず、硬化阻害が生じにくい二液硬化型組成物セット、及び当該二液硬化型組成物セットから得られる硬化物または熱伝導性硬化物、並びに当該熱伝導性硬化物を備える電子機器を提供することを目的とする。The present invention has been made in consideration of the above problems, and aims to provide a two-component curing composition set that does not require moisture for the curing reaction, has high uniform curing properties, does not require a platinum catalyst, and is less susceptible to curing inhibition, as well as a cured product or thermally conductive cured product obtained from the two-component curing composition set, and an electronic device equipped with the thermally conductive cured product.
すなわち、本発明は以下のとおりである。
〔１〕
エポキシ基含有基を有するエポキシ変性オルガノポリシロキサンＡ１、及び熱伝導性フィラーＢ１を含む第一剤と、
アミノ基含有基を有するアミノ変性オルガノポリシロキサンＡ２、及び熱伝導性フィラーＢ２を含む第二剤と、を備える、
二液硬化型組成物セット。
〔２〕
前記エポキシ変性オルガノポリシロキサンＡ１の１分子中におけるエポキシ基の官能基当量が、１００～１１０００ｇ／ｍｏｌである、
〔１〕に記載の二液硬化型組成物セット。
〔３〕
前記アミノ変性オルガノポリシロキサンＡ２の１分子中におけるアミノ基の官能基当量が、１００～８０００ｇ／ｍｏｌである、
〔１〕又は〔２〕に記載の二液硬化型組成物セット。
〔４〕
前記第二剤における前記アミノ変性オルガノポリシロキサンＡ２が、両末端に水酸基含有基を有する、
〔１〕～〔３〕のいずれか一項に記載の二液硬化型組成物セット。
〔５〕
前記熱伝導性フィラーＢ１及び熱伝導性フィラーＢ２が、熱伝導率が１０Ｗ／ｍ・Ｋ以上を示す、酸化アルミニウム、窒化アルミ、窒化ホウ素、窒化ケイ素、酸化亜鉛、水酸化アルミニウム、金属アルミニウム、酸化マグネシウム、銅、銀、ダイヤモンドからなる群より選ばれる少なくとも一種以上を含む、
〔１〕～〔４〕のいずれか一項に記載の二液硬化型組成物セット。
〔６〕
少なくとも末端又は側鎖にビニル基を有するオルガノポリシロキサンと、少なくとも末端又は側鎖にヒドロシリル基を有するオルガノポリシロキサンを含まない前記第一剤、及び、
少なくとも末端又は側鎖にビニル基を有するオルガノポリシロキサンと、少なくとも末端又は側鎖にヒドロシリル基を有するオルガノポリシロキサンを含まない前記第二剤、を備える、
〔１〕～〔５〕のいずれか一項に記載の二液硬化型組成物セット。
〔７〕
ＡＳＴＭ Ｄ５４７０に準拠して測定した、前記第一剤と前記第二剤の混合物の硬化後の熱伝導率が、１．０Ｗ／ｍｋ以上である、
〔１〕～〔６〕のいずれか一項に記載の二液硬化型組成物セット。
〔８〕
熱伝導性放熱材料として使用される、
〔１〕～〔７〕のいずれか一項に記載の二液硬化型組成物セット。
〔９〕
〔１〕～〔８〕のいずれか一項に記載の二液硬化型組成物セットにおける、第一剤と第二剤の混合物から得られる、
硬化物。
〔１０〕
熱伝導性放熱材料として使用される、
〔９〕に記載の硬化物。
〔１１〕
電子部品と、〔１０〕に記載の硬化物と、前記電子部品及び前記硬化物を収容する筐体と、を備え、
前記電子部品及び前記筐体が、前記硬化物を介して接触している、
電子機器。
That is, the present invention is as follows.
[1]
A first agent including an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and a thermally conductive filler B1;
A second agent including an amino-modified organopolysiloxane A2 having an amino group-containing group and a thermally conductive filler B2;
Two-part curing composition set.
[2]
the functional group equivalent weight of the epoxy group in one molecule of the epoxy-modified organopolysiloxane A1 is 100 to 11,000 g/mol;
The two-component curing composition set according to [1].
[3]
the functional group equivalent weight of the amino group in one molecule of the amino-modified organopolysiloxane A2 is 100 to 8000 g/mol;
The two-component curing composition set according to [1] or [2].
[4]
The amino-modified organopolysiloxane A2 in the second agent has hydroxyl group-containing groups at both ends.
The two-component curing composition set according to any one of [1] to [3].
[5]
The thermally conductive filler B1 and the thermally conductive filler B2 each 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, each of which has a thermal conductivity of 10 W/m·K or more.
The two-component curing composition set according to any one of [1] to [4].
[6]
The first agent does not contain an organopolysiloxane having at least a vinyl group at the end or in a side chain, and an organopolysiloxane having at least a hydrosilyl group at the end or in a side chain; and
The second agent is provided with an organopolysiloxane having at least a vinyl group at the end or in a side chain, and the second agent does not include an organopolysiloxane having at least a hydrosilyl group at the end or in a side chain.
The two-component curing composition set according to any one of [1] to [5].
[7]
The thermal conductivity of the mixture of the first agent and the second agent after curing, measured in accordance with ASTM D5470, is 1.0 W/mK or more.
The two-component curing composition set according to any one of [1] to [6].
[8]
Used as a thermally conductive heat dissipation material,
The two-component curing composition set according to any one of [1] to [7].
[9]
[1] to [8], wherein the first agent and the second agent are mixed together to obtain a two-component curing composition set according to any one of [1] to [8].
Hardened material.
[10]
Used as a thermally conductive heat dissipation material,
The cured product according to [9].
[11]
An electronic component, the cured product according to [10], and a housing that accommodates the electronic component and the cured product,
The electronic component and the housing are in contact with each other via the cured product.
Electronic devices.
本発明によれば、硬化反応に湿気が不要で、均一硬化性が高く、また、白金触媒を必要とせず、硬化阻害が生じにくい二液硬化型組成物セット、及び当該二液硬化型組成物セットから得られる硬化物または熱伝導性硬化物、並びに当該熱伝導性硬化物を備える電子機器を提供することが可能となる。 According to the present invention, it is possible to provide a two-component curing composition set that does not require moisture for the curing reaction, has high uniform curing properties, does not require a platinum catalyst, and is less susceptible to curing inhibition, as well as a cured product or thermally conductive cured product obtained from the two-component curing composition set, and an electronic device equipped with the thermally conductive cured product.
以下、本発明の実施形態（以下、「本実施形態」という。）について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。An embodiment of the present invention (hereinafter referred to as the "present embodiment") is described in detail below. However, the present invention is not limited to the following embodiment, and various modifications are possible without departing from the gist of the present invention.
［二液硬化型組成物セット］
本実施形態に係る二液硬化型組成物セットは、エポキシ基含有基を有するエポキシ変性オルガノポリシロキサンＡ１、及び熱伝導性フィラーＢ１を含む第一剤と、アミノ基含有基を有するアミノ変性オルガノポリシロキサンＡ２、及び熱伝導性フィラーＢ２を含む第二剤と、を備える。
[Two-component curing composition set]
The two-component curing composition set according to this embodiment includes a first agent containing an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and a thermally conductive filler B1, and a second agent containing an amino-modified organopolysiloxane A2 having an amino group-containing group and a thermally conductive filler B2.
従来の二液硬化型のシリコーン組成物は、縮合反応や付加反応を利用する。しかしながら、水酸基やアルコキシ基等を有するオルガノポリシロキサンを用いた縮合反応は、硬化に湿気が必要であり、反応副生成物（アウトガス）が発生する上、収縮率が高いという問題がある。一方で、ビニル基を有するオルガノポリシロキサンとヒドロシリル基を有するオルガノポリシロキサンなどを用いた付加反応では、収縮率に優れアウトガスも発生せず、湿気も必要ないものの、白金触媒などの付加反応触媒が必要であり、共存する化合物によっては硬化阻害が生じるという問題がある。Conventional two-part curing silicone compositions utilize condensation reactions or addition reactions. However, condensation reactions using organopolysiloxanes with hydroxyl or alkoxy groups require moisture for curing, generate reaction by-products (outgassing), and have problems with high shrinkage. On the other hand, addition reactions using organopolysiloxanes with vinyl groups and organopolysiloxanes with hydrosilyl groups have excellent shrinkage, do not generate outgassing, and do not require moisture, but require an addition reaction catalyst such as a platinum catalyst, and have problems with curing inhibition depending on the coexisting compound.
これに対して、本実施形態においては、上記のようにエポキシ基含有基を有するエポキシ変性オルガノポリシロキサンＡ１とアミノ変性オルガノポリシロキサンＡ２とを用いることにより、白金触媒などの付加反応触媒が不要であり、硬化阻害も生じないうえ、硬化に湿気が必要なく、アウトガスも発生しない二液硬化型組成物セットを提供することができる。In contrast, in this embodiment, by using an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and an amino-modified organopolysiloxane A2 as described above, it is possible to provide a two-component curing composition set that does not require an addition reaction catalyst such as a platinum catalyst, does not cause curing inhibition, does not require moisture for curing, and does not generate outgassing.
また、上記理由のため、本実施形態においては、第一剤及び第二剤が、共に、少なくとも末端又は側鎖にビニル基を有するオルガノポリシロキサンと、少なくとも末端又は側鎖にヒドロシリル基を有するオルガノポリシロキサンを含まないことが好ましい。 Also, for the above reasons, in this embodiment, it is preferable that neither the first agent nor the second agent contains an organopolysiloxane having at least a vinyl group at the end or in the side chain, nor an organopolysiloxane having at least a hydrosilyl group at the end or in the side chain.
以下、第一剤及び第二剤に含まれる各成分について詳説する。 Below, we will explain in detail each ingredient contained in the first and second agents.
＜第一剤＞
第一剤は、エポキシ基含有基を有するエポキシ変性オルガノポリシロキサンＡ１、及び熱伝導性フィラーＢ１を含み、必要に応じて、ポリジメチルシロキサンＣ、オルガノシランＤ、着色剤Ｅ等の添加剤を含んでもよい。
<First drug>
The first agent contains an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group, and a thermally conductive filler B1, and may contain additives such as polydimethylsiloxane C, organosilane D, and colorant E, as necessary.
（エポキシ変性オルガノポリシロキサンＡ１）
本実施形態のエポキシ変性オルガノポリシロキサンＡ１は、末端又は側鎖にエポキシ基を有する置換基（エポキシ基含有基）を有する。エポキシ基を有するオルガノポリシロキサンは、オルガノポリシロキサン分子におけるＳｉ－Ｒ部分（ただし、Ｒは置換又は非置換の１価の炭化水素基である）のＲの少なくとも一部がエポキシ基を有する置換基であるものである。
(Epoxy-modified organopolysiloxane A1)
The epoxy-modified organopolysiloxane A1 of this embodiment has a substituent (epoxy group-containing group) having an epoxy group at the end or in the side chain. The organopolysiloxane having an epoxy group is one in which at least a part of the R in the Si-R portion (wherein R is a substituted or unsubstituted monovalent hydrocarbon group) in the organopolysiloxane molecule is a substituent having an epoxy group.
エポキシ基含有基としては、特に制限されないが、例えば、下記式（ａ１１）で表される脂肪族エポキシ基、下記式（ａ１２）で表される脂環式エポキシ基が挙げられる。このなかでも、硬化反応性の観点からはグリシジル基などの脂肪族エポキシ基が好ましく、得られる硬化物のガラス転移点を高くする観点からはエチルシクロヘキセンオキシド基などの脂環式エポキシ基が好ましい。また、エポキシ変性オルガノポリシロキサンＡ１は、脂肪族エポキシ基と脂環式エポキシ基の両方を有していてもよい。
（式中、Ｒ１は、炭素数１～６のアルキル基を示す。）
The epoxy group-containing group is not particularly limited, but examples thereof include an aliphatic epoxy group represented by the following formula (a11) and an alicyclic epoxy group represented by the following formula (a12). Among these, an aliphatic epoxy group such as a glycidyl group is preferred from the viewpoint of curing reactivity, and an alicyclic epoxy group such as an ethylcyclohexene oxide group is preferred 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.
(In the formula, R 1 represents an alkyl group having 1 to 6 carbon atoms.)
エポキシ変性オルガノポリシロキサンＡ１は、直鎖状構造、分岐状構造、又は環状構造のいずれを有していてもよく、直鎖状構造と環状構造を組み合わせた構造又は分岐状構造と環状構造を組み合わせた構造を有していてもよい。このなかでも、液体としての取扱性の観点からは直鎖状構造が好ましく、得られる硬化物の機械物性の観点からは分岐状構造が好ましい。The epoxy-modified organopolysiloxane A1 may have a linear structure, a branched structure, or a cyclic structure, or may have a structure in which a linear structure and a cyclic structure are combined, or a structure in which a branched structure and a cyclic structure are combined. Among these, a linear structure is preferred from the viewpoint of handleability as a liquid, and a branched structure is preferred from the viewpoint of the mechanical properties of the resulting cured product.
エポキシ変性オルガノポリシロキサンＡ１におけるエポキシ基含有基の結合位置は、特に制限されず、末端又は側鎖であってもよいし、末端及び側鎖であってもよい。側鎖にエポキシ基含有基を有する場合には、エポキシ変性オルガノポリシロキサンＡ１は、例えば、下記一般式（ａ１－１）又は（ａ１－２）で表される構成単位を有する。また、末端にエポキシ基含有基を有する場合には、エポキシ変性オルガノポリシロキサンＡ１は、例えば、下記一般式（ａ１－３）で表される末端構造（但し、ｎが１以上のもの）を有する。さらに、エポキシ基含有基が結合していない構成単位としては、下記一般式（ａ１－４）で表される構成単位が挙げられる。なお、エポキシ変性オルガノポリシロキサンＡ１の有する構成単位は以下に限定されるもではなく、例えば、分岐状構造を有する場合には分岐型の構成単位を有していてもよい、環状構造を有する場合には末端構造を有しなくてもよい。
（式中、Ｘは、各々独立して、エポキシ基含有基を示し、Ｒ２は、各々独立して、炭素数１～１２の置換又は非置換の炭化水素基、又はポリエーテル基を示し、ｎは０～３の整数を示す。）
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. When the epoxy group-containing group is present in the side chain, the epoxy-modified organopolysiloxane A1 has, for example, a structural unit represented by the following general formula (a1-1) or (a1-2). When the epoxy group-containing group is present in the terminal, the epoxy-modified organopolysiloxane A1 has, for example, a terminal structure represented by the following general formula (a1-3) (wherein n is 1 or more). Furthermore, an example of a structural unit to which an epoxy group-containing group is not bonded is a structural unit represented by the following general formula (a1-4). The structural units contained in the epoxy-modified organopolysiloxane A1 are not limited to the following, and for example, when the epoxy-modified organopolysiloxane A1 has a branched structure, the epoxy-modified organopolysiloxane A1 may have a branched structural unit, and when the epoxy-modified organopolysiloxane A1 has a cyclic structure, the epoxy-modified organopolysiloxane A1 may not have a terminal structure.
(In the formula, each X independently represents an epoxy group-containing group, each R2 independently represents a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms or a polyether group, and n represents an integer of 0 to 3.)
Ｒ２で示される置換又は非置換の炭化水素基としては、特に制限されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基；クロロメチル基、３，３，３－トリフルオロプロピル基、３－クロロプロピル基等のハロゲン化アルキル基が挙げられる。 The substituted or unsubstituted hydrocarbon group represented by R2 is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 2-phenylpropyl groups; and halogenated alkyl groups such as chloromethyl, 3,3,3-trifluoropropyl, and 3-chloropropyl groups.
また、Ｒ２で示されるポリエーテル基としては、特に制限されないが、例えば、ポリエチレングリコール基（－（Ｃ２Ｈ４Ｏ）ｌ－ＣＨ２Ｈ５，－（Ｃ２Ｈ４Ｏ）ｌ－ＣＨ２Ｈ４ＯＨ）、ポリプロピレングリコール基（－（Ｃ３Ｈ６Ｏ）ｌ－ＣＨ３Ｈ７，－（Ｃ３Ｈ６Ｏ）ｌ－ＣＨ３Ｈ６ＯＨ）、ポリエチレングリコール－ポリプロピレングリコール共重合基が挙げられる。なお、ｌは２～１０００の整数を示す。 The polyether group represented by R2 is not particularly limited, but examples thereof include 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), a polypropylene glycol group (-(C 3 H 6 O) l -CH 3 H 7 , -(C 3 H 6 O) l -CH 3 H 6 OH), and a polyethylene glycol-polypropylene glycol copolymer group. Here, l represents an integer of 2 to 1000.
このなかでも、エポキシ変性オルガノポリシロキサンＡ１としては、側鎖にエポキシ基含有基を有する直鎖状構造のオルガノポリシロキサンが好ましい。このようなエポキシ変性オルガノポリシロキサンＡ１を用いることにより、第一剤と第二剤の反応性がより向上する傾向にある。Among these, the epoxy-modified organopolysiloxane A1 is preferably an organopolysiloxane having a linear structure with an epoxy group-containing group in the side chain. By using such an epoxy-modified organopolysiloxane A1, the reactivity of the first agent and the second agent tends to be further improved.
エポキシ変性オルガノポリシロキサンＡ１のエポキシ基の官能基当量は、好ましくは１００～１１０００ｇ／ｍｏｌであり、より好ましくは２００～６０００ｇ／ｍｏｌであり、さらに好ましくは２５０～５０００ｇ／ｍｏｌである。エポキシ基の官能基当量が上記範囲内であることにより、第一剤と第二剤の反応性がより向上し、均一反応性がより向上する傾向にある。The functional group equivalent of the epoxy group of the epoxy-modified organopolysiloxane A1 is preferably 100 to 11,000 g/mol, more preferably 200 to 6,000 g/mol, and even more preferably 250 to 5,000 g/mol. When the functional group equivalent of the epoxy group is within the above range, the reactivity of the first agent and the second agent is improved, and the uniform reactivity tends to be improved.
また、エポキシ変性オルガノポリシロキサンＡ１の２５℃における粘度は、好ましくは５～１５０００ｍｍ２／ｓであり、より好ましくは５～１２０００ｍｍ２／ｓであり、さらに好ましくは５～１００００ｍｍ２／ｓである。粘度が上記範囲内であることにより、二液硬化型の組成物セットとしての取扱性がより向上する傾向にある。 The viscosity of the epoxy-modified organopolysiloxane A1 at 25° C. is preferably 5 to 15,000 mm 2 /s, more preferably 5 to 12,000 mm 2 /s, and even more preferably 5 to 10,000 mm 2 /s. Having a viscosity within the above range tends to improve the handleability of the composition set as a two-component curing type.
（熱伝導性フィラーＢ１）
熱伝導性フィラーＢ１は、例えば熱伝導率が１０Ｗ／ｍ・Ｋ以上のフィラーである。このような熱伝導性フィラーＢ１としては、特に制限されないが、例えば、酸化アルミニウム（以下、「アルミナ」ともいう）、窒化アルミニウム、シリカ、窒化ホウ素、窒化ケイ素、酸化亜鉛、水酸化アルミニウム、金属アルミニウム、酸化マグネシウム、ダイヤモンド、カーボン、インジウム、ガリウム、銅、銀、鉄、ニッケル、金、錫、金属ケイ素等が挙げられる。
(Thermal conductive filler B1)
The thermally conductive filler B1 is, for example, a filler having a thermal conductivity of 10 W/m·K or more. Although there is no particular limitation on such a thermally conductive filler B1, examples thereof include aluminum oxide (hereinafter also referred to as "alumina"), aluminum nitride, silica, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metallic aluminum, magnesium oxide, diamond, carbon, indium, gallium, copper, silver, iron, nickel, gold, tin, metallic silicon, and the like.
このなかでも、酸化アルミニウム、窒化アルミニウム、窒化ホウ素、窒化ケイ素、酸化亜鉛、水酸化アルミニウム、金属アルミニウム、酸化マグネシウム、銅、銀、ダイヤモンドからなる群より選ばれる少なくとも一種以上を含むことが好ましく、アルミナがより好ましい。このような熱伝導性フィラーＢ１を用いることにより、充填性が向上し、得られる硬化物の熱伝導率がより向上する傾向にある。これら熱伝導性フィラーＢ１は１種単独で用いても、２種以上を併用してもよい。Among these, it is preferable to include 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. By using such a thermally conductive filler B1, the filling property is improved and the thermal conductivity of the obtained cured product tends to be further improved. These thermally conductive fillers B1 may be used alone or in combination of two or more types.
熱伝導性フィラーＢ１の平均粒径は、好ましくは０．１～１２０μｍであり、より好ましくは０.１～６０μｍである。熱伝導性フィラーＢ１の平均粒径が上記範囲内であることにより、流動性や分散性、充填性がより向上する傾向にある。The average particle size of the thermally conductive filler B1 is preferably 0.1 to 120 μm, and more preferably 0.1 to 60 μm. When the average particle size of the thermally conductive filler B1 is within the above range, the fluidity, dispersibility, and filling properties tend to be improved.
また、熱伝導性フィラーＢ１は、平均粒径の異なるフィラーを混合して用いてもよい。例えば、平均粒径が４０～５０μｍである熱伝導性フィラー（Ｂ１－１）、及び平均粒径が１～１０μｍである熱伝導性フィラー（Ｂ１－２）を組み合わせて用いることがより好ましい。この場合、熱伝導性フィラー（Ｂ１－１）の含有量は、熱伝導性フィラーＢ１の総量に対して、好ましくは４０～８０質量％であり、より好ましくは５０～７０質量％である。また、熱伝導性フィラー（Ｂ１－１）の含有量は、熱伝導性フィラーＢ１の総量に対して、好ましくは２０～６０質量％であり、より好ましくは３０～５０質量％である。このような熱伝導性フィラーＢ１を用いることにより、流動性や分散性、充填性がより向上する傾向にある。なお、本実施形態における平均粒径は、Ｄ５０（メジアン径）を意味するものとする。 The thermally conductive filler B1 may be a mixture of fillers having different average particle sizes. For example, it is more preferable to use a combination of a thermally conductive filler (B1-1) having an average particle size of 40 to 50 μm and a thermally conductive filler (B1-2) having an average particle size of 1 to 10 μm. In this case, the content of the thermally conductive filler (B1-1) is preferably 40 to 80 mass%, more preferably 50 to 70 mass%, based on the total amount of the thermally conductive filler B1. The content of the thermally conductive filler (B1-1) is preferably 20 to 60 mass%, more preferably 30 to 50 mass%, based on the total amount of the thermally conductive filler B1. By using such a thermally conductive filler B1, the fluidity, dispersibility, and filling property tend to be further improved. In addition, the average particle size in this embodiment means D50 (median diameter).
熱伝導性フィラーＢ１の含有量は、上記エポキシ変性オルガノポリシロキサンＡ１の含有量１００重量部に対して、好ましくは４００～３０００重量部であり、より好ましくは６００～２８００重量部であり、更に好ましくは７００～２６００重量部である。熱伝導性フィラーの含有量が、上記エポキシ変性オルガノポリシロキサンＡ１の含有量１００重量部に対して、４００重量部以上であれば、得られる硬化物の熱伝導率がより良好となり、３０００重量部以下であれば、流動性の低下をより効果的に抑え、塗布性を確保することができる。The content of the thermally conductive filler B1 is preferably 400 to 3000 parts by weight, more preferably 600 to 2800 parts by weight, and even more preferably 700 to 2600 parts by weight, per 100 parts by weight of the epoxy-modified organopolysiloxane A1. If the content of the thermally conductive filler is 400 parts by weight or more per 100 parts by weight of the epoxy-modified organopolysiloxane A1, the thermal conductivity of the resulting cured product will be better, and if it is 3000 parts by weight or less, the decrease in fluidity can be more effectively suppressed and coatability can be ensured.
（ポリジメチルシロキサンＣ）
ポリジメチルシロキサンＣは、第一剤の粘度や得られる硬化物の硬度を調整するために添加することができる。ポリジメチルシロキサンの粘度は特に制限されず、粘度の異なる複数種類のポリジメチルシロキサンを併用してもよい。
(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 multiple types of polydimethylsiloxanes with different viscosities may be used in combination.
ポリジメチルシロキサンＣの含有量は、上記エポキシ変性オルガノポリシロキサンＡ１とポリジメチルシロキサンの合計１００重量部に対して、好ましくは０～８０重量部である。The content of polydimethylsiloxane C is preferably 0 to 80 parts by weight per 100 parts by weight of the combined total of the epoxy-modified organopolysiloxane A1 and polydimethylsiloxane.
（オルガノシランＤ）
オルガノシランＤは、上記熱伝導性フィラーＢ１とエポキシ変性オルガノポリシロキサンＡ１との濡れ性を調整するために添加することができる。このようなオルガノシランとしては、特に制限されないが、例えば、下記一般式（ｄ）で表されるオルガノシランが好適に用いられる。
Ｒ３
ａＲ４
ｂＳｉ（ＯＲ５）４－（ａ＋ｂ） （ｄ）
（式中、Ｒ３は、各々独立して、炭素数１～１５のアルキル基を示し、Ｒ４は、各々独立して、炭素数１～８の不飽和の一価の炭化水素基を示し、Ｒ５は、各々独立して、炭素数１～６のアルキル基を示し、ａは１～３の整数であり、ｂは０～２の整数であり、ａ＋ｂは１～３の整数である。）
(Organosilane D)
Organosilane D can be added to adjust the wettability between the thermally conductive filler B1 and the epoxy-modified organopolysiloxane A1. Although there is no particular limitation on the organosilane, for example, an organosilane represented by the following general formula (d) is preferably used.
R 3 a R 4 b Si(OR 5 ) 4-(a+b) (d)
(In the formula, each R3 independently represents an alkyl group having 1 to 15 carbon atoms, each R4 independently represents an unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms, each R5 independently represents 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, and a+b is an integer of 1 to 3.)
式（ｄ）中、Ｒ３が示す炭素数１～１５のアルキル基としては、特に制限されないが、例えば、メチル基、エチル基、プロピル基、ヘキシル基、ノニル基、デシル基、ドデシル基、テトラデシル基、３，３，３－トリフロロプロピル基、２－（パーフロロブチル）エチル基、２－（パーフロロオクチル）エチル基等が挙げられる。このなかでもＲ３は、炭素数６～１２のアルキル基であることが好ましい。 In formula (d), the alkyl group having 1 to 15 carbon atoms represented by R 3 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a 3,3,3-trifluoropropyl group, a 2-(perfluorobutyl)ethyl group, a 2-(perfluorooctyl)ethyl group, etc. Among these, it is preferable that R 3 is an alkyl group having 6 to 12 carbon atoms.
Ｒ４が示す炭素数１～８の不飽和の一価の炭化水素基としては、特に制限されないが、例えば、ビニル基、アリル基等のアルケニル基；フェニル基、トリル基等のアリール基；２－フェニルエチル基、２－メチル－２－フェニルエチル基等のアラルキル基；、ｐ－クロロフェニル基等のハロゲン化炭化水素基等が挙げられる。 The unsaturated monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R4 is not particularly limited, and examples thereof include alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; and halogenated hydrocarbon groups such as p-chlorophenyl group.
Ｒ５が示す炭素数１～６のアルキル基としては、特に制限されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。このなかでも、Ｒ５はメチル基又はエチル基であることが好ましい。 The alkyl group having 1 to 6 carbon atoms represented by R5 is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. Among these, it is preferable that R5 is a methyl group or an ethyl group.
ａは１～３の整数であり、好ましくは１である。ｂは０～２の整数であり、好ましくは０である。ａ＋ｂは１～３の整数であり、好ましくは１である。 a is an integer from 1 to 3, preferably 1. b is an integer from 0 to 2, preferably 0. a+b is an integer from 1 to 3, preferably 1.
上記オルガノシランＤの含有量は、上記エポキシ変性オルガノポリシロキサンＡ１の含有量１００重量部に対して、好ましくは０．０１～３０重量部であり、より好ましくは０．１～５．０重量部である。オルガノシランＤの含有量が上記範囲内であれば、濡れ性を効果的に向上させることができる。The content of the organosilane D is preferably 0.01 to 30 parts by weight, and more preferably 0.1 to 5.0 parts by weight, per 100 parts by weight of the epoxy-modified organopolysiloxane A1. If the content of organosilane D is within the above range, wettability can be effectively improved.
（着色剤Ｅ）
着色剤Ｅとしては、特に制限されないが、例えば、任意の顔料が挙げられる。着色剤Ｅの含有量は、特に限定されず、例えば、第一剤及び後述する第二剤の合計１００重量部に対して、好ましくは０．０５～０．２重量部である。
(Colorant E)
There is no particular limitation on the colorant E, and examples thereof include any pigment. There is no particular limitation on the content of colorant E, and for example, it is preferably 0.05 to 0.2 parts by weight with respect to 100 parts by weight in total of the first agent and the second agent described below.
＜第二剤＞
第二剤は、アミノ基含有基を有するアミノ変性オルガノポリシロキサンＡ２及び熱伝導性フィラーＢ２を含み、必要に応じて、ポリジメチルシロキサンＣ、オルガノシランＤ、着色剤Ｅ等の添加剤を含んでもよい。
<Second Agent>
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 colorant E, as necessary.
（アミノ変性オルガノポリシロキサンＡ２）
本実施形態のアミノ変性オルガノポリシロキサンＡ２は、末端又は側鎖にアミノ基を有する置換基（アミノ基含有基）を有する。アミノ基を有するオルガノポリシロキサンは、オルガノポリシロキサン分子におけるＳｉ－Ｒ部分（ただし、Ｒは置換又は非置換の１価の炭化水素基である）のＲの少なくとも一部がアミノ基を有する置換基であるものである。
(Amino-modified organopolysiloxane A2)
The amino-modified organopolysiloxane A2 of this embodiment has a substituent (amino group-containing group) having an amino group at the end or in the side chain. The organopolysiloxane having an amino group is one in which at least a part of the R in the Si-R portion (wherein R is a substituted or unsubstituted monovalent hydrocarbon group) in the organopolysiloxane molecule is a substituent having an amino group.
アミノ基含有基としては、特に制限されないが、例えば、下記式（ａ２１）で表されるアミノ基が挙げられる。このようなアミノ基含有基は、１級アミノ基及び２級アミノ基であってもよいが、このなかでもＲ６が水素原子である１級アミノ基が好ましい。
（式中、Ｒ６は、水素原子、又は水素原子がアミノ基に置換されていてもよい炭素数１～６のアルキル基を示し、Ｒ７は、炭素数１～６のアルキル基を示す。）
The amino group-containing group is not particularly limited, and examples thereof include the 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 preferred.
(In the formula, 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, and R 7 represents an alkyl group having 1 to 6 carbon atoms.)
Ｒ６は、水素原子又は水素原子がアミノ基に置換されていてもよい炭素数１～６のアルキル基を示す。Ｒ６が水素原子の場合、式（ａ２１）で表されるアミノ基は３－アミノプロピル基のような末端に１級アミノ基を有する。また、Ｒ６が炭素数１～６のアルキル基の場合、式（ａ２１）で表されるアミノ基は２級アミノ基を有する。さらに、Ｒ６が水素原子がアミノ基に置換された炭素数１～６のアルキル基の場合、式（ａ２１）で表されるアミノ基はアミノエチルアミノプロピル基のように、１級アミノ基と２級アミノ基を有する基や、複数の１級アミノ基を有する基又は複数２級アミノ基を有する基となる。 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. When R 6 is a hydrogen atom, the amino group represented by formula (a21) has a primary amino group at the terminal, such as a 3-aminopropyl group. When R 6 is an alkyl group having 1 to 6 carbon atoms, the amino group represented by formula (a21) has a secondary amino group. When R 6 is an alkyl group having 1 to 6 carbon atoms in which a hydrogen atom is substituted with an amino group, the amino group represented by formula (a21) is a group having a primary amino group and a secondary amino group, such as an aminoethylaminopropyl group, or a group having multiple primary amino groups or multiple secondary amino groups.
アミノ変性オルガノポリシロキサンＡ２は、直鎖状構造、分岐状構造、又は環状構造のいずれを有していてもよく、直鎖状構造と環状構造を組み合わせた構造又は分岐状構造と環状構造を組み合わせた構造を有していてもよい。このなかでも、液体としての取扱性の観点からは直鎖状構造が好ましく、得られる硬化物の機械物性の観点からは分岐状構造が好ましい。The amino-modified organopolysiloxane A2 may have a linear structure, a branched structure, or a cyclic structure, or may have a structure in which a linear structure and a cyclic structure are combined, or a structure in which a branched structure and a cyclic structure are combined. Among these, a linear structure is preferred from the viewpoint of handleability as a liquid, and a branched structure is preferred from the viewpoint of the mechanical properties of the resulting cured product.
アミノ変性オルガノポリシロキサンＡ２におけるアミノ基含有基の結合位置は、特に制限されず、末端又は側鎖であってもよいし、末端及び側鎖であってもよい。側鎖にアミノ基含有基を有する場合には、アミノ変性オルガノポリシロキサンＡ２は、例えば、下記一般式（ａ２－１）又は（ａ２－２）で表される構成単位を有する。また、末端にアミノ基含有基を有する場合には、アミノ変性オルガノポリシロキサンＡ２は、例えば、下記一般式（ａ２－３）で表される末端構造（但し、ｍが１以上のもの）を有する。さらに、アミノ基含有基が結合していない構成単位としては、下記一般式（ａ２－４）で表される構成単位が挙げられる。なお、アミノ変性オルガノポリシロキサンＡ２の有する構成単位は以下に限定されるもではなく、例えば、分岐状構造を有する場合には分岐型の構成単位を有していてもよい、環状構造を有する場合には末端構造を有しなくてもよい。
（式中、Ｙは、各々独立して、アミノ基含有基を示し、Ｒ８は、各々独立して、炭素数１～１２の置換又は非置換の炭化水素基を示し、ｍは０～３の整数を示す。）
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. When the amino group-containing group is present in the side chain, the amino-modified organopolysiloxane A2 has, for example, a structural unit represented by the following general formula (a2-1) or (a2-2). When the amino group-containing group is present in the terminal, the amino-modified organopolysiloxane A2 has, for example, a terminal structure represented by the following general formula (a2-3) (wherein m is 1 or more). Furthermore, an example of a structural unit to which an amino group-containing group is not bonded is a structural unit represented by the following general formula (a2-4). The structural units contained in the amino-modified organopolysiloxane A2 are not limited to the following, and for example, when the amino-modified organopolysiloxane A2 has a branched structure, the amino-modified organopolysiloxane A2 may have a branched structural unit, and when the amino-modified organopolysiloxane A2 has a cyclic structure, the amino-modified organopolysiloxane A2 may not have a terminal structure.
(In the formula, each Y independently represents an amino group-containing group, each R8 independently represents a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and m represents an integer of 0 to 3.)
Ｒ８で示される置換又は非置換の炭化水素基としては、特に制限されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基；クロロメチル基、３，３，３－トリフルオロプロピル基、３－クロロプロピル基等のハロゲン化アルキル基が挙げられる。 The substituted or unsubstituted hydrocarbon group represented by R8 is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 2-phenylpropyl groups; and halogenated alkyl groups such as chloromethyl, 3,3,3-trifluoropropyl, and 3-chloropropyl groups.
このなかでも、アミノ変性オルガノポリシロキサンＡ２としては、末端又は側鎖にアミノ基含有基を有する直鎖状構造のオルガノポリシロキサン、あるいは、末端に水酸基を有し側鎖にアミノ基含有基を有する直鎖状構造のオルガノポリシロキサンが好ましい。このようなアミノ変性オルガノポリシロキサンＡ２を用いることにより、第一剤と第二剤の反応性がより向上する傾向にある。Among these, preferred amino-modified organopolysiloxane A2 is an organopolysiloxane having a linear structure with an amino group-containing group at the end or side chain, or an organopolysiloxane having a linear structure with a hydroxyl group at the end and an amino group-containing group at the side chain. By using such amino-modified organopolysiloxane A2, the reactivity of the first agent and the second agent tends to be further improved.
アミノ変性オルガノポリシロキサンＡ２のアミノ基の官能基当量は、好ましくは１００～８０００ｇ／ｍｏｌであり、より好ましくは２００～６０００ｇ／ｍｏｌであり、より好ましくは３００～４０００ｇ／ｍｏｌであり、よりさらに好ましくは３００～２０００ｇ／ｍｏｌである。アミノ基の官能基当量が上記範囲内であることにより、第一剤と第二剤の反応性がより向上し、均一反応性がより向上する傾向にある。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 300 to 2000 g/mol. By having the functional group equivalent of the amino group within the above range, the reactivity of the first agent and the second agent is further improved, and the uniform reactivity tends to be further improved.
また、アミノ変性オルガノポリシロキサンＡ２の２５℃における粘度は、好ましくは５～２０００ｍｍ２／ｓであり、より好ましくは５～１７５０ｍｍ２／ｓであり、さらに好ましくは５～１５００ｍｍ２／ｓである。粘度が上記範囲内であることにより、二液硬化型の組成物セットとしての取扱性がより向上する傾向にある。 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. Having a viscosity within the above range tends to improve the handleability of the composition set as a two-component curing type.
また、アミノ変性オルガノポリシロキサンＡ２は、ケイ素原子に水酸基が結合した水酸基含有基をさらに有することが好ましい。水酸基含有基の結合位置は、特に制限されず、末端又は側鎖であってもよいし、末端及び側鎖であってもよい。このなかでも、両末端にアミノ基含有基を有する直鎖状構造のアミノ変性オルガノポリシロキサンＡ２が好ましい。このようなアミノ変性オルガノポリシロキサンＡ２を使用することにより、エポキシ変性オルガノポリシロキサンＡ１との相溶性がより向上し、均一反応性がより向上する傾向にある。In addition, it is preferable that 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 at the end or the side chain, or at the end and the side chain. Among these, amino-modified organopolysiloxane A2 having a linear structure with amino group-containing groups at both ends is preferable. By using such amino-modified organopolysiloxane A2, compatibility with epoxy-modified organopolysiloxane A1 is further improved, and uniform reactivity tends to be further improved.
（熱伝導性フィラーＢ２）
熱伝導性フィラーＢ２は、例えば熱伝導率が１０Ｗ／ｍ・Ｋ以上のフィラーであり、熱伝導性フィラーＢ１と同様のものが挙げられる。このなかでも、酸化アルミニウム、窒化アルミニウム、窒化ホウ素、窒化ケイ素、酸化亜鉛、水酸化アルミニウム、金属アルミニウム、酸化マグネシウム、銅、銀、ダイヤモンドからなる群より選ばれる少なくとも一種以上を含むことが好ましい。このような熱伝導性フィラーＢ２を用いることにより、充填性が向上し、得られる硬化物の熱伝導率がより向上する傾向にある。これら熱伝導性フィラーＢ２は１種単独で用いても、２種以上を併用してもよい。
(Thermal conductive filler B2)
The thermally conductive filler B2 is, for example, a filler having a thermal conductivity of 10 W/m·K or more, and may be the same as the thermally conductive filler B1. Among these, it is preferable to include 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. By using such a thermally conductive filler B2, the filling property is 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.
また、熱伝導性フィラーＢ２の平均粒径及び含有量についても、熱伝導性フィラーＢ１と同様とすることができ、上記熱伝導性フィラーＢ１に関する記載は、熱伝導性フィラーＢ２に読み替えて適用することができる。In addition, the average particle size and content of thermally conductive filler B2 can be the same as those of thermally conductive filler B1, and the above description of thermally conductive filler B1 can be read and applied to thermally conductive filler B2.
（添加剤）
その他、第二剤に含まれ得る、ポリジメチルシロキサンＣ、オルガノシランＤ、及び着色剤Ｅの種類や含有量は、上述した第一剤と同様であり、第一剤におけるこれらに関する記載は第二剤に関するものとして読み替えて適用することができるため、ここでは重複する説明を省略する。
(Additives)
In addition, the types and contents of polydimethylsiloxane C, organosilane D, and colorant E that may be contained in the second agent are the same as those of the first agent described above, and the descriptions regarding these in the first agent can be read and applied as those regarding the second agent, so duplicated descriptions will be omitted here.
なお、第二剤としての熱伝導性フィラー、ポリジメチルシロキサン、オルガノシラン、着色剤と、第一剤としての熱伝導性フィラー、ポリジメチルシロキサン、オルガノシラン、着色剤とは、同種のものであっても異種のものであってもよい。In addition, the thermally conductive filler, polydimethylsiloxane, organosilane, and colorant as the second agent and the thermally conductive filler, polydimethylsiloxane, organosilane, and colorant as the first agent may be of the same type or of different types.
＜第一剤と第二剤の比率＞
本実施形態の二液硬化型組成物セットにおいて、第一剤におけるエポキシ変性オルガノポリシロキサンＡ１と、第二剤におけるアミノ変性オルガノポリシロキサンＡ２の割合は、第一剤におけるエポキシ変性オルガノポリシロキサンＡ１のエポキシ基の含有量および第二剤におけるアミノ変性オルガノポリシロキサンＡ２のアミノ基の含有量に応じて適宜設定することができる。
エポキシ基の含有量＝エポキシ変性オルガノポリシロキサンＡ１の含有量／官能基当量
アミノ基の含有量 ＝アミノ変性オルガノポリシロキサンＡ２の含有量／官能基当量
<Ratio of first and second agent>
In the two-component curing composition set of this embodiment, the ratio of the epoxy-modified organopolysiloxane A1 in the first agent and the amino-modified organopolysiloxane A2 in the second agent can be appropriately set according to the epoxy group content of the epoxy-modified organopolysiloxane A1 in the first agent and the amino group content of the amino-modified organopolysiloxane A2 in the second agent.
Epoxy group content = epoxy-modified organopolysiloxane A1 content / functional group equivalent Amino group content = amino-modified organopolysiloxane A2 content / functional group equivalent
第一剤と第二剤の組み合わせが満たすエポキシ基の含有量／アミノ基の含有量は、好ましくは７０／３０～１０／９０であり、より好ましくは５５／４５～２０／８０である。エポキシ基の含有量及びアミノ基の含有量の比が上記範囲内であることにより、均一反応性が向上し、十分に架橋構造が形成された硬化物を得ることができる。The ratio of epoxy group content to amino group content satisfied by the combination of the first and second agents is preferably 70/30 to 10/90, and more preferably 55/45 to 20/80. By having the ratio of epoxy group content to amino group content within the above range, uniform reactivity is improved, and a cured product with a sufficiently formed crosslinked structure can be obtained.
＜用途＞
ＡＳＴＭ Ｄ５４７０に準拠して測定した、第一剤と第二剤の混合物の硬化後の熱伝導率は、好ましくは１．０Ｗ／ｍｋ以上であり、より好ましくは２．０Ｗ／ｍｋ以上である。このような本実施形態の二液硬化型組成物セットは、熱伝導性放熱材料として好適に使用することができる。
<Applications>
The thermal conductivity of the mixture of the first and second parts after curing, measured in accordance with ASTM D 5470, is preferably 1.0 W/mK or more, and more preferably 2.0 W/mK or more. Such a two-component curing composition set of the present embodiment can be suitably used as a thermally conductive heat dissipating material.
［硬化物］
本実施形態に係る硬化物は、例えば、上述した二液硬化型組成物セットにおける第一剤及び第二剤を混合することにより得られる。より具体的には、硬化物（架橋硬化物）は、当該第一剤及び第二剤を混合して得られる混合物において、第一剤に含まれるエポキシ変性オルガノポリシロキサンＡ１のエポキシ基と、第二剤に含まれるアミノ変性オルガノポリシロキサンＡ２のアミノ基との付加反応が進行し、架橋結合を有する３次元網目構造を形成することにより、上記硬化物が得られる。
[Cured product]
The cured product according to this embodiment can be obtained, for example, by mixing the first and second parts in the two-part curing composition set described above. More specifically, the cured product (crosslinked cured product) is obtained by forming a three-dimensional network structure having crosslinked bonds through an addition reaction between the epoxy group of the epoxy-modified organopolysiloxane A1 contained in the first part and the amino group of the amino-modified organopolysiloxane A2 contained in the second part in the mixture obtained by mixing the first and second parts.
本実施形態の硬化物は、第一剤及び第二剤を混合した後に、所望の形に成形してもよい。また、本実施形態に係る硬化物は熱伝導性フィラーを含むため熱伝導性放熱材料として好適に用いることができる。The cured product of this embodiment may be molded into a desired shape after mixing the first and second parts. In addition, since the cured product of this embodiment contains a thermally conductive filler, it can be suitably used as a thermally conductive heat dissipation material.
混合には、例えば、ロールミル、ニーダー、バンバリーミキサー、ラインミキサー等の混合機が用いられ、例えば、万能混合撹拌機、ハイブリッドミキサー、トリミックス（井上製作所製）、スタティックミキサーを用いて混練する方法等が挙げられる。成形方法はドクターブレード法が好ましいが、樹脂の粘度によって押出法、プレス法、カレンダーロール法等を用いることができる。付加反応の進行における反応条件は、特に限定されないが、通常、室温（例えば２５℃）から１５０℃、０．１～２４時間で行われる。For mixing, a mixer such as a roll mill, kneader, Banbury mixer, or line mixer is used, and examples of the method include kneading using a universal mixer, hybrid mixer, Trimix (manufactured by Inoue Seisakusho), or static mixer. The doctor blade method is preferred as the molding method, but extrusion, pressing, calendar roll, and other methods can be used depending on the viscosity of the resin. The reaction conditions for the addition reaction are not particularly limited, but are usually performed at room temperature (e.g., 25°C) to 150°C for 0.1 to 24 hours.
第一剤と第二剤の混合割合は、用いる第一剤及び第二剤の種類、及び使用目的に応じて適宜設定できるが、例えば、体積比で第一剤：第二剤＝１．５：１．０～１．０：１．５であってよく、１．０：１．０であってよい。The mixing ratio of the first agent and the second agent can be set appropriately depending on the type of the first agent and the second agent used and the purpose of use, but for example, the volume ratio of first agent:second agent may be 1.5:1.0 to 1.0:1.5, or may be 1.0:1.0.
［電子機器］
本実施形態の電子機器は、電子部品と上記硬化物と電子部品及び硬化物を収容する筐体とを備え、電子部品及び筐体が前記硬化物を介して接触しているものである。
[Electronic devices]
The electronic device of the present embodiment includes an electronic component, the above-mentioned cured product, and a housing that houses the electronic component and the cured product, the electronic component and the housing being in contact with each other via the cured product.
ここで、電子部品としては、特に制限されないが、例えば、モーター、電池パック、車載電源システムに持つ売られる回路基板、パワートランジスタ、マイクロプロセッサ等の発熱する電子部品等が挙げられる。また、金属筐体としては、特に制限されないが、例えば、放熱や吸熱を目的として構成されたヒートシンクなどが挙げられる。Here, the electronic components are not particularly limited, but examples thereof include heat-generating electronic components such as motors, battery packs, circuit boards for on-board power supply systems, power transistors, microprocessors, etc. In addition, the metal housing is not particularly limited, but examples thereof include heat sinks configured for the purpose of dissipating or absorbing heat.
以下、実施例により本発明を更に詳述するが、本発明は以下の実施例に限定されるものではない。The present invention will be described in further detail below with reference to examples, but the present invention is not limited to the following examples.
［第一剤］
以下に示す、Ａ１成分～Ｃ１成分を、表１に記載の配合比（重量部）に基づき混合し、第一剤Ｉ－１～Ｉ～３を作製した。各成分の混合はハイブリッドミキサーＡＲＥ－３１０（シンキー株式会社製、商品名）を用いて行った。
[First Agent]
First agents I-1 to I-3 were prepared by mixing the following A1 to C1 components based on the compounding ratios (parts by weight) shown in Table 1. Each component was mixed using a hybrid mixer ARE-310 (manufactured by Thinky Corporation, product name).
＜Ａ１成分：オルガノポリシロキサン＞
Ａ１－１：ＤＯＷＳＩＬ ＢＹ １６－８３９ Ｆｌｕｉｄ（ダウ・東レ株式会社製、商品名）、エポキシ変性オルガノポリシロキサン、２５℃における粘度：６０００ｍｍ２／ｓ、エポキシ基の官能基当量：３７００ｇ／ｍｏｌ、脂環式タイプ（エチルシクロヘキセンオキシド基）、エポキシ基結合位置：側鎖
Ａ１－２：ＤＯＷＳＩＬ ＢＹ ８４１１ Ｆｌｕｉｄ（ダウ・東レ株式会社製、商品名）、エポキシ変性オルガノポリシロキサン、２５℃における粘度：８０００ｍｍ２／ｓ、エポキシ基の官能基当量：３３００ｇ／ｍｏｌ、脂肪族タイプ（グリシジル基）、エポキシ基結合位置：側鎖
Ａ１－３：ＤＯＷＳＩＬ ＳＥ １８８５Ａ（ダウ・東レ株式会社製、商品名）ビニル基を有するオルガノポリシロキサン（白金触媒含有）
<Component A1: Organopolysiloxane>
A1-1: DOWSIL BY 16-839 Fluid (trade name, manufactured by Dow Toray Co., Ltd.), epoxy-modified organopolysiloxane, viscosity at 25° C.: 6000 mm 2 /s, epoxy functional group equivalent: 3700 g/mol, alicyclic type (ethylcyclohexene oxide group), epoxy group bond position: side chain A1-2: DOWSIL BY 8411 Fluid (trade name, manufactured by Dow Toray Co., Ltd.), epoxy-modified organopolysiloxane, viscosity at 25° C.: 8000 mm 2 /s, epoxy functional group equivalent: 3300 g/mol, aliphatic type (glycidyl group), epoxy group bond position: side chain A1-3: DOWSIL SE 1885A (trade name, manufactured by Dow Toray Co., Ltd.) Organopolysiloxane having vinyl groups (containing platinum catalyst)
＜Ｂ１成分：熱伝導性フィラー＞
Ｂ１－１：球状アルミナ、平均粒径：４５μｍ、ＤＡＷ４５Ｓ（デンカ株式会社製、商品名）、熱伝導率３５Ｗ／ｍＫ
Ｂ１－２：球状アルミナ、平均粒径：５μｍ、ＤＡＷ０５（デンカ株式会社製、商品名）、熱伝導率３５Ｗ／ｍＫ
<Component B1: Thermally conductive filler>
B1-1: Spherical alumina, average particle size: 45 μm, DAW45S (product name, manufactured by Denka Co., Ltd.), thermal conductivity 35 W/mK
B1-2: Spherical alumina, average particle size: 5 μm, DAW05 (product name, manufactured by Denka Co., Ltd.), thermal conductivity 35 W/mK
＜Ｃ１成分：着色剤＞
Ｃ１：レジノブラック＃４４２（レジノカラー工業株式会社、商品名）
<Component C1: Colorant>
C1: Resino Black #442 (product name, Resino Color Kogyo Co., Ltd.)
［第二剤］
以下に示す、Ａ２成分～Ｂ２成分を、表２に記載の配合比（重量部）に基づき混合し、第二剤ＩＩ－１～ＩＩ－６を作製した。各成分の混合はハイブリッドミキサーＡＲＥ－３１０（シンキー株式会社製、商品名）を用いて行った。
[Second Agent]
The following components A2 to B2 were mixed based on the compounding ratios (parts by weight) shown in Table 2 to prepare second agents II-1 to II-6. Each component was mixed using a hybrid mixer ARE-310 (manufactured by Thinky Corporation, product name).
＜Ａ２成分：オルガノポリシロキサン＞
Ａ２－１：ＤＯＷＳＩＬ ＢＹ １６－２１３（ダウ・東レ株式会社製、商品名）、アミノ変性オルガノポリシロキサン、２５℃における粘度：６０ｍｍ２／ｓ、アミノ基の官能基当量：２７００ｇ／ｍｏｌ、一級アミン（３－アミノプロピル基）、アミノ基結合位置：側鎖
Ａ２－２：ＤＯＷＳＩＬ ＢＹ １６－８５３Ｕ（ダウ・東レ株式会社製、商品名）、アミノ変性オルガノポリシロキサン、２５℃における粘度１４ｍｍ２／ｓ、アミノ基の官能基当量４５０ｇ／ｍｏｌ、一級アミン（３－アミノプロピル基）、アミノ基結合位置：末端
Ａ２－３：ＤＯＷＳＩＬ ＢＹ １６－８９２（ダウ・東レ株式会社製、商品名）、アミノ変性オルガノポリシロキサン、２５℃における粘度１４００ｍｍ２／ｓ、アミノ基の官能基当量１９００ｇ／ｍｏｌ、一級アミン及び二級アミン（アミノエチルアミノプロピル基）、アミノ基結合位置：側鎖、両末端ＯＨ含有
Ａ２－４：ＤＯＷＳＩＬ ＳＥ １８８５Ｂ（ダウ・東レ株式会社製、商品名）ビニル基を有するオルガノポリシロキサンとヒドロシリル基を有するオルガノポリシロキサンの混合物
Ａ２－５：ＤＯＷＳＩＬ ＢＹ ８４２８ Ｆｌｕｉｄ（ダウ・東レ株式会社製、商品名）、カルビノール変性オルガノポリシロキサン、２５℃における粘度１４０ｍｍ２／ｓ、官能基当量１６００ｇ／ｍｏｌ
Ａ２－６：ＤＯＷＳＩＬ ＢＹ １６－８８０ Ｆｌｕｉｄ（ダウ・東レ株式会社製、商品名）カルボキシル変性オルガノポリシロキサン２５℃における粘度２５００ｍｍ２／ｓ、官能基当量３３００ｇ／ｍｏｌ
<Component A2: Organopolysiloxane>
A2-1: DOWSIL BY 16-213 (trade name, manufactured by Dow Toray Co., Ltd.), 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 bonding position: side chain A2-2: DOWSIL BY 16-853U (trade name, manufactured by Dow Toray Co., Ltd.), amino-modified organopolysiloxane, viscosity at 25°C: 14 mm 2 /s, functional group equivalent of amino group: 450 g/mol, primary amine (3-aminopropyl group), amino group bonding position: terminal A2-3: DOWSIL BY 16-892 (trade name, manufactured by Dow Toray Co., Ltd.), amino-modified organopolysiloxane, viscosity at 25°C: 1400 mm 2 /s, amino functional group equivalent 1900 g/mol, primary amine and secondary amine (aminoethylaminopropyl group), amino group bonding position: side chain, both terminal OH-containing A2-4: DOWSIL SE 1885B (trade name, manufactured by Dow Toray Co., Ltd.), mixture of organopolysiloxane having a vinyl group and organopolysiloxane having a hydrosilyl group A2-5: DOWSIL BY 8428 Fluid (trade name, manufactured by Dow Toray Co., Ltd.), carbinol-modified organopolysiloxane, viscosity at 25°C 140 mm 2 /s, functional group equivalent 1600 g/mol
A2-6: DOWSIL BY 16-880 Fluid (trade name, manufactured by Dow Toray Co., Ltd.) Carboxyl-modified organopolysiloxane, viscosity at 25° C.: 2500 mm 2 /s, functional group equivalent: 3300 g/mol
＜Ｂ２成分：熱伝導性フィラー＞
Ｂ２－１：球状アルミナ、平均粒径：４５μｍ、ＤＡＷ４５Ｓ（デンカ株式会社製、商品名）
Ｂ２－２：球状アルミナ、平均粒径：５μｍ、ＤＡＷ０５（デンカ株式会社製、商品名）
<Component B2: Thermally conductive filler>
B2-1: Spherical alumina, average particle size: 45 μm, DAW45S (manufactured by Denka Co., Ltd., product name)
B2-2: Spherical alumina, average particle size: 5 μm, DAW05 (manufactured by Denka Co., Ltd., product name)
＜熱伝導率＞
株式会社日立テクノロジー社製の樹脂材料熱抵抗測定装置を用い、ＡＳＴＭ Ｄ５４７０に準拠した方法により、熱伝導性硬化物の熱伝導率を測定した。具体的には、第一剤及び第二剤を各実施例および比較例に記載の体積比で混合して得られた混合物を、０．２ｍｍ、０．５ｍｍ及び１．０ｍｍの厚さにそれぞれ成形し、得られたそれぞれの成形物を２５℃で２４時間保持して硬化反応を進行させ、熱伝導性硬化物を得た。得られた熱伝導性硬化物に対し、測定面積１０ｍｍ×１０ｍｍでそれぞれの熱抵抗値を測定した。熱抵抗値を縦軸とし、熱伝導性硬化物の厚さを横軸として得られる直線の傾きを算出し、熱伝導性硬化物の熱伝導率とした。
<Thermal Conductivity>
The thermal conductivity of the thermally conductive cured product was measured by a method conforming to 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 ratio described in each Example and Comparative Example was molded into thicknesses of 0.2 mm, 0.5 mm, and 1.0 mm, and each of the obtained molded products was kept at 25 ° C. for 24 hours to allow the curing reaction to proceed, thereby obtaining a thermally conductive cured product. The thermal resistance value of each of the obtained thermally conductive cured products was measured in a measurement area of 10 mm x 10 mm. The slope of the straight line obtained by setting the thermal resistance value as the vertical axis and the thickness of the thermally conductive cured product as the horizontal axis was calculated, and this was taken as the thermal conductivity of the thermally conductive cured product.
［平均粒径の測定］
熱伝導性フィラーの平均粒径は、島津製作所製「レーザー回折式粒度分布測定装置ＳＡＬＤ－２０」（商品名）を用いて測定を行った。評価サンプルは、ガラスビーカーに５０ｍｌの純水と測定する熱伝導性フィラー粉末を５ｇ添加して、スパチュラを用いて撹拌し、その後超音波洗浄機で１０分間、分散処理を行った。分散処理を行った熱伝導性フィラー粉末の溶液を、スポイトを用いて、装置のサンプラ部に一滴ずつ添加して、吸光度が安定したところで測定を行った。レーザー回折式粒度分布測定装置では、センサで検出した粒子による回折／散乱孔の光強度分布のデータから粒度分布を計算する。平均粒径は、測定される粒子径の値に相対粒子量（差分％）を掛け、相対粒子量の合計（１００％）で割って求められる。なお、平均粒径は粒子の平均直径であり、極大値又はピーク値である累積重量平均値Ｄ５０（又はメジアン径）として求めることができる。なお、Ｄ５０は、出現率が最も大きい粒子径になる。
[Measurement of average particle size]
The average particle size of the thermally conductive filler was measured using a laser diffraction particle size distribution measuring device SALD-20 (product name) manufactured by Shimadzu Corporation. The evaluation sample was prepared by adding 50 ml of pure water and 5 g of the thermally conductive filler powder to be measured to a glass beaker, stirring with a spatula, and then dispersing the powder in an ultrasonic cleaner for 10 minutes. The solution of the thermally conductive filler powder that had been dispersed was added drop by drop to the sampler section of the device using a dropper, and the measurement was performed when the absorbance was stabilized. In the laser diffraction particle size distribution measuring device, 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 calculated 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 calculated as the cumulative weight average value D50 (or median diameter), which is the maximum value or peak value. The D50 is the particle size with the highest occurrence rate.
［硬化物］
上記で得られた第一剤及び第二剤を、表３及び表４に示す組合せおよび体積比で混合して混合物を得た。得られた混合物を１５０℃で１時間保持して硬化反応を進行させ、硬化物を得た。なお、硬化反応における各評価を以下の方法に従って実施した。評価結果を表３及び表４にまとめて示す。
[Cured product]
The first and second agents obtained above were mixed in the combinations and volume ratios shown in Tables 3 and 4 to obtain mixtures. The mixtures obtained were held at 150°C for 1 hour to allow the curing reaction to proceed, and cured products were obtained. The curing reaction was evaluated according to the following methods. The evaluation results are summarized in Tables 3 and 4.
＜均一反応性の評価＞
上記第一剤及び第二剤を混合した混合物を厚さ５ｍｍ、縦横２ｃｍ程度に成形し、１５０℃で１時間保持して硬化反応を進行させ、硬化物を得た。得られた硬化物の場所による硬化状態の違いを確認し、硬化物全体で硬化反応が均一に進行しているかどうか（均一反応性）を以下の基準で評価した。
（評価基準）
◎：完全に硬化し、中央部と端部の硬さが同等であった
〇：完全に硬化したが、中央部が端部よりも少し柔らかかった
×：硬化しなかった
<Evaluation of uniform reactivity>
The mixture of the first and second agents was molded into a shape of about 5 mm thick and 2 cm long and wide, and the curing reaction was allowed to proceed for 1 hour at 150° C. to obtain a cured product. Differences in the cured state depending on the location of the obtained cured product were confirmed, and whether the curing reaction proceeded uniformly throughout the entire cured product (uniform reactivity) was evaluated according to the following criteria.
(Evaluation Criteria)
◎: Completely cured, with the center and edges having the same hardness. ◯: Completely cured, but the center was slightly softer than the edges. ×: Not cured.
＜高温安定性の評価＞
上記第一剤及び第二剤をそれぞれ６０℃の乾燥機で７日間加熱状態で保管した。加熱保管後の第一剤及び第二剤を上記と同様の手法にて混合し、１５０℃で１時間保持して硬化反応を進行させた。その際の硬化状態を確認し、第一剤及び第二剤が加熱保管後においても硬化性能を有するかどうか（高温安定性）を以下の基準で評価した。
（評価基準）
〇：硬化した
×：硬化しなかった
<Evaluation of high temperature stability>
The first and second agents were each stored in a heated state in a dryer at 60° C. for 7 days. The first and second agents after the heated storage were mixed in the same manner as above, and the curing reaction was allowed to proceed by holding at 150° C. for 1 hour. The cured state at that time was confirmed, and whether the first and second agents had curing performance even after the heated storage (high temperature stability) was evaluated according to the following criteria.
(Evaluation Criteria)
◯: Cured ×: Not cured
上記表３，４から明らかなように、実施例１～６の本発明の二液硬化型組成物セットは、混合性および均一反応性が良く、保存安定性に優れていた。As is clear from Tables 3 and 4 above, the two-component curing composition sets of the present invention in Examples 1 to 6 had good mixability and uniform reactivity, and excellent storage stability.
比較例１は白金触媒による付加反応型の二液硬化型組成物セットであるため、高温保存により触媒が失活し保存安定性が劣っていた。 Comparative Example 1 was a two-component curing composition set of the addition reaction type using a platinum catalyst, so the catalyst was deactivated when stored at high temperatures, resulting in poor storage stability.
比較例２はエポキシ変性オルガノポリシロキサンとカルビノール変性オルガノポリシロキサンとの混合物であるが、硬化物が形成されず、評価できなかった。 Comparative Example 2 was a mixture of epoxy-modified organopolysiloxane and carbinol-modified organopolysiloxane, but no cured product was formed and it could not be evaluated.
比較例３はエポキシ変性オルガノポリシロキサンとカルボキシル変性オルガノポリシロキサンとの混合物であるが、硬化物が形成されず、評価できなかった。 Comparative Example 3 was a mixture of epoxy-modified organopolysiloxane and carboxyl-modified organopolysiloxane, but no cured product was formed and it could not be evaluated.
実施例５および実施例６は第二剤のアミノ変性オルガノポリシロキサンの種類が異なること以外は略同条件である実施例１および実施例３よりも均一反応性が良好であった。実施例５および実施例６では第二剤に両末端ＯＨ変性のアミノ変性オルガノポリシロキサンを使用している点が実施例１および実施例３と相違している。このことから、使用するアミノ変性オルガノポリシロキサンは両末端ＯＨ変性であるものがより好ましいことが確認された。 Examples 5 and 6 had better uniform reactivity than Examples 1 and 3, which were roughly the same conditions except for the type of amino-modified organopolysiloxane in the second agent. Examples 5 and 6 differ from Examples 1 and 3 in that an amino-modified organopolysiloxane with OH groups at both ends is used in the second agent. From this, it was confirmed that it is more preferable to use an amino-modified organopolysiloxane with OH groups at both ends.
本発明の二液硬化型熱伝導性グリース用組成物は、第一剤と第二剤を混合して硬化させることで熱伝導性の硬化物、特には、発熱体と金属筐体とを熱的に結合して用いる熱伝導性グリースの材料として産業上の利用可能性を有する。The two-component curing thermally conductive grease composition of the present invention has industrial applicability as a thermally conductive cured product produced by mixing the first and second components and curing them, in particular as a thermally conductive grease material used to thermally bond a heating element to a metal housing.
Claims (10)
アミノ基含有基を有するアミノ変性オルガノポリシロキサンＡ２、及び熱伝導性フィラーＢ２を含む第二剤と、を備え、
熱伝導性フィラーＢ１の含有量は、上記エポキシ変性オルガノポリシロキサンＡ１の含有量１００重量部に対して、４００～３０００重量部であり、
熱伝導性フィラーＢ２の含有量は、上記エポキシ変性オルガノポリシロキサンＡ２の含有量１００重量部に対して、４００～３０００重量部であり、
前記熱伝導性フィラーＢ１及び熱伝導性フィラーＢ２が、熱伝導率が１０Ｗ／ｍ・Ｋ以上を示す、酸化アルミニウム、窒化アルミ、窒化ホウ素、窒化ケイ素、酸化亜鉛、水酸化アルミニウム、金属アルミニウム、酸化マグネシウム、銅、銀、ダイヤモンドからなる群より選ばれる少なくとも一種以上を含む、
二液硬化型組成物セット。 A first agent including an epoxy-modified organopolysiloxane A1 having an epoxy group-containing group and a thermally conductive filler B1;
A second agent including an amino-modified organopolysiloxane A2 having an amino group-containing group and a thermally conductive filler B2;
The content of the thermally conductive filler B1 is 400 to 3,000 parts by weight per 100 parts by weight of the epoxy-modified organopolysiloxane A1 ,
The content of the thermally conductive filler B2 is 400 to 3,000 parts by weight per 100 parts by weight of the epoxy-modified organopolysiloxane A2 ,
The thermally conductive filler B1 and the thermally conductive filler B2 each 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, each of which has a thermal conductivity of 10 W/m·K or more.
Two-part curing composition set.
請求項１に記載の二液硬化型組成物セット。 the functional group equivalent weight of the epoxy group in one molecule of the epoxy-modified organopolysiloxane A1 is 100 to 11,000 g/mol;
The two-component curing composition set according to claim 1 .
請求項１又は２に記載の二液硬化型組成物セット。 the functional group equivalent weight of the amino group in one molecule of the amino-modified organopolysiloxane A2 is 100 to 8000 g/mol;
The two-component curing composition set according to claim 1 or 2.
請求項１～３のいずれか一項に記載の二液硬化型組成物セット。 The amino-modified organopolysiloxane A2 in the second agent has hydroxyl group-containing groups at both ends.
The two-component curing composition set according to any one of claims 1 to 3.
少なくとも末端又は側鎖にビニル基を有するオルガノポリシロキサンと、少なくとも末端又は側鎖にヒドロシリル基を有するオルガノポリシロキサンを含まない前記第二剤、を備える、
請求項１～４のいずれか一項に記載の二液硬化型組成物セット。 The first agent does not contain an organopolysiloxane having at least a vinyl group at the end or in a side chain, and an organopolysiloxane having at least a hydrosilyl group at the end or in a side chain; and
The second agent is provided with an organopolysiloxane having at least a vinyl group at the end or in a side chain, and the second agent does not include an organopolysiloxane having at least a hydrosilyl group at the end or in a side chain.
The two-component curing composition set according to any one of claims 1 to 4 .
請求項１～５のいずれか一項に記載の二液硬化型組成物セット。 The thermal conductivity of the mixture of the first agent and the second agent after curing, measured in accordance with ASTM D5470, is 1.0 W/mK or more.
The two-component curing composition set according to any one of claims 1 to 5 .
請求項１～６のいずれか一項に記載の二液硬化型組成物セット。 Used as a thermally conductive heat dissipation material,
The two-component curing composition set according to any one of claims 1 to 6 .
硬化物。 The two-component curing composition set according to any one of claims 1 to 7 , wherein the first component and the second component are mixed together.
Hardened material.
請求項８に記載の硬化物。 Used as a thermally conductive heat dissipation material,
The cured product according to claim 8 .
前記電子部品及び前記筐体が、前記硬化物を介して接触している、
電子機器。 An electronic component, the cured product according to claim 9 , and a housing that houses the electronic component and the cured product,
The electronic component and the housing are in contact with each other via the cured product.
Electronic devices.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020168548 | 2020-10-05 | ||
| JP2020168548 | 2020-10-05 | ||
| PCT/JP2021/036402 WO2022075213A1 (en) | 2020-10-05 | 2021-10-01 | Two-part curing composition set, thermally conductive cured article, and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2022075213A1 JPWO2022075213A1 (en) | 2022-04-14 |
| JP7629935B2 true JP7629935B2 (en) | 2025-02-14 |
Family
ID=81126900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022555438A Active JP7629935B2 (en) | 2020-10-05 | 2021-10-01 | Two-component curing composition set, thermally conductive cured product, and electronic device |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7629935B2 (en) |
| WO (1) | WO2022075213A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003528198A (en) | 2000-03-16 | 2003-09-24 | クロムプトン コーポレイション | Silicone amino-epoxy crosslinkable system |
| JP2011151280A (en) | 2010-01-25 | 2011-08-04 | Denki Kagaku Kogyo Kk | Heat dissipating member and method of manufacturing the same |
| CN107325782A (en) | 2017-05-19 | 2017-11-07 | 天永诚高分子材料（常州）有限公司 | A kind of bi-component casting glue and preparation method thereof |
| WO2019097852A1 (en) | 2017-11-14 | 2019-05-23 | 株式会社高木化学研究所 | Filler-filled highly thermally conductive dispersion composition having excellent segregation stability, method for producing said dispersion composition, filler-filled highly thermally conductive material using said dispersion composition, method for producing said material, and molded article obtained using said material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5590554A (en) * | 1978-12-29 | 1980-07-09 | Toray Silicone Co Ltd | Silicone-epoxy resin composition |
| JPS60179417A (en) * | 1984-02-27 | 1985-09-13 | Shin Etsu Chem Co Ltd | Liquid silicone rubber composition |
| DE4309700C2 (en) * | 1993-03-25 | 1995-02-23 | Sigri Great Lakes Carbon Gmbh | Process for the production of a laminate from metal and graphite |
| JP3498823B2 (en) * | 1996-04-30 | 2004-02-23 | 電気化学工業株式会社 | Heat radiation spacer and its use |
| JP3697645B2 (en) * | 1996-12-25 | 2005-09-21 | 株式会社ジェルテック | Thermal conductive gel |
-
2021
- 2021-10-01 WO PCT/JP2021/036402 patent/WO2022075213A1/en not_active Ceased
- 2021-10-01 JP JP2022555438A patent/JP7629935B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003528198A (en) | 2000-03-16 | 2003-09-24 | クロムプトン コーポレイション | Silicone amino-epoxy crosslinkable system |
| JP2011151280A (en) | 2010-01-25 | 2011-08-04 | Denki Kagaku Kogyo Kk | Heat dissipating member and method of manufacturing the same |
| CN107325782A (en) | 2017-05-19 | 2017-11-07 | 天永诚高分子材料（常州）有限公司 | A kind of bi-component casting glue and preparation method thereof |
| WO2019097852A1 (en) | 2017-11-14 | 2019-05-23 | 株式会社高木化学研究所 | Filler-filled highly thermally conductive dispersion composition having excellent segregation stability, method for producing said dispersion composition, filler-filled highly thermally conductive material using said dispersion composition, method for producing said material, and molded article obtained using said material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022075213A1 (en) | 2022-04-14 |
| WO2022075213A1 (en) | 2022-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5233325B2 (en) | Thermally conductive cured product and method for producing the same | |
| JP6531238B2 (en) | One-component curable heat conductive silicone grease composition and electronic / electrical parts | |
| TWI828778B (en) | Two-component curable composition group, thermally conductive cured material and electronic equipment | |
| JPH08208993A (en) | Thermally conductive silicone composition | |
| KR102132243B1 (en) | Thermal conductive silicone composition and cured product, and composite sheet | |
| TWI635169B (en) | Thermally conductive composite sheet | |
| CN112867765B (en) | Thermally conductive silicone composition and cured product thereof | |
| JPH0536456B2 (en) | ||
| TWI822790B (en) | Thermal conductive polysiloxane composition and manufacturing method thereof | |
| JP2010018646A (en) | Heat-conductive silicone composition | |
| JP2010150399A (en) | Thermally conductive silicone grease composition | |
| JP7136065B2 (en) | THERMALLY CONDUCTIVE SILICONE COMPOSITION AND THERMALLY CONDUCTIVE SILICONE SHEET | |
| TW201943768A (en) | Heat-conductive silicone composition and cured product thereof | |
| KR20080003835A (en) | Curable Silicone Compositions and Cured Products Prepared therefrom | |
| JP2009235279A (en) | Heat-conductive molding and manufacturing method therefor | |
| CN115698222A (en) | Composition for two-component curing type thermally conductive grease, thermally conductive grease, and electronic device | |
| JP2022042170A (en) | Thermosetting silicone composition | |
| WO2020153217A1 (en) | Highly thermally conductive silicone composition and method for producing same | |
| JP2004099842A (en) | Adhesive silicone composition for heat dissipation member | |
| JP7629935B2 (en) | Two-component curing composition set, thermally conductive cured product, and electronic device | |
| JP2008150439A (en) | Thermally conductive silicone composition and coating apparatus using the same | |
| JP7577126B2 (en) | Two-component curing composition set, thermally conductive cured product, and electronic device | |
| KR102821250B1 (en) | Thermally conductive silicone composition and its cured product | |
| JP7656559B2 (en) | Thermally conductive silicone resin sheet and manufacturing method thereof | |
| JP7530864B2 (en) | Thermally conductive silicone composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230627 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240521 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240621 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240919 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20241015 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20250117 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20250203 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7629935 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |