JP6486192B2 - Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet - Google Patents
Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet Download PDFInfo
- Publication number
- JP6486192B2 JP6486192B2 JP2015101797A JP2015101797A JP6486192B2 JP 6486192 B2 JP6486192 B2 JP 6486192B2 JP 2015101797 A JP2015101797 A JP 2015101797A JP 2015101797 A JP2015101797 A JP 2015101797A JP 6486192 B2 JP6486192 B2 JP 6486192B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive composition
- meth
- composition precursor
- 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 101
- 239000002243 precursor Substances 0.000 title claims description 84
- 239000000853 adhesive Substances 0.000 title description 102
- 230000001070 adhesive effect Effects 0.000 title description 102
- 238000004519 manufacturing process Methods 0.000 title description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 128
- 150000002736 metal compounds Chemical class 0.000 claims description 71
- 239000000178 monomer Substances 0.000 claims description 67
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 61
- 239000012765 fibrous filler Substances 0.000 claims description 55
- 239000000835 fiber Substances 0.000 claims description 43
- 125000000524 functional group Chemical group 0.000 claims description 25
- 229920006243 acrylic copolymer Polymers 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 230000000379 polymerizing effect Effects 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 3
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000002270 dispersing agent Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 229920002799 BoPET Polymers 0.000 description 14
- -1 acryl Chemical group 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 239000006188 syrup Substances 0.000 description 9
- 235000020357 syrup Nutrition 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000005865 ionizing radiation Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012711 adhesive precursor Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CWNNYYIZGGDCHS-UHFFFAOYSA-N 2-methylideneglutaric acid Chemical compound OC(=O)CCC(=C)C(O)=O CWNNYYIZGGDCHS-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical class FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Description
本発明は、粘着組成物前駆体、粘着組成物及びその製造方法、粘着シート及びその製造方法、並びに粘着シートを含む電子機器に関する。 The present invention relates to an adhesive composition precursor, an adhesive composition and a manufacturing method thereof, an adhesive sheet and a manufacturing method thereof, and an electronic device including the adhesive sheet.
近年、発光ダイオード（ＬＥＤ）、エレクトロルミネセンス（ＥＬ）のような半導体発光素子の実用化に伴い、これらの素子から発生する熱の対策が重要となってきている。これは、発光素子の輝度向上に伴い発熱量が増加する傾向にあり、発熱に対する対策が十分でないと、素子寿命が低下するなどの問題を生じるためである。また、他の電子機器においても部品の高集積化、高性能化に伴い、機器の内部温度が上昇する傾向にあり、発熱対策が重要となってきている。 In recent years, with the practical application of semiconductor light emitting devices such as light emitting diodes (LEDs) and electroluminescence (EL), countermeasures against heat generated from these devices have become important. This is because the amount of heat generation tends to increase as the luminance of the light-emitting element increases, and problems such as a decrease in element life occur if measures against heat generation are not sufficient. Also, in other electronic devices, the internal temperature of the devices tends to increase with the high integration and performance of components, and countermeasures against heat generation are becoming important.
従来、電子機器等の発熱対策として、素子、部品等の発熱体と、ヒートシンク、放熱フィン等の放熱部材との間を、熱伝導率の高い熱伝導性シートを介して接合することが行われている。この熱伝導性シートに求められる特性としては、接着性及び高熱伝導性が求められることが多い。 Conventionally, as a countermeasure against heat generation of electronic devices, etc., a heating element such as an element or a component and a heat radiation member such as a heat sink or a heat radiation fin are joined via a heat conductive sheet having a high thermal conductivity. ing. As the characteristics required for this heat conductive sheet, adhesion and high heat conductivity are often required.
このため、上記特性を満足するため、種々の検討が行われており、その一例として、アルミナと炭素繊維とアクリル樹脂とを含む粘着剤を用いた粘着テープが提案されている（特許文献１）。この提案では、熱伝導性の観点からアルミナを用い、更に炭素繊維を用いることで熱伝導性の向上を図っている。また、上記炭素繊維には、熱伝導性の向上の点から、カーボンナノチューブ等のカーボンナノ材料を用いることが好ましいとしている。 For this reason, in order to satisfy the above characteristics, various studies have been conducted, and as an example, an adhesive tape using an adhesive containing alumina, carbon fiber, and acrylic resin has been proposed (Patent Document 1). . In this proposal, the thermal conductivity is improved by using alumina from the viewpoint of thermal conductivity and further using carbon fiber. Moreover, it is said that it is preferable to use carbon nanomaterials, such as a carbon nanotube, for the said carbon fiber from the point of a heat conductive improvement.
また、炭素繊維を無機材料と組み合わせて熱伝導率の向上を図ることは粘着性を有しない樹脂材料、樹脂組成物においても行われている。例えば、鱗片状フィラーと繊維状フィラーと樹脂とを組み合わせた熱伝導性樹脂組成物が提案されている（特許文献２）。特許文献２に記載の熱伝導性樹脂組成物では、鱗片状フィラーは同一平面内に並んで平面構造を形成し、この平面構造が複数の層構造を形成しており、その層の間に繊維状フィラーを含む樹脂層が存在し、樹脂層中の繊維状フィラーが層間に熱伝導パスを形成するものである。特に、鱗片状フィラーにはグラファイト、グラフェンといった炭素系材料を用い、繊維状フィラーにはカーボンナノチューブ、カーボンナノファイバーといった炭素系繊維を用い、高熱伝導性の炭素材料を組み合わせた樹脂組成物を提案している。 Further, improvement of thermal conductivity by combining carbon fiber with an inorganic material is also performed in resin materials and resin compositions having no adhesiveness. For example, a thermally conductive resin composition combining a scaly filler, a fibrous filler, and a resin has been proposed (Patent Document 2). In the thermally conductive resin composition described in Patent Document 2, the scale-like fillers are arranged in the same plane to form a planar structure, and the planar structure forms a plurality of layer structures, and fibers are formed between the layers. There is a resin layer containing a fibrous filler, and the fibrous filler in the resin layer forms a heat conduction path between the layers. In particular, we proposed a resin composition that uses carbon-based materials such as graphite and graphene for the scale-like filler, carbon-based fibers such as carbon nanotubes and carbon nanofibers for the fibrous filler, and a high thermal conductivity carbon material. ing.
ところで、最近、粘着シートは、電子機器分野において、単に粘着力だけでなく、接合後の保持力も含めた粘着性能の向上が求められている。 By the way, recently, pressure-sensitive adhesive sheets are required to improve adhesive performance including not only adhesive strength but also holding strength after bonding in the field of electronic equipment.
本発明は、上記状況を鑑みてなされたもので、熱伝導性が高く、粘着性能が良好な粘着シートを提供するものである。 The present invention has been made in view of the above situation, and provides a pressure-sensitive adhesive sheet having high thermal conductivity and good pressure-sensitive adhesive performance.
本発明の粘着組成物前駆体は、（メタ）アクリル共重合体と、（メタ）アクリルモノマーと、板状又は鱗片状の含水金属化合物と、繊維状フィラーとを含む粘着組成物前駆体であって、前記含水金属化合物の平均粒子径が、２μｍ以上５０μｍ以下であり、前記含水金属化合物のアスペクト比が、５以上であり、前記含水金属化合物の含有量は、前記粘着組成物前駆体の全質量に対して、３０質量％以上７０質量％以下であり、前記繊維状フィラーの平均繊維長が、０．５ｍｍ以上１０ｍｍ以下であり、前記繊維状フィラーの平均繊維径が、５μｍ以上２０μｍ以下であり、前記繊維状フィラーの含有量は、前記粘着組成物前駆体の全質量に対して、０．２質量％以上５質量％以下であり、前記（メタ）アクリルモノマーの含有量は、前記（メタ）アクリル共重合体と前記（メタ）アクリルモノマーとの合計質量に対して、７５質量％以上９９質量％以下であることを特徴とする。 The pressure-sensitive adhesive composition precursor of the present invention is a pressure-sensitive adhesive composition precursor containing a (meth) acrylic copolymer, a (meth) acrylic monomer, a plate-like or scaly hydrated metal compound, and a fibrous filler. The hydrous metal compound has an average particle diameter of 2 μm or more and 50 μm or less, the hydrous metal compound has an aspect ratio of 5 or more, and the content of the hydrous metal compound is the total amount of the adhesive composition precursor. 30 mass% or more and 70 mass% or less with respect to mass, The average fiber length of the said fibrous filler is 0.5 mm or more and 10 mm or less, The average fiber diameter of the said fibrous filler is 5 micrometers or more and 20 micrometers or less. Yes, the content of the fibrous filler is 0.2% by mass or more and 5% by mass or less based on the total mass of the pressure-sensitive adhesive composition precursor, and the content of the (meth) acrylic monomer is ( Me ) Characterized in that the total weight of the acrylic copolymer and the a (meth) acrylic monomer, at least 75 wt% 99 wt% or less.
また、本発明の粘着組成物は、上記本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーを重合して形成したものであることを特徴とする。 The pressure-sensitive adhesive composition of the present invention is characterized by being formed by polymerizing a (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention.
また、本発明の粘着シートは、上記本発明の粘着組成物をシート状あるいはテープ状に成形したものであることを特徴とする。 The pressure-sensitive adhesive sheet of the present invention is characterized in that the pressure-sensitive adhesive composition of the present invention is formed into a sheet shape or a tape shape.
また、本発明の電子機器は、上記本発明の粘着シートを含むことを特徴とする。 Moreover, the electronic device of the present invention includes the pressure-sensitive adhesive sheet of the present invention.
また、本発明の粘着組成物の製造方法は、上記本発明の粘着組成物前駆体を調製する工程と、前記粘着組成物前駆体に含まれる前記（メタ）アクリルモノマーを重合する工程とを含むことを特徴とする。 Moreover, the manufacturing method of the adhesion composition of this invention includes the process of preparing the adhesion composition precursor of the said invention, and the process of superposing | polymerizing the said (meth) acryl monomer contained in the said adhesion composition precursor. It is characterized by that.
また、本発明の粘着シートの製造方法は、上記本発明の粘着組成物前駆体を調製する工程と、前記粘着組成物前駆体に含まれる前記（メタ）アクリルモノマーを重合してシート状に成形する工程とを含むことを特徴とする。 Moreover, the manufacturing method of the adhesive sheet of this invention is the process of preparing the said adhesive composition precursor of this invention, and superposing | polymerizing the said (meth) acryl monomer contained in the said adhesive composition precursor, and shape | molding in a sheet form. And a step of performing.
本発明によれば、熱伝導性が高く、粘着性能に優れた粘着シートを提供できる。 According to the present invention, it is possible to provide an adhesive sheet having high thermal conductivity and excellent adhesive performance.
（本発明の粘着組成物前駆体）
本発明の発明者らは、粘着剤の粘着性能について鋭意検討した結果、粘着剤に含まれるフィラーの形状及びサイズが粘着性能に影響することを見出し、本発明を完成させた。より具体的には、粘着剤の粘着性能、特に粘着剤の保持力の向上には、粘着剤に板状又は鱗片状の含水金属化合物と、繊維状フィラーとを含めることが有効であることを見出し、本発明を完成させた。
(Adhesive composition precursor of the present invention)
The inventors of the present invention have intensively studied the adhesive performance of the adhesive, and as a result, found that the shape and size of the filler contained in the adhesive affect the adhesive performance, and completed the present invention. More specifically, in order to improve the adhesive performance of the adhesive, particularly the holding power of the adhesive, it is effective to include a plate-like or scale-like hydrated metal compound and a fibrous filler in the adhesive. The headline and the present invention were completed.
即ち、本発明の粘着組成物前駆体は、（メタ）アクリル共重合体と、（メタ）アクリルモノマーと、板状又は鱗片状の含水金属化合物と、繊維状フィラーとを含んでいる。また、上記含水金属化合物の平均粒子径は２μｍ以上５０μｍ以下であり、上記含水金属化合物のアスペクト比は５以上であり、上記含水金属化合物の含有量は上記粘着組成物前駆体の全質量に対して、３０質量％以上７０質量％以下であり、上記繊維状フィラーの平均繊維長は０．５ｍｍ以上１０ｍｍ以下であり、上記繊維状フィラーの平均繊維径は５μｍ以上２０μｍ以下であり、上記繊維状フィラーの含有量は上記粘着組成物前駆体の全質量に対して、０．２質量％以上５質量％以下であり、上記（メタ）アクリルモノマーの含有量は上記（メタ）アクリル共重合体と上記（メタ）アクリルモノマーとの合計質量に対して、７５質量％以上９９質量％以下である。 That is, the pressure-sensitive adhesive composition precursor of the present invention contains a (meth) acrylic copolymer, a (meth) acrylic monomer, a plate-like or scaly hydrated metal compound, and a fibrous filler. The average particle diameter of the hydrated metal compound is 2 μm or more and 50 μm or less, the aspect ratio of the hydrated metal compound is 5 or more, and the content of the hydrated metal compound is based on the total mass of the pressure-sensitive adhesive composition precursor. 30 mass% or more and 70 mass% or less, the average fiber length of the fibrous filler is 0.5 mm or more and 10 mm or less, the average fiber diameter of the fibrous filler is 5 μm or more and 20 μm or less, and the fibrous The content of the filler is 0.2% by mass or more and 5% by mass or less with respect to the total mass of the pressure-sensitive adhesive composition precursor, and the content of the (meth) acrylic monomer is the same as that of the (meth) acrylic copolymer. It is 75 mass% or more and 99 mass% or less with respect to the total mass with the said (meth) acryl monomer.
本発明の粘着組成物前駆体は、含水金属化合物を含んでいるため、高い熱伝導性を有する粘着剤を提供できる。即ち、上記含水金属化合物は、高い熱伝導性を有する無機フィラーであり、粘着剤に上記含水金属化合物を含ませることにより、粘着剤に高い熱伝導性を付与できる。また、本発明において、含水金属化合物とは、加熱することにより水を放出する金属化合物であると定義する。このため、粘着剤に上記含水金属化合物を含ませることにより、粘着剤に難燃性を付与できる。 Since the pressure-sensitive adhesive composition precursor of the present invention contains a hydrated metal compound, a pressure-sensitive adhesive having high thermal conductivity can be provided. That is, the hydrated metal compound is an inorganic filler having high thermal conductivity, and the adhesive can be provided with high thermal conductivity by including the hydrated metal compound in the adhesive. In the present invention, the hydrous metal compound is defined as a metal compound that releases water when heated. For this reason, a flame retardance can be provided to an adhesive by including the said hydrous metal compound in an adhesive.
上記含水金属化合物は、板状又は鱗片状の形状を有し、上記含水金属化合物の平均粒子径は２μｍ以上５０μｍ以下であり、上記含水金属化合物のアスペクト比は５以上のものである。このため、従来の粒状の無機フィラーを用いた粘着剤に比べて大きな粘着力を得ることができる。これは、アスペクト比が５以上の含水金属化合物を含む粘着組成物前駆体を粘着剤とする際、シート状に加工する必要があるが、加工時に上記前駆体にかかる“ずり”により、上記前駆体シートの少なくとも表面近傍では、上記前駆体シートの厚み方向と上記含水金属化合物の厚み方向とがほぼ一致するため、シート状粘着剤の表面が平坦化するためと考えられる。 The hydrated metal compound has a plate-like or scale-like shape, the average particle diameter of the hydrated metal compound is 2 μm or more and 50 μm or less, and the aspect ratio of the hydrated metal compound is 5 or more. For this reason, compared with the adhesive using the conventional granular inorganic filler, a big adhesive force can be obtained. This is because when a pressure-sensitive adhesive composition precursor containing a hydrous metal compound having an aspect ratio of 5 or more is used as a pressure-sensitive adhesive, it needs to be processed into a sheet shape. It is considered that at least near the surface of the body sheet, the thickness direction of the precursor sheet and the thickness direction of the hydrated metal compound almost coincide with each other, so that the surface of the sheet-like pressure-sensitive adhesive is flattened.
また、上記含水金属化合物の含有量は、上記粘着組成物前駆体の全質量に対して３０質量％以上７０質量％以下に設定する必要があり、３５質量％以上６５質量％以下がより好ましい。上記含水金属化合物の含有量が上記粘着組成物前駆体の全質量に対して３０質量％を下回ると、粘着剤の熱伝導性及び難燃性が低下し、上記含水金属化合物の含有量が上記粘着組成物前駆体の全質量に対して７０質量％を超えると、粘着剤の粘着力が低下し、粘着剤の柔軟性が低下する。粘着剤の柔軟性が低下すると、接合部材への追従性が低下して好ましくない。 Moreover, it is necessary to set content of the said hydrated metal compound to 30 to 70 mass% with respect to the total mass of the said adhesion composition precursor, and 35 to 65 mass% is more preferable. When the content of the hydrated metal compound is less than 30% by mass with respect to the total mass of the pressure-sensitive adhesive composition precursor, the thermal conductivity and flame retardancy of the pressure-sensitive adhesive are reduced, and the content of the hydrated metal compound is When it exceeds 70 mass% with respect to the total mass of an adhesive composition precursor, the adhesive force of an adhesive will fall and the softness | flexibility of an adhesive will fall. If the flexibility of the pressure-sensitive adhesive is lowered, the followability to the joining member is lowered, which is not preferable.
また、本発明の粘着組成物前駆体は、上記含水金属化合物とともに上記繊維状フィラーを含んでいるため、熱伝導率が高く、保持力の良好な粘着剤を提供できる。熱伝導率が高くなるのは、上記粘着組成物前駆体が上記繊維状フィラーを含むことにより、粘着剤作製時の“ずり”による板状又は鱗片状の含水金属化合物の配向を繊維状フィラーが乱すためと考えられる。板状又は鱗片状の含水金属化合物では、その厚み方向とこれに垂直な面内方向の熱伝導率を比較した場合、面内方向の熱伝導率が高いことが知られている。本発明では、板状又は鱗片状の含水金属化合物の配向が繊維状フィラーを加えることで乱されているので、粘着剤の熱伝導率は均一化されて高くなったと考えられる。更に、上記繊維状フィラーは粘着剤にかかる応力を分散するため保持力が良好になったと考えられる。 Moreover, since the adhesive composition precursor of this invention contains the said fibrous filler with the said hydrous metal compound, it can provide an adhesive with high heat conductivity and favorable holding power. The thermal conductivity increases because the adhesive composition precursor contains the fibrous filler, so that the fibrous filler can orient the plate-like or scale-like hydrated metal compound due to “slipping” during the preparation of the adhesive. It is thought to disturb. It is known that the plate-like or scale-like hydrous metal compound has a high thermal conductivity in the in-plane direction when the thickness direction and the in-plane direction perpendicular to the thickness direction are compared. In the present invention, since the orientation of the plate-like or scale-like hydrated metal compound is disturbed by adding a fibrous filler, it is considered that the thermal conductivity of the pressure-sensitive adhesive is made uniform and high. Further, the fibrous filler is considered to have good holding power because it disperses the stress applied to the pressure-sensitive adhesive.
上記繊維状フィラーの平均繊維長は０．５ｍｍ以上１０ｍｍ以下であり、上記繊維状フィラーの平均繊維径は５μｍ以上２０μｍ以下であり、上記繊維状フィラーの含有量は上記粘着組成物前駆体の全質量に対して、０．２質量％以上５質量％以下である。これにより、高い保持力を有し、熱伝導性が均一な粘着剤を提供できる。 The average fiber length of the fibrous filler is 0.5 mm or more and 10 mm or less, the average fiber diameter of the fibrous filler is 5 μm or more and 20 μm or less, and the content of the fibrous filler is the total of the pressure-sensitive adhesive composition precursor. It is 0.2 mass% or more and 5 mass% or less with respect to mass. Thereby, it is possible to provide an adhesive having high holding power and uniform thermal conductivity.
更に、本発明の粘着組成物前駆体は、（メタ）アクリル共重合体と、（メタ）アクリルモノマーとを含み、上記（メタ）アクリルモノマーを重合させることにより、粘着力が発生する。従って、本発明の粘着組成物前駆体自体は、粘着力を有しないか、又は小さな粘着力しか有さないものである。 Furthermore, the pressure-sensitive adhesive composition precursor of the present invention contains a (meth) acrylic copolymer and a (meth) acrylic monomer, and an adhesive force is generated by polymerizing the (meth) acrylic monomer. Accordingly, the pressure-sensitive adhesive composition precursor of the present invention itself has no adhesive force or only a small adhesive force.
また、上記（メタ）アクリルモノマーの含有量は、上記（メタ）アクリル共重合体と上記（メタ）アクリルモノマーとの合計質量に対して、７５質量％以上９９質量％以下に設定する必要がある。上記（メタ）アクリルモノマーの含有量が７５質量％を下回ると、本発明の粘着組成物前駆体の流動性が低下し、上記（メタ）アクリルモノマーの含有量が９９質量％を超えると、本発明の粘着組成物前駆体の流動性が高くなりすぎて、本発明の粘着組成物前駆体を用いた粘着シートの形成が困難となる。 Moreover, it is necessary to set content of the said (meth) acryl monomer to 75 to 99 mass% with respect to the total mass of the said (meth) acryl copolymer and the said (meth) acryl monomer. . When the content of the (meth) acrylic monomer is less than 75% by mass, the fluidity of the pressure-sensitive adhesive composition precursor of the present invention is reduced, and when the content of the (meth) acrylic monomer exceeds 99% by mass, the present The fluidity of the pressure-sensitive adhesive composition precursor of the invention becomes too high, and it becomes difficult to form a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition precursor of the present invention.
以下、本発明の粘着組成物前駆体の各成分について詳細に説明する。 Hereinafter, each component of the pressure-sensitive adhesive composition precursor of the present invention will be described in detail.
＜含水金属化合物＞
上記のとおり、本発明の板状又は鱗片状の含水金属化合物は、加熱することにより水を放出する金属化合物であり、特に水酸化アルミニウム又はベーマイトが好ましい。これらは、高い熱伝導性、難燃性及び電気絶縁性を有しているからである。本発明の粘着組成物前駆体は、水酸化アルミニウム及びベーマイトをともに含んでいてもよい。本発明の粘着組成物前駆体は、上記含水金属化合物を含んでいるため、高い熱伝導性と難燃性とを有する粘着剤を提供できる。
<Hydrous metal compound>
As described above, the plate-like or scale-like hydrated metal compound of the present invention is a metal compound that releases water by heating, and aluminum hydroxide or boehmite is particularly preferable. This is because they have high thermal conductivity, flame retardancy, and electrical insulation. The pressure-sensitive adhesive composition precursor of the present invention may contain both aluminum hydroxide and boehmite. Since the pressure-sensitive adhesive composition precursor of the present invention contains the hydrated metal compound, a pressure-sensitive adhesive having high thermal conductivity and flame retardancy can be provided.
上記含水金属化合物の平均粒子径は、２μｍ以上５０μｍ以下に設定され、２μｍ以上１０μｍ以下がより好ましい。上記含水金属化合物の平均粒子径が２μｍを下回ると、粘着剤の粘着力が低下し、上記含水金属化合物の平均粒子径が５０μｍを超えると、粘着剤の表面起伏が大きくなり、粘着剤の粘着力が低下する。本発明において上記含水金属化合物の平均粒子径は、走査型電子顕微鏡（ＳＥＭ）又は透過型電子顕微鏡（ＴＥＭ）で上記含水金属化合物の粒子を観察し、１００個の粒子の長軸径を測定し、その算術平均値として求めるものとする。 The average particle diameter of the hydrated metal compound is set to 2 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less. When the average particle diameter of the hydrated metal compound is less than 2 μm, the adhesive strength of the adhesive decreases, and when the average particle diameter of the hydrated metal compound exceeds 50 μm, the surface undulation of the adhesive increases, Power is reduced. In the present invention, the average particle diameter of the hydrated metal compound is determined by observing the particles of the hydrated metal compound with a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and measuring the major axis diameter of 100 particles. The arithmetic average value is obtained.
上記含水金属化合物のアスペクト比は、５以上に設定され、８以上がより好ましく、１０以上が更に好ましい。上記アスペクト比が５を下回ると、上記含水金属化合物の粒子形状が粒状に類似するためか、粘着剤の粘着力が低下する。本発明において上記含水金属化合物のアスペクト比は、ＳＥＭ又はＴＥＭで上記含水金属化合物の粒子を観察し、上記含水金属化合物の厚み方向の長さをｔとし、その板面の最大の長さをｄとし、ｄ／ｔで算出される値を１００個の粒子についてそれぞれ求め、その算術平均値として求めるものとする。 The aspect ratio of the hydrated metal compound is set to 5 or more, more preferably 8 or more, and still more preferably 10 or more. When the aspect ratio is less than 5, the adhesive strength of the pressure-sensitive adhesive decreases because the particle shape of the hydrated metal compound is similar to a granular shape. In the present invention, the aspect ratio of the hydrated metal compound is determined by observing the particles of the hydrated metal compound with SEM or TEM, the length in the thickness direction of the hydrated metal compound is t, and the maximum length of the plate surface is d. The value calculated by d / t is obtained for each of 100 particles, and the arithmetic average value thereof is obtained.
本発明では、上記アスペクト比が５以上の場合には、板状の粒子とし、上記アスペクト比が１５以上の場合には、鱗片状の粒子とする。 In the present invention, when the aspect ratio is 5 or more, it is a plate-like particle, and when the aspect ratio is 15 or more, it is a scaly particle.
上記含水金属化合物の含有量は、上記粘着組成物前駆体の全質量に対して３０質量％以上７０質量％以下に設定する必要があるが、粘着剤の難燃性がＪＩＳ Ｋ７２０１−２で規定する酸素指数において２１以上を達成できるように調整することが好ましい。 The content of the hydrated metal compound needs to be set to 30% by mass or more and 70% by mass or less with respect to the total mass of the adhesive composition precursor, but the flame retardancy of the adhesive is specified in JIS K7201-2. It is preferable to adjust so that an oxygen index of 21 or more can be achieved.
本発明の粘着組成物前駆体に含まれる含水金属化合物の含有量は、例えば、熱分析法により測定できる。即ち、上記粘着組成物前駆体を７００℃付近まで加熱して、残渣（水が抜けた金属化合物）の質量を測定し、その残渣の質量から上記粘着組成物前駆体に含まれる含水金属化合物の質量を求めて、その含水金属化合物の質量から粘着組成物前駆体に含まれる含水金属化合物の含有率を求めることができる。また、同様にして後述する粘着組成物（粘着剤）に含まれる含水金属化合物の含有量も測定できる。 The content of the hydrated metal compound contained in the pressure-sensitive adhesive composition precursor of the present invention can be measured by, for example, a thermal analysis method. That is, the pressure-sensitive adhesive composition precursor is heated to around 700 ° C., the mass of the residue (the metal compound from which water has been removed) is measured, and the water-containing metal compound contained in the pressure-sensitive adhesive composition precursor is measured from the mass of the residue. By obtaining the mass, the content of the hydrated metal compound contained in the pressure-sensitive adhesive composition precursor can be obtained from the mass of the hydrated metal compound. Similarly, the content of the hydrated metal compound contained in the adhesive composition (adhesive) described later can also be measured.
＜繊維状フィラー＞
本発明の繊維状フィラーは、粘着剤の粘着力、保持力及び粘着組成物前駆体の作製の観点から、平均繊維長が０．５ｍｍ以上１０ｍｍ以下であり、平均繊維径が５μｍ以上２０μｍ以下に設定される。本発明において上記繊維状フィラーの平均繊維径は、ＳＥＭで上記繊維状フィラーを観察し、１０本の異なる繊維状フィラーの径を測定し、その算術平均値として求めるものとする。上記繊維状フィラーの繊維が扁平な場合、その長軸径の算術平均値を平均繊維径とする。また、上記繊維状フィラーの平均繊維長は、肉眼、顕微鏡観察、ＳＥＭ観察等の適当な手段・方法で１０本の異なる繊維状フィラーの長さを測定し、その算術平均値として求めるものとする。
<Fibrous filler>
The fibrous filler of the present invention has an average fiber length of 0.5 mm or more and 10 mm or less and an average fiber diameter of 5 μm or more and 20 μm or less from the viewpoint of adhesive strength, holding power of the pressure-sensitive adhesive, and preparation of the adhesive composition precursor. Is set. In the present invention, the average fiber diameter of the fibrous filler is determined by observing the fibrous filler with an SEM, measuring the diameters of 10 different fibrous fillers, and calculating the arithmetic average value thereof. When the fiber of the fibrous filler is flat, the arithmetic average value of the major axis diameter is defined as the average fiber diameter. Further, the average fiber length of the fibrous filler is obtained as an arithmetic average value by measuring the lengths of ten different fibrous fillers by appropriate means and methods such as visual observation, microscopic observation, SEM observation, and the like. .
また、上記繊維状フィラーの材質は特に限定されないが、粘着剤内での応力分散の観点から、高弾性率材料からなる繊維状物が好ましく、例えば、ポリベンズアゾール系繊維、パラ系アラミド繊維、超高分子量ポリエチレン繊維、及びポリアリレート繊維等が好ましい。ここで、上記超高分子量ポリエチレン繊維は従来公知のものを用いればよく、平均分子量１００万以上のものを用いることが好ましい。 Further, the material of the fibrous filler is not particularly limited, but from the viewpoint of stress dispersion in the pressure-sensitive adhesive, a fibrous material made of a high elastic modulus material is preferable, for example, polybenzazole fiber, para-aramid fiber, Ultra high molecular weight polyethylene fibers and polyarylate fibers are preferred. Here, as the ultra high molecular weight polyethylene fiber, a conventionally known one may be used, and one having an average molecular weight of 1 million or more is preferably used.
上記繊維状フィラーとしては、特にポリベンズアゾール系繊維のポリパラフェニレンベンゾビスオキサゾール（以下、ＰＢＯという。）を用いることが好ましい。ＰＢＯは他の繊維に比較して熱伝導率が高く、粘着層の熱伝導率の向上が期待される。但し、上記繊維状フィラーには、粘着剤の耐電圧性及び絶縁性が低下するため炭素繊維は用いないほうが好ましい。 As the fibrous filler, it is particularly preferable to use polyparaphenylene benzobisoxazole (hereinafter referred to as PBO), which is a polybenzazole fiber. PBO has a higher thermal conductivity than other fibers, and is expected to improve the thermal conductivity of the adhesive layer. However, it is preferable not to use carbon fiber for the fibrous filler because the voltage resistance and insulation of the adhesive are reduced.
＜（メタ）アクリル共重合体＞
本発明の粘着組成物前駆体に含まれる（メタ）アクリル共重合体は、（メタ）アクリルモノマーをモノマー成分とするポリマーである。上記モノマー成分となる（メタ）アクリルモノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステル又はその誘導体が挙げられる。上記（メタ）アクリル酸エステルとしては、例えば、炭素数が１〜１８のアルキル基を有する（メタ）アクリレートが使用でき、具体的には、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸２エチルヘキシル、メタクリル酸２エチルヘキシル、アクリル酸イソボルニル、アクリル酸デシル、アクリル酸ステアリル等が使用できる。上記モノマー成分となる（メタ）アクリルモノマーは、１種又は２種以上を使用できる。
<(Meth) acrylic copolymer>
The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition precursor of the present invention is a polymer having a (meth) acrylic monomer as a monomer component. Examples of the (meth) acrylic monomer serving as the monomer component include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof. As said (meth) acrylic acid ester, the (meth) acrylate which has a C1-C18 alkyl group can be used, for example, Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid Ethyl, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, decyl acrylate, stearyl acrylate, and the like can be used. 1 type (s) or 2 or more types can be used for the (meth) acryl monomer used as the said monomer component.
本発明の粘着組成物前駆体に含まれる（メタ）アクリル共重合体は、官能基を有することが好ましい。上記（メタ）アクリル共重合体が官能基を有することにより、上記含水金属化合物との結合力が向上し、粘着力が向上するからである。上記官能基としては、ヒドロキシル基、カルボキシル基、アミノ基、置換アミノ基、エポキシ基等が挙げられる。中でもカルボキシル基等の酸性官能基がより好ましい。カルボキシル基等の酸性官能基を有する（メタ）アクリル共重合体は、上記含水金属化合物との結合力がより向上するからである。 The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition precursor of the present invention preferably has a functional group. This is because, when the (meth) acrylic copolymer has a functional group, the binding force with the hydrated metal compound is improved and the adhesive strength is improved. Examples of the functional group include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group. Of these, acidic functional groups such as carboxyl groups are more preferred. This is because the (meth) acrylic copolymer having an acidic functional group such as a carboxyl group further improves the binding force with the hydrated metal compound.
本発明の粘着組成物前駆体に含まれる（メタ）アクリル共重合体に官能基を付与するためには、そのモノマー成分となる上記（メタ）アクリルモノマーに、官能基を有する（メタ）アクリルモノマーを含めればよい。上記官能基を有する（メタ）アクリルモノマーとしては、例えば、アクリル酸、メタクリル酸、アクリル酸２ヒドロキシエチル、アクリル酸２ヒドロキシプロピル、アクリル酸２ヒドロキシブチル、βカルボキシエチルアクリル酸、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド等が挙げられる。上記官能基を有する（メタ）アクリルモノマーも１種又は２種以上を使用できる。 In order to impart a functional group to the (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition precursor of the present invention, the (meth) acrylic monomer having a functional group in the (meth) acrylic monomer serving as the monomer component Should be included. Examples of the (meth) acrylic monomer having the above functional group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, β-carboxyethylacrylic acid, acrylamide, N, N -Dimethylacrylamide etc. are mentioned. One or more (meth) acrylic monomers having the above functional group can also be used.
上記官能基の効果を確保するために、上記官能基を有する（メタ）アクリルモノマーの含有量は、上記モノマー成分となる上記（メタ）アクリルモノマーの全質量に対して、１質量％以上３０質量％以下が好ましく、１〜１５質量％がより好ましい。 In order to ensure the effect of the functional group, the content of the (meth) acrylic monomer having the functional group is 1% by mass or more and 30% by mass with respect to the total mass of the (meth) acrylic monomer serving as the monomer component. % Or less is preferable and 1-15 mass% is more preferable.
＜（メタ）アクリルモノマー＞
本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーとしては、従来公知のものを好適に用いることができるが、特に前述の本発明の粘着組成物前駆体に含まれる（メタ）アクリル共重合体のモノマー成分となる（メタ）アクリルモノマーと同様のモノマーを用いることが好ましい。本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーとしても、官能基を有する（メタ）アクリルモノマーを含めることが好ましく、特に酸性官能基を有する（メタ）アクリルモノマーを含めることがより好ましい。上記（メタ）アクリルモノマーが官能基を有することにより、上記含水金属化合物と上記（メタ）アクリルモノマーとが結合し、上記粘着組成物前駆体中での上記含水金属化合物の濡れ性が向上し、上記粘着組成物前駆体の組成の均質化を図ることができる。
<(Meth) acrylic monomer>
As the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention, conventionally known ones can be suitably used, and in particular, the (meth) acrylic contained in the above-mentioned pressure-sensitive adhesive composition precursor of the present invention. It is preferable to use the same monomer as the (meth) acrylic monomer that becomes the monomer component of the copolymer. As the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention, it is preferable to include a (meth) acrylic monomer having a functional group, and more particularly to include a (meth) acrylic monomer having an acidic functional group. preferable. When the (meth) acrylic monomer has a functional group, the hydrated metal compound and the (meth) acrylic monomer are combined to improve the wettability of the hydrated metal compound in the adhesive composition precursor, The composition of the pressure-sensitive adhesive composition precursor can be homogenized.
上記官能基の効果を確保するために、上記官能基を有する（メタ）アクリルモノマーの含有量は、上記粘着組成物前駆体に含まれる（メタ）アクリルモノマーの全質量に対して、１質量％以上３０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましい。 In order to ensure the effect of the functional group, the content of the (meth) acrylic monomer having the functional group is 1% by mass with respect to the total mass of the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor. The content is preferably 30% by mass or less and more preferably 1% by mass or more and 15% by mass or less.
＜アクリルシロップ＞
本発明の粘着組成物前駆体に含まれる上記（メタ）アクリル共重合体と、上記（メタ）アクリルモノマーとは、それぞれ別々に準備してもよいが、当初から上記（メタ）アクリル共重合体と上記（メタ）アクリルモノマーとを含む市販のアクリルシロップを用いることが簡便で好ましい。上記アクリルシロップとしては、例えば、綜研化学社製の無溶剤型アクリル粘着剤“ＳＫダインシロップシリーズ”、東亜合成社製のＵＶ硬化型粘着剤“アロンタックＵＶＡシリーズ”等が挙げられる。
<Acrylic syrup>
The (meth) acrylic copolymer and the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention may be prepared separately, but the (meth) acrylic copolymer from the beginning. And a commercially available acrylic syrup containing the above (meth) acrylic monomer is convenient and preferable. Examples of the acrylic syrup include a solvent-free acrylic adhesive “SK Dyne Syrup Series” manufactured by Soken Chemical Co., Ltd., and a UV curable adhesive “Arontack UVA Series” manufactured by Toa Gosei Co., Ltd.
上記アクリルシロップには、本発明の粘着組成物前駆体の粘度又は特性を調整するため、（メタ）アクリルモノマーを更に加えてもよい。追加する（メタ）アクリルモノマーとしては、前述した本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーと同様のモノマーを用いることができる。 In order to adjust the viscosity or characteristics of the pressure-sensitive adhesive composition precursor of the present invention, a (meth) acrylic monomer may be further added to the acrylic syrup. As the (meth) acrylic monomer to be added, the same monomer as the (meth) acrylic monomer contained in the above-mentioned pressure-sensitive adhesive composition precursor of the present invention can be used.
＜分散剤＞
上記含水金属化合物を上記アクリルシロップと混合すると、増粘することがある。これは、上記含水金属化合物と上記アクリルシロップ中の（メタ）アクリル共重合体との相互作用によると考えられる。このため、本発明の粘着組成物前駆体には、増粘現象を抑制するため、分散剤を添加してもよい。上記分散剤としては、上記（メタ）アクリル共重合体及び上記（メタ）アクリルモノマーとの親和性が良好な高分子系分散剤が好ましい。上記高分子系分散剤としては、例えば、アクリル系、ビニル系、ポリエステル系、ポリウレタン系、ポリエーテル系、エポキシ系、ポリスチレン系、アミノ系等の高分子化合物が挙げられる。上記分散剤は、１種類を単独で用いることもできるが、２種類以上を混合して用いてもよい。
<Dispersant>
When the hydrated metal compound is mixed with the acrylic syrup, viscosity may increase. This is considered to be due to the interaction between the hydrated metal compound and the (meth) acrylic copolymer in the acrylic syrup. Therefore, a dispersant may be added to the pressure-sensitive adhesive composition precursor of the present invention in order to suppress the thickening phenomenon. As the dispersant, a polymer dispersant having good affinity with the (meth) acrylic copolymer and the (meth) acrylic monomer is preferable. Examples of the polymer dispersant include polymer compounds such as acrylic, vinyl, polyester, polyurethane, polyether, epoxy, polystyrene, and amino. Although the said dispersing agent can also be used individually by 1 type, you may mix and use 2 or more types.
上記分散剤は、分散機能を高めるために官能基を有していることが好ましい。上記官能基としては、カルボキシル基、リン酸基、スルホン酸基、カルボン酸エステル基、リン酸エステル基、スルホン酸エステル基、ヒドロキシル基、アミノ基、四級アンモニウム塩基、アミド基等が挙げられるが、上記分散剤は、酸性官能基と塩基性官能基の両方を有している両性分散剤であることがより好ましい。 The dispersant preferably has a functional group in order to enhance the dispersion function. Examples of the functional group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a carboxylic acid ester group, a phosphoric acid ester group, a sulfonic acid ester group, a hydroxyl group, an amino group, a quaternary ammonium base, and an amide group. The dispersant is more preferably an amphoteric dispersant having both an acidic functional group and a basic functional group.
上記分散剤の酸性度はその酸価を基準として決定し、上記分散剤の塩基性度はそのアミン価を基準として決定する。酸価が２０ｍｇＫＯＨ／ｇ以上である分散剤を用いることで、上記粘着組成物前駆体の増粘現象を防止できる。また、アミン価が５ｍｇＫＯＨ／ｇ以上である分散剤を用いることで、粘着剤の保存時の粘着力の変化を防止できる。上記分散剤の酸性官能基は上記含水金属化合物の塩基性活性点を覆い、上記含水金属化合物と上記（メタ）アクリル共重合体との相互作用を抑制するため、上記粘着組成物前駆体の増粘現象を防止すると考えられる。また、上記分散剤中の塩基性官能基は上記（メタ）アクリル共重合体中の酸性官能基と相互作用し、上記分散剤が上記粘着組成物前駆体の界面に移行することを抑制するため、粘着剤の保存時の粘着力の変化を防止すると考えられる。 The acidity of the dispersant is determined on the basis of its acid value, and the basicity of the dispersant is determined on the basis of its amine value. By using a dispersant having an acid value of 20 mgKOH / g or more, the thickening phenomenon of the pressure-sensitive adhesive composition precursor can be prevented. Moreover, the change of the adhesive force at the time of preservation | save of an adhesive can be prevented by using the dispersing agent whose amine value is 5 mgKOH / g or more. The acidic functional group of the dispersant covers the basic active site of the hydrated metal compound and suppresses the interaction between the hydrated metal compound and the (meth) acrylic copolymer. It is thought to prevent stickiness. In addition, the basic functional group in the dispersant interacts with the acidic functional group in the (meth) acrylic copolymer to suppress the dispersant from moving to the interface of the pressure-sensitive adhesive composition precursor. It is considered that the adhesive force change during storage of the adhesive is prevented.
上記分散剤の含有量は、上記含水金属化合物１００質量部に対して０．１〜１５質量部とすることが好ましく、０．３〜１０質量部がより好ましい。上記分散剤の含有量が０．１質量部未満では充分な分散性が得られず、上記分散剤の含有量が１５質量部を超えると、高温下での接着性が低下し易く、粘着力や保持力への影響が懸念される。 The content of the dispersant is preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the hydrated metal compound. If the content of the dispersant is less than 0.1 parts by mass, sufficient dispersibility cannot be obtained. If the content of the dispersant exceeds 15 parts by mass, the adhesiveness at high temperatures tends to decrease, and the adhesive strength And there is concern about the impact on holding power.
＜光重合開始剤＞
本発明の粘着組成物前駆体は、光重合開始剤を更に含むことが好ましい。上記光重合開始剤としては、例えば、アセトフェノン類、べンゾフェノン類、ケタール類、アントラキノン類、チオキサントン類、アゾ化合物、過酸化物、２，３−ジアルキルジオン化合物、ジスルフィド化合物、チウラム化合物、フルオロアミン化合物等を使用できる。これらの光重合開始剤は少なくとも１種を使用すればよい。上記光重合開始剤の使用量は特に限定されないが、樹脂成分である（メタ）アクリル共重合体と（メタ）アクリルモノマーとの合計１００質量部に対して、０．０１〜３質量部とすればよく、０．１〜２質量部が好ましい。
<Photopolymerization initiator>
The pressure-sensitive adhesive composition precursor of the present invention preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, and fluoroamine compounds. Etc. can be used. These photopolymerization initiators may be used at least one kind. Although the usage-amount of the said photoinitiator is not specifically limited, It is 0.01-3 mass parts with respect to a total of 100 mass parts of the (meth) acryl copolymer and (meth) acryl monomer which are resin components. What is necessary is just 0.1-2 mass parts.
＜架橋剤＞
本発明の粘着組成物前駆体は、架橋剤を更に含んでいてもよい。上記架橋剤としては、例えば、１，６−ヘキサンジオールジアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリプロピレンジ（メタ）アクリレート、ジペンタエリスリトールヘキサアクリレート等の多官能（メタ）アクリレートモノマーが挙げられる。上記架橋剤の添加量は、樹脂成分である（メタ）アクリル共重合体と（メタ）アクリルモノマーとの合計１００質量部に対して、０．０５〜５質量部とすればよい。
<Crosslinking agent>
The pressure-sensitive adhesive composition precursor of the present invention may further contain a crosslinking agent. Examples of the crosslinking agent include 1,6-hexanediol diacrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. And polyfunctional (meth) acrylate monomers such as tripropylene di (meth) acrylate and dipentaerythritol hexaacrylate. What is necessary is just to let the addition amount of the said crosslinking agent be 0.05-5 mass parts with respect to a total of 100 mass parts of the (meth) acryl copolymer and (meth) acryl monomer which are resin components.
＜その他の成分＞
本発明の粘着組成物前駆体には、必要に応じ粘着付与剤を添加してもよい。上記粘着付与剤としては、例えば、テルペン系樹脂、テルペンフェノール樹脂、ロジン系樹脂、石油系樹脂（Ｃ５系石油樹脂、Ｃ９系石油樹脂）、フェノール系樹脂、マロン−インデン樹脂、脂環族系石油樹脂、脂環族系水添石油樹脂、スチレン系樹脂、ジシクロペンタジエン樹脂等が挙げられる。上記粘着付与剤の配合量は、樹脂成分である上記（メタ）アクリル共重合体と上記（メタ）アクリルモノマーとの合計１００質量部に対して、２〜２００質量部が好ましい。
<Other ingredients>
You may add a tackifier to the adhesive composition precursor of this invention as needed. Examples of the tackifier include terpene resins, terpene phenol resins, rosin resins, petroleum resins (C5 petroleum resins, C9 petroleum resins), phenol resins, malon-indene resins, and alicyclic petroleum oils. Examples thereof include resins, alicyclic hydrogenated petroleum resins, styrene resins, and dicyclopentadiene resins. As for the compounding quantity of the said tackifier, 2-200 mass parts is preferable with respect to a total of 100 mass parts of the said (meth) acryl copolymer which is a resin component, and the said (meth) acryl monomer.
本発明の粘着組成物前駆体の製造方法は特に限定されず、例えば、上記各成分を混合して、各固形成分を十分に分散すればよい。上記混合方法は特に限定されないが、例えば、ディスパー、ホモミキサー、リボンミキサー、パドルミキサー、プラネタリミキサー、ロールミル、ニーダー、ボールミル、サンドミル、超音波分散機等を用いて混合することができる。 The method for producing the pressure-sensitive adhesive composition precursor of the present invention is not particularly limited. For example, the above-described components may be mixed and the solid components may be sufficiently dispersed. Although the said mixing method is not specifically limited, For example, it can mix using a disper, a homomixer, a ribbon mixer, a paddle mixer, a planetary mixer, a roll mill, a kneader, a ball mill, a sand mill, an ultrasonic disperser etc.
（本発明の粘着組成物）
本発明の粘着組成物は、上記本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーを重合して形成したものである。上記（メタ）アクリルモノマーを重合することにより、上記粘着組成物前駆体が粘着力を有する粘着組成物、即ち粘着剤となる。本発明の粘着組成物は、上記本発明の粘着組成物前駆体に含まれる（メタ）アクリルモノマーを重合して形成したものであるため、熱伝導性が高く、粘着性能が良好となる。
(Adhesive composition of the present invention)
The pressure-sensitive adhesive composition of the present invention is formed by polymerizing a (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention. By polymerizing the (meth) acrylic monomer, the pressure-sensitive adhesive composition precursor becomes a pressure-sensitive adhesive composition having adhesive strength, that is, a pressure-sensitive adhesive. Since the pressure-sensitive adhesive composition of the present invention is formed by polymerizing the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor of the present invention, the thermal conductivity is high and the pressure-sensitive adhesive performance is good.
従って、本発明の粘着組成物は、上記本発明の粘着組成物前駆体を調製する工程と、上記粘着組成物前駆体に含まれる上記（メタ）アクリルモノマーを重合する工程とを備える製造方法で製造できる。上記（メタ）アクリルモノマーを重合する方法は特に限定されないが、上記粘着組成物前駆体に紫外線等の電離放射線を照射する方法を用いることができる。 Therefore, the pressure-sensitive adhesive composition of the present invention is a production method comprising a step of preparing the pressure-sensitive adhesive composition precursor of the present invention and a step of polymerizing the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor. Can be manufactured. A method for polymerizing the (meth) acrylic monomer is not particularly limited, and a method of irradiating the pressure-sensitive adhesive composition precursor with ionizing radiation such as ultraviolet rays can be used.
上記電離放射線としては、例えば、紫外線、電子線、β線等を用いることができるが、簡便に利用できることから、紫外線が多用される。紫外線の光源としては、高圧水銀灯、メタルハライドランプ、紫外線ＬＥＤランプ等が使用できる。上記電離放射線として紫外線を用いる場合には、上記粘着組成物前駆体には光重合開始剤を含めることが好ましい。 As the ionizing radiation, for example, ultraviolet rays, electron beams, β rays, and the like can be used, but ultraviolet rays are frequently used because they can be easily used. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, an ultraviolet LED lamp, or the like can be used. When ultraviolet rays are used as the ionizing radiation, it is preferable to include a photopolymerization initiator in the pressure-sensitive adhesive composition precursor.
（本発明の粘着シート）
本発明の粘着シートは、上記本発明の粘着組成物をシート状に成形したものである。本発明の粘着シートは、上記本発明の粘着組成物を成形したものであるため、熱伝導性が高く、粘着性能が良好となる。
(Adhesive sheet of the present invention)
The pressure-sensitive adhesive sheet of the present invention is obtained by molding the pressure-sensitive adhesive composition of the present invention into a sheet shape. Since the pressure-sensitive adhesive sheet of the present invention is obtained by molding the pressure-sensitive adhesive composition of the present invention, it has high thermal conductivity and good pressure-sensitive adhesive performance.
本発明の粘着シートの厚さは特に限定されず、例えば、１０〜８００μｍとすることができる。 The thickness of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and can be, for example, 10 to 800 μm.
本発明の粘着シートは、両面に剥離基材を更に備えていてもよい。上記剥離基材を備えることにより、本発明の粘着シートの取り扱いが容易となる。 The pressure-sensitive adhesive sheet of the present invention may further include a release substrate on both sides. By providing the release substrate, it is easy to handle the pressure-sensitive adhesive sheet of the present invention.
また、本発明の粘着シートは、上記本発明の粘着組成物前駆体を調製する工程と、上記粘着組成物前駆体に含まれる上記（メタ）アクリルモノマーを重合してシート状に成形する工程とを備える製造方法で製造できる。 The pressure-sensitive adhesive sheet of the present invention includes a step of preparing the pressure-sensitive adhesive composition precursor of the present invention, a step of polymerizing the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor and molding the sheet into a sheet shape, It can manufacture with a manufacturing method provided with.
上記（メタ）アクリルモノマーを重合してシート状に成形する方法は特に限定されないが、例えば、基材の上に上記粘着組成物前駆体を塗布して塗膜を形成した後に、更にその塗膜の上に基材を配置し、その後に上記塗膜に上記基材を通して、前述の紫外線等の電離放射線を照射する方法を用いることができる。その際には、上記基材として剥離基材を用いれば、剥離基材付き粘着シートを簡便に得ることができる。また。電離放射線に紫外線を用いる場合、上記基材の少なくとも一方である紫外線の照射側には透明基材を用いることが好ましい。 The method for polymerizing the (meth) acrylic monomer to form a sheet is not particularly limited. For example, after the adhesive composition precursor is applied on a substrate to form a coating film, the coating film is further formed. A method of irradiating ionizing radiation such as ultraviolet rays as described above can be used by arranging a substrate on the substrate and then passing the substrate through the substrate. In that case, if a peeling base material is used as said base material, an adhesive sheet with a peeling base material can be obtained simply. Also. When ultraviolet rays are used for ionizing radiation, it is preferable to use a transparent substrate on the ultraviolet irradiation side, which is at least one of the substrates.
また、上記粘着組成物前駆体を塗布する方法は、平滑な塗膜を形成しうる塗布方法であれば特に制限されるものではなく、例えば、グラビアロール法、マイクログラビアロール法、マイクログラビアコータ法、スリットダイコート法、コンマコート法、スプレイ法、スピン法、ナイフ法、キス法、スクイズ法、リバースロール法、ディップ法、バーコート法等が挙げられる。 Further, the method for applying the pressure-sensitive adhesive composition precursor is not particularly limited as long as it is a coating method capable of forming a smooth coating film. For example, a gravure roll method, a micro gravure roll method, a micro gravure coater method , Slit die coat method, comma coat method, spray method, spin method, knife method, kiss method, squeeze method, reverse roll method, dip method, bar coat method and the like.
上記基材としては特に限定されないが、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、ポリオレフィン類、セルローストリアセテート等のセルロース系樹脂、ナイロン、アラミド等のアミド系樹脂、ポリフェニレンエーテル、ポリスルホンエーテル等のポリエーテル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、芳香族ポリアミド系樹脂、シクロオレフィンポリマー類、紙等の材料からなる、フィルム又はシートを用いることができる。 The base material is not particularly limited. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefin resins, cellulose resins such as cellulose triacetate, amide resins such as nylon and aramid, polyphenylene ether, polysulfone ether, etc. A film or sheet made of a material such as a polyether resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, aromatic polyamide resin, cycloolefin polymer, or paper can be used.
また、上記基材に剥離性を付与するには、上記基材の少なくとも片面にシリコーン樹脂等からなる離形層を形成すればよい。 Moreover, what is necessary is just to form the release layer which consists of a silicone resin etc. in the at least single side | surface of the said base material in order to provide peelability to the said base material.
次に、本発明の粘着シートを図面に基づき説明する。図１は、本発明の粘着シートの一例を示す模式断面図である。図１において、本発明の粘着シート１０は、剥離フィルム１１及び１３の間にシート状の粘着剤１２を備えている。粘着シート１０を使用する場合には、剥離フィルム１１及び１３を除去して、シート状の粘着剤１２を接合部材の間に配置して加圧等して接合すればよい。 Next, the adhesive sheet of this invention is demonstrated based on drawing. FIG. 1 is a schematic cross-sectional view showing an example of the pressure-sensitive adhesive sheet of the present invention. In FIG. 1, the pressure-sensitive adhesive sheet 10 of the present invention includes a sheet-like pressure-sensitive adhesive 12 between release films 11 and 13. When using the pressure-sensitive adhesive sheet 10, the release films 11 and 13 may be removed, and the sheet-like pressure-sensitive adhesive 12 may be disposed between the bonding members and bonded by pressing or the like.
本発明の粘着シートの粘着力は、９０°ピール試験による粘着力が５Ｎ／１０ｍｍ以上であることが好ましい。上記粘着力が５Ｎ／１０ｍｍ未満であると、例えば、発熱する電子部品等と、ヒートシンク、放熱フィン等の放熱部材との間で剥離が生じる懸念がある。 The adhesive strength of the pressure-sensitive adhesive sheet of the present invention is preferably 5 N / 10 mm or higher as determined by a 90 ° peel test. If the adhesive force is less than 5 N / 10 mm, for example, there is a concern that peeling occurs between a heat generating electronic component or the like and a heat radiating member such as a heat sink or a heat radiating fin.
また、本発明の粘着シートの保持力は、後述する測定条件で測定した場合、落下時間換算で２４時間以上であることが好ましい。上記保持力が落下時間換算で２４時間未満であると、例えば、発熱する電子部品等と、ヒートシンク、放熱フィン等の放熱部材との間で接合位置にズレが生じる懸念がある。 In addition, the holding force of the pressure-sensitive adhesive sheet of the present invention is preferably 24 hours or more in terms of drop time when measured under the measurement conditions described later. If the holding force is less than 24 hours in terms of drop time, for example, there is a concern that a joining position may be deviated between a heat generating electronic component or the like and a heat radiating member such as a heat sink or a heat radiating fin.
本発明の粘着シートの熱伝導率は、熱伝達性を十分発現させるために、０．５Ｗ／ｍ・Ｋ以上であることが好ましい。 The thermal conductivity of the pressure-sensitive adhesive sheet of the present invention is preferably 0.5 W / m · K or more in order to sufficiently exhibit heat transferability.
（本発明の電子機器）
本発明の電子機器は、上記本発明の粘着シートを備え、上記粘着シートにより、発熱する電子部品等と、ヒートシンク、放熱フィン等の放熱部材とを接合している。本発明の電子機器は、本発明の粘着シートを用いて発熱部材と放熱部材とを接合しているため、上記電子機器の温度上昇を抑制できる。
(Electronic device of the present invention)
An electronic device according to the present invention includes the pressure-sensitive adhesive sheet according to the present invention, and uses the pressure-sensitive adhesive sheet to join an electronic component that generates heat and a heat radiating member such as a heat sink or a heat radiating fin. Since the electronic device of this invention has joined the heat generating member and the heat radiating member using the adhesive sheet of this invention, it can suppress the temperature rise of the said electronic device.
以下、実施例により本発明を詳細に説明する。但し、本発明は以下の実施例に限定されるものではない。また、以下の実施例では「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following examples, “part” means “part by mass”.
（実施例１）
＜粘着組成物前駆体（粘着剤前駆体）の調製＞
先ず、以下の成分（１）〜（６）をプラネタリーミキサーに入れて混合して混合液を調製した。
（１）アクリルシロップ（綜研化学社製、商品名“ＳＫダインシロップＢ”、２エチルヘキシルアクリレート：９０質量部／アクリル酸：９質量部／２ヒドロキシエチルアクリレート：１質量部からなる部分共重合物）：３５．４部
（２）２エチルヘキシルアクリレート：３１．９部
（３）アクリル酸：３．５４部
（４）架橋剤（トリメチロールプロパントリアクリレート）：０．１８部
（５）分散剤（ビックケミー社製、商品名“ＤＩＳＰＥＲＢＹＫ１４５”、両性分散剤）：５部
（６）光重合開始剤〔ビス（２,４,６−トリメチルベンゾイル）フェニルフォスフィンオキサイド〕：０．３５部
Example 1
<Preparation of adhesive composition precursor (adhesive precursor)>
First, the following components (1) to (6) were put in a planetary mixer and mixed to prepare a mixed solution.
(1) Acrylic syrup (manufactured by Soken Chemical Co., Ltd., trade name “SK Dyne Syrup B”, 2-ethylhexyl acrylate: 90 parts by mass / acrylic acid: 9 parts by mass / 2 hydroxyethyl acrylate: 1 part by mass) : 35.4 parts (2) 2-ethylhexyl acrylate: 31.9 parts (3) Acrylic acid: 3.54 parts (4) Crosslinker (trimethylolpropane triacrylate): 0.18 parts (5) Dispersant (Big Chemie) Product name “DISPERBYK145”, amphoteric dispersant): 5 parts (6) Photopolymerization initiator [bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide]: 0.35 parts
次に、上記混合液に下記成分（７）及び（８）を配合して混合した後、更にディスパーを用いて水冷しながら攪拌して粘着剤前駆体（粘着組成物前駆体）を得た。
（７）含水金属化合物（板状ベーマイト、平均粒子径：４μｍ、アスペクト比：１０）：１００部
（８）繊維状フィラー（ＰＢＯ繊維、東洋紡社製、“ザイロンＨＭチョップドファイバー”、平均繊維長：１ｍｍ、平均繊維径：１２μｍ）：１．７６部
Next, the following components (7) and (8) were blended into the above mixed solution and mixed, and then further stirred with water using a disper to obtain an adhesive precursor (adhesive composition precursor).
(7) Hydrous metal compound (plate boehmite, average particle size: 4 μm, aspect ratio: 10): 100 parts (8) Fibrous filler (PBO fiber, manufactured by Toyobo Co., Ltd., “Zylon HM chopped fiber”, average fiber length: 1 mm, average fiber diameter: 12 μm): 1.76 parts
＜粘着シートの作製＞
厚さ３８μｍの離型ポリエチレンテレフタレート（ＰＥＴ）フィルム（中本パックス社製、“ＮＳ-５０−ＭＢ”）の上に、上記粘着剤前駆体を塗布して塗膜を形成した後、その塗膜の上に、厚さ５０μｍの離型ＰＥＴフィルム（中本パックス社製、“ＮＳ−３８−Ａ”）を重ねた後、コンマコーターで塗膜の厚さの調整を行い、その後に紫外線を照射して上記塗膜の硬化処理を行い、離型ＰＥＴフィルム付きの粘着シートを作製した。上記コンマコーターでの厚さ調整は、バックアップロールとナイフロールとのギャップ間隔を硬化処理後の粘着シートの厚さが２５０μｍになるように設定して行った。上記紫外線照射は、波長３６５ｎｍにピークを持つブラックライトを用いて積算光量を３００ｍＪ／ｃｍ2とし、更に高圧水銀灯用いて積算光量を２５０ｍＪ／ｃｍ2となるように行った。
<Production of adhesive sheet>
On the release polyethylene terephthalate (PET) film of 38 μm thickness (“NS-50-MB”, manufactured by Nakamoto Pax Co., Ltd.) On top of this, a 50 μm thick release PET film (Nakamoto Pax, NS-38-A) is stacked, and then the thickness of the coating film is adjusted with a comma coater, and then irradiated with ultraviolet rays. Then, the coating film was cured to produce an adhesive sheet with a release PET film. The thickness adjustment with the comma coater was performed by setting the gap interval between the backup roll and the knife roll so that the thickness of the pressure-sensitive adhesive sheet after the curing treatment was 250 μm. The ultraviolet irradiation was performed using a black light having a peak at a wavelength of 365 nm so that the integrated light amount was 300 mJ / cm 2 and further using a high-pressure mercury lamp so that the integrated light amount was 250 mJ / cm 2 .
（実施例２）
繊維状フィラーの配合量を５．２９部とした以外は、実施例１と同様にして粘着シートを作製した。
(Example 2)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount of the fibrous filler was 5.29 parts.
（実施例３）
繊維状フィラーをアラミド繊維（デュポン社製、“ケブラーチョップドファイバー”、平均繊維長：５ｍｍ、平均繊維径：１３μｍ）：０．５３部に変更した以外は、実施例１と同様にして粘着シートを作製した。
(Example 3)
An adhesive sheet was prepared in the same manner as in Example 1 except that the fibrous filler was changed to aramid fiber (manufactured by DuPont, “Kevlar chopped fiber”, average fiber length: 5 mm, average fiber diameter: 13 μm): 0.53 parts. Produced.
（比較例１）
繊維状フィラーを添加しなかった以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 1)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the fibrous filler was not added.
（比較例２）
含水金属化合物を粒状ベーマイト（平均粒子径：１μｍ、アスペクト比：１．５）：１００部に変更した以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 2)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the hydrous metal compound was changed to granular boehmite (average particle size: 1 μm, aspect ratio: 1.5): 100 parts.
（比較例３）
含水金属化合物を粒状ベーマイト（平均粒子径：１μｍ、アスペクト比：１．５）：１００部に変更し、繊維状フィラーを添加しなかった以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 3)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the hydrous metal compound was changed to granular boehmite (average particle size: 1 μm, aspect ratio: 1.5): 100 parts and no fibrous filler was added. .
（比較例４）
繊維状フィラーをカーボンナノファイバー（昭和電工社製、“ＶＧＣＦ−Ｈ”、平均繊維長：０．０１ｍｍ、平均繊維径：０．１５μｍ）：０．０１８部に変更した以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 4)
Example 1 except that the fibrous filler was changed to carbon nanofiber (Showa Denko, “VGCF-H”, average fiber length: 0.01 mm, average fiber diameter: 0.15 μm): 0.018 part. An adhesive sheet was produced in the same manner.
（比較例５）
繊維状フィラーをアラミド繊維（帝人社製、“コーネックスチョップドファイバー”、平均繊維長：１ｍｍ、平均繊維径：２５μｍ）：１．７６部に変更した以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 5)
Adhesive sheet in the same manner as in Example 1 except that the fibrous filler was changed to aramid fiber (manufactured by Teijin Ltd., “Conex chopped fiber”, average fiber length: 1 mm, average fiber diameter: 25 μm): 1.76 parts. Was made.
（比較例６）
繊維状フィラーの配合量を０．１８部とした以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 6)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the blending amount of the fibrous filler was 0.18 part.
（比較例７）
繊維状フィラーの配合量を１０．５８部とした以外は、実施例１と同様にして粘着シートを作製した。
(Comparative Example 7)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the amount of the fibrous filler was 10.58 parts.
＜粘着シートの評価＞
実施例１〜３及び比較例１〜７で作製した離型ＰＥＴフィルム付きの粘着シートの粘着性能と熱伝導率を下記のようにして評価した。
<Evaluation of adhesive sheet>
The pressure-sensitive adhesive performance and thermal conductivity of the pressure-sensitive adhesive sheets with release PET films prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were evaluated as follows.
＜粘着力＞
作製した離型ＰＥＴフィルム付きの粘着シートからＰＥＴフィルムを全て剥離し、ＰＥＴフィルムを剥離した後の粘着シートを、厚さ５０μｍの離型処理していない通常のＰＥＴフィルムに貼り付け、そのＰＥＴフィルム付き粘着シートを幅２５ｍｍ、長さ２５０ｍｍに切断して評価サンプルを作製し、その評価サンプルの粘着シート側をステンレス鋼板に貼りつけて、質量２ｋｇのローラーにて速度３００ｍｍ／分で評価サンプルの上を１往復して、評価サンプルをステンレス鋼板に圧着し、２４時間放置した。その後、評価サンプルをステンレス鋼板から剥離する９０°ピール試験を剥離速度３００ｍｍ／分で行い、測定した剥離荷重を１０ｍｍ幅に換算して、粘着力の測定値とした。
<Adhesive strength>
All of the PET film is peeled from the produced pressure-sensitive adhesive sheet with a release PET film, and the pressure-sensitive adhesive sheet after peeling the PET film is attached to a normal PET film having a thickness of 50 μm which has not been subjected to release treatment, and the PET film. The attached adhesive sheet is cut into a width of 25 mm and a length of 250 mm to prepare an evaluation sample, the adhesive sheet side of the evaluation sample is attached to a stainless steel plate, and the evaluation sample is put on the evaluation sample at a speed of 300 mm / min with a 2 kg roller. Was reciprocated once, and the evaluation sample was pressure-bonded to a stainless steel plate and left for 24 hours. Thereafter, a 90 ° peel test for peeling the evaluation sample from the stainless steel plate was performed at a peeling speed of 300 mm / min, and the measured peeling load was converted to a width of 10 mm to obtain a measured value of adhesive strength.
＜保持力＞
作製した離型ＰＥＴフィルム付きの粘着シートからＰＥＴフィルムを全て剥離し、ＰＥＴフィルムを剥離した後の粘着シートを、２５×２５ｍｍの形状でステンレス鋼板に貼りつけ、粘着シートの他方の面をアルミニウム箔で裏打ちして評価サンプルを作製した。次に、質量５ｋｇのローラーにて速度３００ｍｍ／分で評価サンプルの上を１往復して、評価サンプルをステンレス鋼板に圧着し、２４時間放置した。その後、評価サンプルを１２０℃の環境に２０分間保存した後、評価サンプルに０．５ｋｇの荷重を加えて放置した。その後、粘着部分が剥離して落下するまでの時間を測定して、落下時間換算の保持力とした。
<Retention force>
All of the PET film is peeled from the prepared pressure-sensitive adhesive sheet with a release PET film, and the pressure-sensitive adhesive sheet after peeling the PET film is attached to a stainless steel plate in a 25 × 25 mm shape, and the other surface of the pressure-sensitive adhesive sheet is aluminum foil. A sample for evaluation was prepared. Next, the evaluation sample was reciprocated once at a speed of 300 mm / min with a 5 kg roller, and the evaluation sample was pressed onto a stainless steel plate and left for 24 hours. Thereafter, the evaluation sample was stored in an environment of 120 ° C. for 20 minutes, and then a 0.5 kg load was applied to the evaluation sample and left standing. Thereafter, the time until the adhesive part peeled off and dropped was measured, and the retention time in terms of dropping time was obtained.
＜熱伝導率＞
作製した離型ＰＥＴフィルム付きの粘着シートからＰＥＴフィルムを全て剥離し、ＰＥＴフィルムを剥離した後の粘着シートを、幅５０ｍｍ、長さ１５０ｍｍに切断して評価サンプルを作製し、その評価サンプルを５枚重ねて積層体とし、京都電子工業社製の迅速熱伝導率計“ＱＴＭ−５００”を用い、薄膜測定用ソフトと組み合わせて上記積層体の熱伝導率を測定した。本測定のレファランスには、シリコン樹脂、石英、ジルコニアを用いた。
<Thermal conductivity>
All of the PET film is peeled from the prepared pressure-sensitive adhesive sheet with a release PET film, and the pressure-sensitive adhesive sheet after peeling the PET film is cut into a width of 50 mm and a length of 150 mm to prepare an evaluation sample. The laminated body was made into a laminated body, and the thermal conductivity of the laminated body was measured using a rapid thermal conductivity meter “QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd. in combination with the thin film measurement software. Silicon resin, quartz, and zirconia were used as a reference for this measurement.
以上の結果を表１に示す。また、表１には、用いた含水金属化合物の種類及び繊維状フィラーの材質、平均繊維長、平均繊維径、含有率も示した。 The results are shown in Table 1. Table 1 also shows the type of the hydrated metal compound used, the material of the fibrous filler, the average fiber length, the average fiber diameter, and the content.
表１から明らかなように、板状の含水金属化合物及び繊維状フィラーを用いた実施例１〜３の粘着シートは、粘着力が５Ｎ／１０ｍｍより大きく、落下時間換算の保持力は２４時間以上となり、熱伝導率も０．５Ｗ／ｍ・Ｋ以上となり、粘着性能及び熱伝導率がともに高いことが分かる。ここで、実施例１の粘着シートの粘着層の断面のＳＥＭ写真を図２に示す。図２から、繊維状フィラーの近傍（点線で囲った部分）では、含水金属化合物が粘着層の厚み方向に配向していることが分かる。これにより、粘着層の厚み方向にも熱伝導率が高い方向性が生じるため、粘着層の全体としては均一な熱伝導性を有することになり、粘着層全体の熱伝導率が高くなったものと考えられる。 As is apparent from Table 1, the adhesive sheets of Examples 1 to 3 using a plate-like hydrated metal compound and a fibrous filler have an adhesive strength of more than 5 N / 10 mm and a retention time in terms of fall time of 24 hours or more. Thus, the thermal conductivity is 0.5 W / m · K or more, which indicates that both the adhesive performance and the thermal conductivity are high. Here, the SEM photograph of the cross section of the adhesion layer of the adhesive sheet of Example 1 is shown in FIG. FIG. 2 shows that the hydrated metal compound is oriented in the thickness direction of the adhesive layer in the vicinity of the fibrous filler (portion surrounded by a dotted line). As a result, a direction with high thermal conductivity also occurs in the thickness direction of the adhesive layer, so that the adhesive layer as a whole has uniform thermal conductivity, and the thermal conductivity of the entire adhesive layer is increased. it is conceivable that.
これに対して、繊維状フィラーを添加しなかった比較例１では、保持力が劣ることが分かる。また、ここで、比較例１の粘着シートの粘着層の断面のＳＥＭ写真を図３に示す。図３から、繊維状フィラーを添加しない場合には、含水金属化合物が主として粘着層の塗布方向に配向していることが分かる。これにより、粘着層の塗布方向に熱伝導率が高い方向性が生じ、粘着層の全体としては不均一な熱伝導性を有することになり、粘着層全体の熱伝導率が実施例１よりも低くなったものと考えられる。 On the other hand, in Comparative Example 1 in which the fibrous filler was not added, it can be seen that the holding power is inferior. Moreover, the SEM photograph of the cross section of the adhesion layer of the adhesive sheet of the comparative example 1 is shown in FIG. FIG. 3 shows that when no fibrous filler is added, the hydrated metal compound is mainly oriented in the application direction of the adhesive layer. Thereby, the direction with high thermal conductivity occurs in the application direction of the adhesive layer, the adhesive layer as a whole has non-uniform thermal conductivity, and the thermal conductivity of the entire adhesive layer is higher than that of Example 1. It is thought that it became low.
また、粒状の含水金属化合物を用いた比較例２では、粘着力、保持力及び熱伝導率の全てで劣り、粒状の含水金属化合物を用い、繊維状フィラーを添加しなかった比較例３でも、粘着力、保持力及び熱伝導率の全てで劣り、繊維状フィラーの平均繊維長が０．５ｍｍを下回り、その平均繊維径が５μｍを下回った比較例４では、粘着力及び保持力が劣り、繊維状フィラーの平均繊維径が２０μｍを上回った比較例５では、粘着力及び保持力が劣り、繊維状フィラーの含有率が０．２質量％を下回った比較例６では、保持力が劣り、繊維状フィラーの含有率が５質量％を上回った比較例７では、粘着力及び保持力が劣ることが分かる。 Further, in Comparative Example 2 using a granular hydrated metal compound, the adhesive strength, holding power and thermal conductivity were all inferior, and even in Comparative Example 3 where a granular hydrated metal compound was used and no fibrous filler was added, In Comparative Example 4 in which the average fiber length of the fibrous filler is less than 0.5 mm, and the average fiber diameter is less than 5 μm, the adhesive force and the holding power are poor. In Comparative Example 5 in which the average fiber diameter of the fibrous filler exceeded 20 μm, the adhesive strength and holding power were inferior, and in Comparative Example 6 in which the fibrous filler content was less than 0.2 mass%, the holding power was inferior, In Comparative Example 7 in which the content of the fibrous filler exceeds 5% by mass, it can be seen that the adhesive force and the holding force are inferior.
本発明は、粘着性能及び熱伝導性がともに優れた粘着シートを提供でき、発熱部材と放熱部材との間を大きな粘着力及び保持力で高い熱伝導性を有しながら接合することができ、発熱部材と放熱部材とを備える電子機器の放熱性能を向上できるものである。 The present invention can provide an adhesive sheet excellent in both adhesive performance and thermal conductivity, and can be bonded while having high thermal conductivity with a large adhesive force and holding force between the heat generating member and the heat radiating member, The heat dissipation performance of an electronic device provided with a heat generating member and a heat radiating member can be improved.
１０ 粘着シート
１１、１３ 剥離フィルム
１２ 粘着剤
10 Adhesive Sheets 11, 13 Release Film 12 Adhesive
Claims (12)
前記含水金属化合物の平均粒子径が、２μｍ以上５０μｍ以下であり、
前記含水金属化合物のアスペクト比が、５以上であり、
前記含水金属化合物の含有量は、前記粘着組成物前駆体の全質量に対して、３０質量％以上７０質量％以下であり、
前記繊維状フィラーの平均繊維長が、０．５ｍｍ以上１０ｍｍ以下であり、
前記繊維状フィラーの平均繊維径が、５μｍ以上２０μｍ以下であり、
前記繊維状フィラーの含有量は、前記粘着組成物前駆体の全質量に対して、０．２質量％以上５質量％以下であり、
前記（メタ）アクリルモノマーの含有量は、前記（メタ）アクリル共重合体と前記（メタ）アクリルモノマーとの合計質量に対して、７５質量％以上９９質量％以下であることを特徴とする粘着組成物前駆体。 A pressure-sensitive adhesive composition precursor comprising a (meth) acrylic copolymer, a (meth) acrylic monomer, a plate-like or scaly hydrated metal compound, and a fibrous filler,
The average particle diameter of the hydrated metal compound is 2 μm or more and 50 μm or less,
The aspect ratio of the hydrated metal compound is 5 or more,
The content of the hydrated metal compound is 30% by mass to 70% by mass with respect to the total mass of the pressure-sensitive adhesive composition precursor,
The average fiber length of the fibrous filler is 0.5 mm or more and 10 mm or less,
The average fiber diameter of the fibrous filler is 5 μm or more and 20 μm or less,
Content of the said fibrous filler is 0.2 mass% or more and 5 mass% or less with respect to the total mass of the said adhesion composition precursor,
The content of the (meth) acrylic monomer is 75% by mass or more and 99% by mass or less based on the total mass of the (meth) acrylic copolymer and the (meth) acrylic monomer. Composition precursor.
前記粘着組成物前駆体に含まれる前記（メタ）アクリルモノマーを重合する工程とを含むことを特徴とする粘着組成物の製造方法。 Preparing the pressure-sensitive adhesive composition precursor according to claim 1,
And a step of polymerizing the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor.
前記粘着組成物前駆体に含まれる前記（メタ）アクリルモノマーを重合してシート状に成形する工程とを含むことを特徴とする粘着シートの製造方法。 Preparing the pressure-sensitive adhesive composition precursor according to claim 1,
And a step of polymerizing the (meth) acrylic monomer contained in the pressure-sensitive adhesive composition precursor to form a sheet-like shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015101797A JP6486192B2 (en) | 2015-05-19 | 2015-05-19 | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015101797A JP6486192B2 (en) | 2015-05-19 | 2015-05-19 | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016216587A JP2016216587A (en) | 2016-12-22 |
| JP6486192B2 true JP6486192B2 (en) | 2019-03-20 |
Family
ID=57578090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015101797A Active JP6486192B2 (en) | 2015-05-19 | 2015-05-19 | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6486192B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2044163B1 (en) * | 2006-07-24 | 2012-04-25 | 3M Innovative Properties Company | Electrically conductive pressure sensitive adhesives |
| JP5621592B2 (en) * | 2008-06-25 | 2014-11-12 | 日本ゼオン株式会社 | Thermally conductive pressure sensitive adhesive composition and thermally conductive pressure sensitive adhesive sheet |
| JP2011026531A (en) * | 2009-06-30 | 2011-02-10 | Nippon Zeon Co Ltd | Method for producing heat-conductive pressure-sensitive adhesive composition, heat-conductive pressure-sensitive adhesion sheet and electronic part |
| WO2011102170A1 (en) * | 2010-02-19 | 2011-08-25 | 日本ゼオン株式会社 | Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet, and electronic component |
| JP5815344B2 (en) * | 2010-10-07 | 2015-11-17 | 株式会社日本触媒 | Thermally conductive adhesive |
-
2015
- 2015-05-19 JP JP2015101797A patent/JP6486192B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016216587A (en) | 2016-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2770014B1 (en) | Thermal-conductive sheet, led mounting substrate, and led module | |
| JP5560630B2 (en) | HEAT CONDUCTIVE SHEET, METHOD FOR PRODUCING THE HEAT CONDUCTIVE SHEET, AND HEAT DISCHARGE DEVICE USING HEAT CONDUCTIVE SHEET | |
| JP6454139B2 (en) | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet | |
| JP5423455B2 (en) | HEAT CONDUCTIVE SHEET, ITS MANUFACTURING METHOD, AND HEAT DISCHARGE DEVICE USING HEAT CONDUCTIVE SHEET | |
| JP6069112B2 (en) | Thermally conductive sheet and method for producing the thermally conductive sheet | |
| TWI577959B (en) | Thermal conductive sheet, method of producing thermal conductive sheet and radiator | |
| JP5101862B2 (en) | Sheet-forming monomer composition, thermally conductive sheet and process for producing the same | |
| TW201336910A (en) | Thermal conductive sheet | |
| JP7389014B2 (en) | insulation heat dissipation sheet | |
| KR20210023862A (en) | Thermally conductive sheet | |
| JP2017092345A (en) | Heat conduction sheet and method of manufacturing the same, and semiconductor device | |
| CN111699090A (en) | Thermally conductive sheet | |
| JP2012109313A (en) | Heat conducting sheet, method for producing heat conducting sheet, and heat radiator | |
| JP2012109311A (en) | Heat transfer sheet, production method of heat transfer sheet, and heat radiation device | |
| US20220084902A1 (en) | Thermal Conducting Sheet, Method for Manufacturing Thermal Conducting Sheet, Heat Dissipation Member, and Semiconductor Device | |
| WO2022163027A1 (en) | Thermally conductive adhesive agent composition, adhesive sheet, and production method therefor | |
| JP6486192B2 (en) | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet | |
| JP2020074431A (en) | Thermally conductive sheet | |
| WO2016104169A1 (en) | Method for producing heat-conductive sheet, heat-conductive sheet, and semiconductor device | |
| JP7007161B2 (en) | Resin composition and laminate | |
| JP2013227379A (en) | Thermally-conductive adhesive sheet, method for producing the same, method for affixing thermally-conductive adhesive sheet, and affixed structure | |
| JP2021125688A (en) | Thermally conductive sheet and manufacturing method thereof, and heat dissipation part and manufacturing method thereof | |
| JP2021125687A (en) | Thermally conductive sheet and manufacturing method thereof, and heat dissipation part and manufacturing method thereof | |
| CN116964731A (en) | Heat conductive resin sheet | |
| WO2021157477A1 (en) | Thermally conductive sheet, method for manufacturing thermally conductive sheet, heat-dissipating component, and method for manufacturing heat-dissipating component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190124 |
|
| 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: 20190129 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190219 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6486192 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |