WO2023248906A1 - Sheet provided with heat insulating layer and adhesive layer - Google Patents
Sheet provided with heat insulating layer and adhesive layer Download PDFInfo
- Publication number
- WO2023248906A1 WO2023248906A1 PCT/JP2023/022127 JP2023022127W WO2023248906A1 WO 2023248906 A1 WO2023248906 A1 WO 2023248906A1 JP 2023022127 W JP2023022127 W JP 2023022127W WO 2023248906 A1 WO2023248906 A1 WO 2023248906A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- hollow particles
- heat insulating
- less
- Prior art date
Links
- 239000010410 layer Substances 0.000 title claims abstract description 106
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 65
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 129
- 150000001875 compounds Chemical class 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 121
- -1 2-propylheptyl Chemical group 0.000 description 56
- 125000000217 alkyl group Chemical group 0.000 description 28
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 25
- 238000000034 method Methods 0.000 description 18
- 239000011810 insulating material Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000005702 oxyalkylene group Chemical group 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 229920000728 polyester Polymers 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
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- 239000000654 additive Substances 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 2
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 125000002511 behenyl 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])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 2
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
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- BXBOUPUNKULVKB-UHFFFAOYSA-N 10-trimethoxysilyldecyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCOC(=O)C(C)=C BXBOUPUNKULVKB-UHFFFAOYSA-N 0.000 description 1
- CCQJKEYNLSZZNO-UHFFFAOYSA-N 10-trimethoxysilyldecyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCOC(=O)C=C CCQJKEYNLSZZNO-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 230000006866 deterioration Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000002463 lignoceryl 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])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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 125000002819 montanyl 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])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])C([H])([H])[H] 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
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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 1
- 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 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 239000005373 porous glass Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
Definitions
- the present invention relates to a sheet including a heat insulating layer and an adhesive layer.
- Nonvolatile memory which is characterized by low power consumption and high speed reading and writing, is attracting attention as a next-generation memory.
- PCM phase change memory
- MRAM magnetoresistive memory
- ReRAM resistance change memory
- Nonvolatile memory is sensitive to heat, and maintaining its quality when exposed to high temperature environments during the reflow process during packaging is an issue.
- Patent Document 1 discloses a first step of providing a heat insulating material on the surface of the magnetic recording device exposed in the reflow oven, and passing the magnetic recording device provided with the heat insulating material into the reflow oven.
- a method of manufacturing a magnetic recording device includes a reflow process that includes a second step of heating the magnetic recording device and a third step of removing the heat insulating material from the heated magnetic recording device.
- one aspect of the present invention is to provide a sheet suitable for a heat insulating material that has excellent releasability after a reflow process.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of a sheet.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the sheet.
- the sheet 10 shown in FIG. 1 includes a heat insulating layer 11 and an adhesive layer 12.
- the heat insulating layer 11 and the adhesive layer 12 may be laminated so as to be in contact with each other.
- the adhesive layer 12 includes an acrylic copolymer and a crosslinking agent having an epoxy group.
- the compound having a (meth)acryloyl group may be, for example, an alkyl (meth)acrylate.
- the alkyl group (the alkyl group portion other than the (meth)acryloyl group) in the alkyl (meth)acrylate may be linear, branched, or cyclic.
- the alkyl group may have, for example, 1 to 30 carbon atoms.
- the number of carbon atoms in the alkyl group may be 2 or more, or 3 or more, and may be 25 or less, 20 or less, 15 or less, 10 or less, 7 or less, or 5 or less.
- alkyl (meth)acrylates having a linear alkyl group examples include alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms, and linear alkyl groups having 12 to 30 carbon atoms. Examples include alkyl (meth)acrylates having
- alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. , n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and the like.
- alkyl (meth)acrylates having a branched alkyl group examples include alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms, and alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms. Examples include meth)acrylates.
- alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms examples include isomyristyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl ( Examples include meth)acrylate, isopentadecyl(meth)acrylate, isohexadecyl(meth)acrylate, isoheptadecyl(meth)acrylate, isostearyl(meth)acrylate, decyltetradecanyl(meth)acrylate, and the like.
- alkyl (meth)acrylates having an alicyclic (cyclic) alkyl group include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, Examples include terpene (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.
- Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include N-acryloylmorpholine (ACMO) and tetrahydrofurfuryl (meth)acrylate.
- Examples of compounds having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylate, hydroxyalkylcycloalkane (meth)acrylate, and the like.
- Examples of hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
- Examples thereof include meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, and 12-hydroxylauryl(meth)acrylate.
- Examples of the hydroxyalkylcycloalkane (meth)acrylate include (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
- Examples of compounds having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and monohydroxyethyl phthalate acrylate (for example, Toagosei Co., Ltd.) "Aronix M5400” manufactured by Shin Nakamura Chemical Co., Ltd.), and 2-acryloyloxyethyl succinate (for example, "NK Ester A-SA” manufactured by Shin Nakamura Chemical Co., Ltd.).
- the acrylic copolymer may contain a polymerizable compound other than the compound having a (meth)acryloyl group as a monomer unit.
- examples of other polymerizable compounds (monomer units) in the acrylic copolymer include acrylonitrile.
- the weight average molecular weight (Mw) of the acrylic copolymer may be 200,000 or more, 400,000 or more, 500,000 or more, or 600,000 or more, and is 1.2 million or less, 1.1 million or less, or 1 million or less. Good too.
- the polydispersity (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn)) of the acrylic copolymer may be 1.1 or more, or 1.5 or more, and 7 It may be less than .0.
- the glass transition temperature (Tg) of the acrylic copolymer may be -50°C or higher, or -45°C or higher, or -5°C or lower, or -10°C or lower.
- the acid value of the acrylic copolymer may be 20.0 mgKOH/g or more and 30.0 mgKOH/g or less.
- the concentration of carboxyl groups in the acrylic copolymer may be 2.00 ⁇ 10 ⁇ 4 mol/L or more and 11.00 ⁇ 10 ⁇ 4 mol/L or less.
- the content of the acrylic copolymer may be 70% by mass or more, or 80% by mass or more, and 98% by mass or less, or 95% by mass or less, based on the total mass of the adhesive layer 12.
- the crosslinking agent having an epoxy group may have 2 or more, 3 or more, or 4 or more epoxy groups.
- a crosslinking agent having four epoxy groups for example, N,N,N',N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane (a crosslinking agent represented by the following formula (B-1) ), N,N,N',N'-tetraglycidyl-m-xylene diamine (crosslinking agent represented by the following formula (B-2)), and the like.
- examples of the crosslinking agent having two or more epoxy groups include sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, and the like.
- the content of the crosslinking agent having an epoxy group may be 1% by mass or more, or 5% by mass or more, and 20% by mass or less, or 15% by mass or less, based on the total mass of the adhesive layer 12. .
- the adhesive layer 12 may further contain additives such as an antioxidant.
- an antioxidant examples include phenylamine antioxidants such as 4,4-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine and p,p'-dioctyldiphenylamine.
- the thickness of the adhesive layer 12 may be, for example, 5 ⁇ m or more, or 10 ⁇ m or more, and 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less.
- the heat insulating layer 11 may be any layer as long as it has heat insulating properties.
- the thermal conductivity of the heat insulating layer 11 at 25° C. is preferably 130 mW/(m ⁇ K) or less, 100 mW/(m ⁇ K) or less, or 80 mW/(m ⁇ K) or less.
- the material of the heat insulating layer 11 is not particularly limited.
- the heat insulating layer 11 may be a layer made of porous material.
- the porous material may be an organic porous material or an inorganic porous material.
- organic porous materials include porous materials made of resin.
- An example of a porous material made of resin is a porous material made of melamine resin (melamine sponge).
- inorganic porous materials include carbon porous materials and glass porous materials.
- An example of a porous material made of carbon is carbon felt.
- Examples of porous materials made of glass include glass fiber paper and glass felt.
- the heat insulating layer 11 may be a layer containing hollow particles.
- the heat insulating layer 11 may contain, for example, hollow particles and a matrix polymer.
- a hollow particle is a particle that has an outer shell and a hollow part.
- the hollow particles may be organic hollow particles whose outer shell is made of an organic material, or may be inorganic hollow particles whose outer shell is made of an inorganic material.
- the hollow particles may include either inorganic hollow particles or organic hollow particles, or both.
- Examples of the organic hollow particles include first hollow particles that are thermally expandable organic hollow particles, and second hollow particles that are organic hollow particles other than the first hollow particles.
- the organic hollow particles may include either one or both of the first hollow particles and the second hollow particles, and preferably include both the first hollow particles and the second hollow particles.
- the maximum volumetric expansion ratio of the first hollow particles is determined by thermomechanical analysis (TMA) between the maximum volume of the first hollow particles and the volume at 25°C when the temperature is increased at a temperature increase rate of 10°C/min. It is measured as the ratio (maximum volume/volume at 25°C).
- TMA thermomechanical analysis
- the maximum volumetric expansion factor of the first hollow particles may be, for example, 20 times or more, 30 times or more, or 40 times or more, or 120 times or less.
- the outer shell of the first hollow particle is preferably made of a polymer, more preferably a thermoplastic polymer.
- the outer shell becomes soft due to heating, so even if the liquid contained in the hollow part evaporates and the internal pressure increases, the hollow particle is difficult to break and easily expands.
- the thermoplastic polymer may be, for example, a polymer containing acrylonitrile, vinylidene chloride, etc. as a monomer unit.
- the thickness of the outer shell may be greater than or equal to 2 ⁇ m and less than or equal to 15 ⁇ m.
- a liquid is contained in the hollow part of the first hollow particle.
- the first hollow particles for example, encapsulate a liquid at room temperature and normal pressure (eg, at least atmospheric pressure and 30° C.).
- the liquid is appropriately selected depending on, for example, the heating temperature in the reflow process and the shrinkage start temperature of the second hollow particles, which will be described later.
- the liquid is, for example, a liquid that vaporizes at a temperature below the maximum heating temperature in the reflow process.
- the liquid may be a liquid that vaporizes at a temperature below the contraction start temperature of the second hollow particles.
- the liquid may be, for example, a hydrocarbon having a boiling point (under atmospheric pressure) of 50°C or higher, 100°C or higher, 150°C or higher, or 200°C or higher.
- gas may be further included in the hollow portion of the first hollow particle.
- the components contained in the hollow part of the first hollow particles include, for example, propane, propylene, butene, normal butane, isobutane, normal pentane, isopentane, neopentane, normal hexane, isohexane, heptane, isooctane, normal octane, isoalkane.
- propane propylene
- butene normal butane
- isobutane normal pentane
- isopentane neopentane
- neopentane normal hexane
- isohexane isohexane
- heptane isooctane
- isoalkane isoalkane.
- hydrocarbons such as petroleum ether
- low-boiling compounds such as halides of methane and tetraalkylsilane
- compounds that are gasified by thermal decomposition such as azodi
- the average particle diameter of the first hollow particles may be 5 ⁇ m or more, or 10 ⁇ m or more, and may be 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less.
- the average particle diameter of the first hollow particles is measured by a laser diffraction/scattering method (eg, using "SALD-7500nano" manufactured by Shimadzu Corporation).
- the expansion start temperature of the first hollow particles is the contraction start temperature of the second hollow particles described later. It is preferable that it is below.
- the expansion start temperature of the first hollow particles is preferably 150°C or higher, or 180°C or higher, and preferably 260°C or lower, 240°C or lower, 220°C or lower, or 200°C or lower.
- the expansion start temperature of the first hollow particles was determined by thermomechanical analysis (TMA) to be 3 in the temperature (horizontal axis) - volume change (vertical axis) profile when the temperature was raised at a heating rate of 10°C/min. It means the temperature at the intersection of the tangent at the point where the volume change of 5 times or more/5° C. occurs and the straight line (horizontal axis) where the volume change is zero (initial volume).
- the content of the first hollow particles (the content at 30° C. under atmospheric pressure; the same applies hereinafter) is preferably based on the total mass of the heat insulating layer 11 from the viewpoint of further suppressing the deterioration of the heat insulating property of the sheet 10.
- the content may be 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, particularly preferably 5% by mass or more, and 20% by mass or less, or 15% by mass or less.
- the content of the first hollow particles is preferably 0.5% by volume or more, more preferably 1.0% by volume or more, based on the total volume of the heat insulating layer 11, from the viewpoint of suppressing a decrease in the heat insulation properties of the sheet 10. , more preferably 1.5% by volume or more. From the viewpoint of suppressing excessive expansion of the volume of the sheet 10, the content of the first hollow particles is 10 volume% or less, 7 volume% or less, 5 volume% or less, or 4 volume% or less, based on the total volume of the heat insulating layer 11. It may be less than or equal to % by volume.
- the second hollow particles are organic hollow particles other than the first hollow particles. That is, the second hollow particles are organic hollow particles having a maximum volumetric expansion ratio of less than 10 times the volume at 25°C.
- the maximum volumetric expansion factor of the second hollow particle is measured in the same manner as the maximum volumetric expansion factor of the first hollow particle.
- the outer shell of the second hollow particle is made of an organic material.
- the outer shell of the second hollow particle is preferably composed of a polymer, more preferably a thermoplastic polymer.
- the hollow particles are difficult to break even when pressurized and can maintain their hollow structure, making it easier to maintain the heat insulating properties of the sheet 10.
- the thermoplastic polymer may be, for example, a polymer containing acrylonitrile, vinylidene chloride, etc. as a monomer unit.
- the thickness of the outer shell may be greater than or equal to 0.005 ⁇ m and less than or equal to 15 ⁇ m.
- Examples of the components contained in the hollow part of the second hollow particle include propane, propylene, butene, normal butane, isobutane, normal pentane, isopentane, neopentane, normal hexane, isohexane, heptane, isooctane, normal octane, and isoalkane. (carbon number: 10 to 13), hydrocarbons such as petroleum ether; low-boiling compounds such as halides of methane and tetraalkylsilane; and decomposition products of compounds that are gasified by thermal decomposition such as azodicarbonamide.
- the component included in the hollow part of the second hollow particle may be air.
- the density of the second hollow particles may be 500 kg/m 3 or less, 300 kg/m 3 or less, 100 kg/m 3 or less, 50 kg/m 3 or less, or 40 kg/m 3 or less, and 10 kg/m 3 or more, Or it may be 20 kg/m 3 or more.
- the content of the second hollow particles is preferably 50% by volume or more, more preferably 60% by volume or more, based on the total volume of the heat insulation layer 11, for example. It may be 95% by volume or less.
- the mass ratio of the content of the second hollow particles to the content of the first hollow particles is preferably 1 /5 or more, more preferably 1/3 or more.
- the mass ratio of the content of the second hollow particles to the content of the first hollow particles is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
- the inorganic material constituting the outer shell of the inorganic hollow particles may be, for example, an inorganic glass such as borosilicate glass (sodium borosilicate glass, etc.), aluminosilicate glass, or a composite glass thereof.
- gas is encapsulated in the hollow part of the inorganic hollow particles.
- the inorganic hollow particles for example, encapsulate gas at room temperature and normal pressure (eg, at least atmospheric pressure and 30° C.).
- the total content of hollow particles may be, for example, 50 volume % or more, 60 volume % or more, or 70 volume % or more, and 95 volume % or less, based on the total volume of the sheet 10.
- the matrix polymer may contain a compound represented by the following formula (1) as a monomer unit.
- the matrix polymer may be a polymer of a polymerizable compound containing a compound represented by the following formula (1).
- R 11 and R 12 each independently represent a hydrogen atom or a methyl group
- R 13 represents a divalent group having a polyoxyalkylene chain.
- R 11 and R 12 may be a hydrogen atom, and the other may be a methyl group. In another embodiment, both R 11 and R 12 may be hydrogen atoms. In other embodiments, both R 11 and R 12 can be methyl groups.
- the polyoxyalkylene chain includes a structural unit represented by the following formula (2). Thereby, the strength of the heat insulating layer 11 can be increased.
- R 13 may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by formula (1-2) below (polyethylene glycol di (meth)acrylate).
- formula (1-2) polyethylene glycol di (meth)acrylate
- R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and m is an integer of 2 or more.
- the polyoxyalkylene chain includes a structural unit represented by the following formula (3).
- R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di (meth)acrylate).
- formula (1-3) polypropylene glycol di (meth)acrylate.
- R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and n is an integer of 2 or more.
- the polyoxyalkylene chain is preferably a copolymer chain containing the above-mentioned structural unit represented by formula (2) and the structural unit represented by formula (3).
- the copolymer chain may be an alternating copolymer chain, a block copolymer chain, or a random copolymer chain.
- the copolymer chain is preferably a random copolymer chain.
- a plurality of R 14 and R 15 may be the same or different from each other.
- the plurality of R 14 and R 15 preferably include an ethylene group and a propylene group, respectively. That is, the polyoxyalkylene chain represented by (R 14 O) k1 and the polyoxyalkylene chain represented by (R 15 O) k3 are each preferably an oxyethylene group (represented by the above formula (2)). It is a copolymer chain containing a structural unit represented by the above formula (3)) and an oxypropylene group (a structural unit represented by the above formula (3)).
- the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 100 or more.
- the main chain of the compound represented by formula (1) becomes longer, so that the elongation of the heat insulating layer 11 is further excellent, and the strength of the heat insulating layer 11 is also improved. can be increased.
- the number of oxyalkylene groups corresponds to m in formula (1-2), n in formula (1-3), and k1 and k3 in formula (1-4), respectively.
- the number of oxyalkylene groups in the polyoxyalkylene chain is more preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more.
- the number of oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.
- the weight average molecular weight of the compound represented by formula (1) is preferably 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, or 11,000 or more, from the viewpoint that the heat insulating layer 11 has low elasticity and excellent elongation. 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more.
- the weight average molecular weight of the compound represented by formula (1) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less.
- the matrix polymer may contain only the compound represented by formula (1) as a monomer unit.
- the matrix polymer may further contain other polymerizable compounds (details will be described later) other than the compound represented by formula (1) as a monomer unit.
- the content of the compound represented by formula (1) is the sum of the compound represented by formula (1) and other polymerizable compounds (hereinafter referred to as , "total monomer unit content") is preferably 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more.
- the content of the compound represented by formula (1) may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, based on 100 parts by mass of the total content of monomer units.
- the other polymerizable compound (monomer unit) in the matrix polymer may be, for example, a compound having one (meth)acryloyl group.
- examples of such compounds include the above-mentioned compounds having (meth)acryloyl groups that may be included in the acrylic copolymer as a monomer unit.
- Other polymerizable compounds in the matrix polymer include, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, an alkoxy group, a phenoxy group, a group containing a silane group, and a siloxane group.
- Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, Examples include polybutylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, and the like.
- Examples of compounds having a group containing a (meth)acryloyl group and a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyl Examples include triethoxysilane and 10-acryloyloxydecyltriethoxysilane.
- Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate.
- Examples of compounds having a (meth)acryloyl group and a halogen atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro -2-Propyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, perfluoropentylmethyl (meth)acrylate, perfluorohexylmethyl ( meth)acrylate, perfluoroheptylmethyl(meth)acrylate, perfluorooctylmethyl(meth)acrylate, perfluorononylmethyl(meth)acrylate, perfluorodecylmethyl(meth)acrylate, perfluoroundecylmethyl(meth)acrylate, Perfluorododecylmethyl (meth)acrylate
- Examples of compounds having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, ⁇ -ethyl (meth)glycidyl acrylate, ⁇ -n-propyl (meth)glycidyl acrylate, ⁇ -n-butyl Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, ⁇ -ethyl ( 6,7-epoxyheptyl meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, (meth)acrylic Examples include 5-methyl-5,6-epoxyhexyl acid, ⁇ -methylglycidyl (meth)acrylate, and ⁇ -methylglycidy
- the content of the matrix polymer may be, for example, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 95% by mass or less, based on the total mass of the heat insulating layer 11. It may be 90% by mass or less.
- the heat insulating layer 11 can further contain other additives as necessary.
- Other additives include, for example, plasticizers, antioxidants (e.g. phenolic antioxidants), surface conditioners (e.g. silane coupling agents), dispersants, curing accelerators, colorants, crystal nucleating agents, thermal Stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, flame retardant aids (for example, metal oxides) and the like can be mentioned.
- the content of other additives may be 0.1% by mass or more and 30% by mass or less based on the total mass of the heat insulating layer 11.
- the sheet including other layers includes a surface protection layer (first surface protection layer), a heat insulating layer, an adhesive layer (first adhesive layer), and a support layer (first support layer).
- the sheet may include an adhesive layer (second adhesive layer), a support layer (second support layer), an adhesive layer, and a surface protection layer (second surface protection layer).
- the surface protective layer may be composed of, for example, a resin film (such as a PET film) whose surface in contact with the heat insulating layer or the adhesive layer has been subjected to easy-peel treatment.
- the adhesive layer may contain, for example, an acrylic adhesive, an epoxy adhesive, or the like.
- the support layer may be made of, for example, a resin film (such as a polyimide film).
- the sheet 10 can be produced, for example, by separately producing the heat insulating layer 11 and the adhesive layer 12, and then bonding the heat insulating layer 11 and the adhesive layer 12 together.
- a method for producing a sheet including the other layers described above includes a laminate A of a surface protection layer (first surface protection layer) and a heat insulating layer, an adhesive layer (first adhesive layer), a support layer (first A laminate B of a support layer (supporting layer) and an adhesive layer (second adhesive layer), and a laminate C of a support layer (second support layer), an adhesive layer, and a surface protection layer (second surface protection layer) a process of preparing the laminate A and the adhesive layer (first adhesive layer) of the laminate B, and bonding the adhesive layer (second adhesive layer) of the laminate B and the laminate It may also include a step of bonding the support layer (second support layer) of C.
- Laminated body A is produced, for example, by preparing a mixture containing the first hollow particles, second hollow particles, and a polymerizable compound described above, and then applying polymerization in the mixture on a surface protective layer (first surface protective layer). It is obtained by polymerizing a compound to form a matrix polymer.
- the laminate B includes, for example, a support layer (first support layer), and an adhesive layer (first adhesive layer) and an adhesive layer (second adhesive layer) provided on both surfaces of the support layer, respectively. Double-sided adhesive tape can be used.
- the laminate C is produced by coating a pressure-sensitive adhesive composition obtained by mixing materials such as an acrylic pressure-sensitive adhesive on a surface protective layer (second surface protective layer), drying the pressure-sensitive adhesive composition, and drying the pressure-sensitive adhesive composition.
- a support layer (second support layer).
- a roll laminator can be used, for example.
- B-1 Crosslinking agent represented by the following formula (B-1)
- B-2 Crosslinking agent represented by the following formula (B-2) (“Tetrad X” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
- B-1 Crosslinking agent having 3 isocyanate groups (not having epoxy groups) (“Coronate L38ET” manufactured by Tosoh Corporation)
- Antioxidant) C 4,4-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine (“Nonflex DCD” manufactured by Seiko Chemical Co., Ltd.)
- a pressure-sensitive adhesive composition was obtained by mixing each component in the amounts shown in Table 1 and the following solvent, stirring for 5 minutes at a rotational speed of 1000 rpm using a rotational revolution mixer, and then leaving it at room temperature until there were no air bubbles. .
- the types and amounts of solvents used in each example are as follows.
- the amount of the following solvent means the amount with respect to the total of 100 parts by mass of each component shown in Table 1.
- the obtained adhesive composition was applied onto the easily peelable surface of a 38 ⁇ m thick polyester film (trade name: Purex A31, manufactured by Toyobo Co., Ltd.), which had been treated with a silicone release agent on one side for easy peeling. After coating, it was dried in a drying oven at 100° C. for 2 minutes to form an adhesive layer with a thickness of 10 ⁇ m. Next, a 25 ⁇ m thick polyimide film base material (trade name: Kapton 100H, manufactured by DuPont Toray) is laminated on the exposed surface of the formed adhesive layer at room temperature (25° C.) to form a surface protective layer.
- the adhesive layer with support layer of the obtained sample was cut to a width of 5 mm, 10 mm of one side in the length direction was peeled off from the Si wafer, and tested using a tensile tester ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation). , 90° peel strength (initial 90° peel strength) was measured.
- the prepared sample was passed through a reflow oven (TNP25-337EM series N2 reflow device manufactured by Tamura Seisakusho) to add a thermal history, and after cooling, the 90° peel strength (90° peel strength after heating) was measured in the same manner. .
- the thermal history was determined by raising the temperature from room temperature (25°C) to 200°C at a heating rate of 47°C/min in a reflow oven, and then from 200°C to 260°C at a heating rate of 38°C/min. Added by heating.
- the cooling was performed by cooling to 60°C in a reflow oven, taking it out from the reflow oven, and cooling it to 25°C. The results are shown in Table 1.
- a release-treated surface of a polyester sheet ("A31" manufactured by Toyobo Co., Ltd.) measuring 200 mm long x 200 mm wide x 0.1 mm thick was placed on a glass plate measuring 200 mm long x 200 mm wide x 5 mm thick.
- Two sets of molded plates were prepared, on which the molded plates were placed facing upward.
- a silicone rubber mold (200 mm x 200 mm) with holes of 120 mm x 120 mm x 2.0 mm is installed on the release-treated surface of one of the molding plates, and a heat insulating layer is prepared inside the mold. Filled with composition.
- the other molded plate was heated at 135° C. for 40 minutes after the release-treated surface was placed on the composition side and the top lid was placed.
- Thermal conductivity of heat insulation layer was measured according to the following procedure.
- the heat insulating layer was cut into 8 cm x 13 cm x 2.0 mm, sandwiched between a reference plate and a measurement probe, and a quick thermal conductivity meter (Kyoto Electronics Co., Ltd. "QTM-710", measurement probe PD-11N, thin film measurement) was used.
- the thermal conductivity (initial thermal conductivity) was measured under the condition of 25° C. (mode).
- a test piece of the heat insulating layer was prepared by cutting the heat insulating layer into 20 mm width x 50 mm length, and the test piece was subjected to heat history in the same manner as described above for [Peel strength of adhesive layer], and after being left to cool, The thermal conductivity (thermal conductivity after heating) was measured in the same manner as above.
- the reference was measured by stacking two release-treated polyester sheets ("A31" manufactured by Toyobo Co., Ltd.) and sandwiching them between a reference plate and a measurement probe. As a result, the initial thermal conductivity was 64 mW/(m ⁇ K), and the thermal conductivity after heating was 67 mW/(m ⁇ K).
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Abstract
Provided is a sheet comprising a heat insulating layer and an adhesive layer, wherein the adhesive layer contains an acrylic copolymer and a crosslinking agent having an epoxy group.
Description
本発明は、断熱層と粘着層とを備えるシートに関する。
The present invention relates to a sheet including a heat insulating layer and an adhesive layer.
低消費電力及び高速読み書きを特徴とする不揮発性メモリが、次世代メモリとして注目を集めている。例えば、相変化メモリ（ＰＣＭ）、磁気抵抗メモリ（ＭＲＡＭ）、抵抗変化型メモリ（ＲｅＲＡＭ）等が知られている。不揮発性メモリは、熱に弱く、実装時のリフロー工程において高温環境に晒されたときの品質維持が課題となっている。
Nonvolatile memory, which is characterized by low power consumption and high speed reading and writing, is attracting attention as a next-generation memory. For example, phase change memory (PCM), magnetoresistive memory (MRAM), resistance change memory (ReRAM), etc. are known. Nonvolatile memory is sensitive to heat, and maintaining its quality when exposed to high temperature environments during the reflow process during packaging is an issue.
この課題に対し、例えば特許文献１では、磁気記録装置のリフロー炉内に露出する表面に断熱材を設ける第１ステップと、断熱材を備えた磁気記録装置をリフロー炉内に通し、磁気記録装置を加熱する第２ステップと、加熱された磁気記録装置から断熱材を取り除く第３ステップとを有するリフロー工程を備えた磁気記録装置の製造方法が開示されている。
To address this issue, for example, Patent Document 1 discloses a first step of providing a heat insulating material on the surface of the magnetic recording device exposed in the reflow oven, and passing the magnetic recording device provided with the heat insulating material into the reflow oven. A method of manufacturing a magnetic recording device is disclosed that includes a reflow process that includes a second step of heating the magnetic recording device and a third step of removing the heat insulating material from the heated magnetic recording device.
本発明者らは、上記のような断熱材として、断熱層と粘着層とを備えるシートの使用を検討した。このような断熱材を用いる場合、粘着層を被着体（磁気記録装置）に粘着させることにより断熱材を被着体上に設けるが、リフロー工程の後に断熱材を取り除く際には、断熱材を容易に剥がすことができること（すなわち、断熱材が優れた剥離性を有していること）が好ましい。
The present inventors studied the use of a sheet including a heat insulating layer and an adhesive layer as a heat insulating material as described above. When using such a heat insulating material, the heat insulating material is provided on the adherend by adhering the adhesive layer to the adherend (magnetic recording device), but when removing the heat insulating material after the reflow process, the heat insulating material It is preferable that the heat insulating material can be easily peeled off (that is, the heat insulating material has excellent peelability).
そこで、本発明の一側面は、リフロー工程後の剥離性に優れた断熱材に適したシートを提供することを目的とする。
Therefore, one aspect of the present invention is to provide a sheet suitable for a heat insulating material that has excellent releasability after a reflow process.
本発明者らの検討によれば、粘着層がアクリル共重合体と架橋剤とを含む場合に、架橋剤の種類によって、リフロー工程後のシートのピール強度が異なり、その結果、剥離性も異なることが明らかとなった。そして、本発明者らは、架橋剤としてエポキシ系架橋剤を用いることにより、リフロー工程後のシートのピール強度を小さくすることができ、リフロー工程後の剥離性に優れたシートを提供することができることを見出した。本発明は、いくつかの側面において、下記の［１］～［５］を提供する。
According to studies by the present inventors, when the adhesive layer contains an acrylic copolymer and a crosslinking agent, the peel strength of the sheet after the reflow process varies depending on the type of crosslinking agent, and as a result, the peelability also varies. It became clear that The present inventors have found that by using an epoxy crosslinking agent as a crosslinking agent, the peel strength of the sheet after the reflow process can be reduced, and it is possible to provide a sheet with excellent peelability after the reflow process. I found out what I can do. In some aspects, the present invention provides the following [1] to [5].
［１］断熱層と、粘着層と、を備え、粘着層が、アクリル共重合体と、エポキシ基を有する架橋剤と、を含む、シート。
［２］断熱層が、中空粒子と、マトリックスポリマーと、を含有する、［１］に記載のシート。
［３］マトリックスポリマーが、下記式（１）で表される化合物をモノマー単位として含む、［２］に記載のシート。
［式（１）中、Ｒ１１及びＲ１２はそれぞれ独立に水素原子又はメチル基を表し、Ｒ１３はポリオキシアルキレン鎖を有する２価の基を表す。］
［４］中空粒子が、有機中空粒子を含む、［２］又は［３］に記載のシート。
［５］有機中空粒子が、熱膨張性の有機中空粒子である第一の中空粒子と、第一の中空粒子以外の有機中空粒子である第二の中空粒子と、を含む、［４］に記載のシート。 [1] A sheet comprising a heat insulating layer and an adhesive layer, the adhesive layer containing an acrylic copolymer and a crosslinking agent having an epoxy group.
[2] The sheet according to [1], wherein the heat insulating layer contains hollow particles and a matrix polymer.
[3] The sheet according to [2], wherein the matrix polymer contains a compound represented by the following formula (1) as a monomer unit.
[In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain. ]
[4] The sheet according to [2] or [3], wherein the hollow particles include organic hollow particles.
[5] In [4], the organic hollow particles include first hollow particles that are thermally expandable organic hollow particles and second hollow particles that are organic hollow particles other than the first hollow particles. Sheet listed.
［２］断熱層が、中空粒子と、マトリックスポリマーと、を含有する、［１］に記載のシート。
［３］マトリックスポリマーが、下記式（１）で表される化合物をモノマー単位として含む、［２］に記載のシート。
［４］中空粒子が、有機中空粒子を含む、［２］又は［３］に記載のシート。
［５］有機中空粒子が、熱膨張性の有機中空粒子である第一の中空粒子と、第一の中空粒子以外の有機中空粒子である第二の中空粒子と、を含む、［４］に記載のシート。 [1] A sheet comprising a heat insulating layer and an adhesive layer, the adhesive layer containing an acrylic copolymer and a crosslinking agent having an epoxy group.
[2] The sheet according to [1], wherein the heat insulating layer contains hollow particles and a matrix polymer.
[3] The sheet according to [2], wherein the matrix polymer contains a compound represented by the following formula (1) as a monomer unit.
[4] The sheet according to [2] or [3], wherein the hollow particles include organic hollow particles.
[5] In [4], the organic hollow particles include first hollow particles that are thermally expandable organic hollow particles and second hollow particles that are organic hollow particles other than the first hollow particles. Sheet listed.
本発明の一側面によれば、リフロー工程後の剥離性に優れた断熱材に適したシートを提供することができる。
According to one aspect of the present invention, it is possible to provide a sheet suitable for a heat insulating material with excellent releasability after a reflow process.
以下、本発明の実施形態について詳細に説明する。なお、本発明は、以下の実施形態に限定されない。
Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments.
本明細書における、「（メタ）アクリロイル」とは、「アクリロイル」及びそれに対応する「メタクリロイル」を意味し、「（メタ）アクリレート」、「（メタ）アクリル」等の類似表現においても同様である。
In this specification, "(meth)acryloyl" means "acryloyl" and its corresponding "methacryloyl", and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic". .
本明細書における重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて以下の条件で測定され、ポリスチレンを標準物質として決定される値を意味する。
・測定機器：ＨＬＣ－８３２０ＧＰＣ（製品名、東ソー（株）製）
・分析カラム：ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ－Ｈ（３本連結）（製品名、東ソー（株）製）
・ガードカラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＭＰ（ＨＺ）－Ｈ（製品名、東ソー（株）製）
・溶離液：ＴＨＦ
・測定温度：２５℃ The weight average molecular weight (Mw) in this specification means a value determined using gel permeation chromatography (GPC) under the following conditions and using polystyrene as a standard substance.
・Measuring equipment: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
・Analytical column: TSKgel SuperMultipore HZ-H (3 columns connected) (product name, manufactured by Tosoh Corporation)
・Guard column: TSKguardcolumn SuperMP (HZ)-H (product name, manufactured by Tosoh Corporation)
・Eluent: THF
・Measurement temperature: 25℃
・測定機器：ＨＬＣ－８３２０ＧＰＣ（製品名、東ソー（株）製）
・分析カラム：ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ－Ｈ（３本連結）（製品名、東ソー（株）製）
・ガードカラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＭＰ（ＨＺ）－Ｈ（製品名、東ソー（株）製）
・溶離液：ＴＨＦ
・測定温度：２５℃ The weight average molecular weight (Mw) in this specification means a value determined using gel permeation chromatography (GPC) under the following conditions and using polystyrene as a standard substance.
・Measuring equipment: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
・Analytical column: TSKgel SuperMultipore HZ-H (3 columns connected) (product name, manufactured by Tosoh Corporation)
・Guard column: TSKguardcolumn SuperMP (HZ)-H (product name, manufactured by Tosoh Corporation)
・Eluent: THF
・Measurement temperature: 25℃
図１は、シートの一実施形態を示す模式断面図である。図１に示されるシート１０は、断熱層１１と、粘着層１２と、を備えている。断熱層１１と粘着層１２とは、互いに接するように積層されていてよい。
FIG. 1 is a schematic cross-sectional view showing one embodiment of the sheet. The sheet 10 shown in FIG. 1 includes a heat insulating layer 11 and an adhesive layer 12. The heat insulating layer 11 and the adhesive layer 12 may be laminated so as to be in contact with each other.
粘着層１２は、アクリル共重合体と、エポキシ基を有する架橋剤と、を含む。
The adhesive layer 12 includes an acrylic copolymer and a crosslinking agent having an epoxy group.
アクリル共重合体は、２種以上の重合性化合物の共重合体である。当該２種以上の重合性化合物が、（メタ）アクリロイル基を有する化合物を１種以上含む。アクリル共重合体は、モノマー単位として、（メタ）アクリロイル基を有する化合物を１種以上含むが、２種以上、３種以上、又は４種以上含んでいてもよい。
An acrylic copolymer is a copolymer of two or more types of polymerizable compounds. The two or more polymerizable compounds include one or more compounds having a (meth)acryloyl group. The acrylic copolymer contains one or more types of compounds having (meth)acryloyl groups as monomer units, but may contain two or more types, three or more types, or four or more types.
（メタ）アクリロイル基を有する化合物は、例えば、アルキル（メタ）アクリレートであってよい。アルキル（メタ）アクリレートにおけるアルキル基（（メタ）アクリロイル基以外のアルキル基部分）は、直鎖状であっても分岐状であっても環状であってもよい。アルキル基の炭素数は、例えば、１～３０であってよい。アルキル基の炭素数は、２以上、又は３以上であってよく、２５以下、２０以下、１５以下、１０以下、７以下、又は５以下であってよい。
The compound having a (meth)acryloyl group may be, for example, an alkyl (meth)acrylate. The alkyl group (the alkyl group portion other than the (meth)acryloyl group) in the alkyl (meth)acrylate may be linear, branched, or cyclic. The alkyl group may have, for example, 1 to 30 carbon atoms. The number of carbon atoms in the alkyl group may be 2 or more, or 3 or more, and may be 25 or less, 20 or less, 15 or less, 10 or less, 7 or less, or 5 or less.
直鎖状のアルキル基を有するアルキル（メタ）アクリレートとしては、例えば、炭素数１～１１の直鎖状アルキル基を有するアルキル（メタ）アクリレート、及び炭素数１２～３０の直鎖状アルキル基を有するアルキル（メタ）アクリレートが挙げられる。
Examples of alkyl (meth)acrylates having a linear alkyl group include alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms, and linear alkyl groups having 12 to 30 carbon atoms. Examples include alkyl (meth)acrylates having
炭素数１～１１の直鎖状アルキル基を有するアルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－へプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート等が挙げられる。
Examples of alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. , n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and the like.
炭素数１２～３０の直鎖状アルキル基を有するアルキル（メタ）アクリレートとしては、ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレート）、テトラデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート（セチル（メタ）アクリレート）、オクタデシル（メタ）アクリレート（ステアリル（メタ）アクリレート）、ドコシル（メタ）アクリレート（ベヘニル（メタ）アクリレート）、テトラコシル（メタ）アクリレート、ヘキサコシル（メタ）アクリレート、オクタコシル（メタ）アクリレート等が挙げられる。
Alkyl (meth)acrylates having a linear alkyl group having 12 to 30 carbon atoms include dodecyl (meth)acrylate (lauryl (meth)acrylate), tetradecyl (meth)acrylate, hexadecyl (meth)acrylate (cetyl (meth)acrylate), acrylate), octadecyl (meth)acrylate (stearyl (meth)acrylate), docosyl (meth)acrylate (behenyl (meth)acrylate), tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, octacosyl (meth)acrylate, etc. .
分岐状のアルキル基を有するアルキル（メタ）アクリレートとしては、例えば、炭素数１～１１の分岐状アルキル基を有するアルキル（メタ）アクリレート、及び炭素数１２～３０の分岐状アルキル基を有するアルキル（メタ）アクリレートが挙げられる。
Examples of alkyl (meth)acrylates having a branched alkyl group include alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms, and alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms. Examples include meth)acrylates.
炭素数１～１１の分岐状アルキル基を有するアルキル（メタ）アクリレートとしては、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート等が挙げられる。
Examples of alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms include s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, isoamyl ( Examples include meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isononyl(meth)acrylate, and isodecyl(meth)acrylate.
炭素数１２～３０の分岐状アルキル基を有するアルキル（メタ）アクリレートとしては、イソミリスチル（メタ）アクリレート、２－プロピルヘプチル（メタ）アクリレート、イソウンデシル（メタ）アクリレート、イソドデシル（メタ）アクリレート、イソトリデシル（メタ）アクリレート、イソペンタデシル（メタ）アクリレート、イソヘキサデシル（メタ）アクリレート、イソヘプタデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、デシルテトラデカニル（メタ）アクリレート等が挙げられる。
Examples of alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms include isomyristyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl ( Examples include meth)acrylate, isopentadecyl(meth)acrylate, isohexadecyl(meth)acrylate, isoheptadecyl(meth)acrylate, isostearyl(meth)acrylate, decyltetradecanyl(meth)acrylate, and the like.
脂環式（環状）であるアルキル基（シクロアルキル基）を有するアルキル（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、テルペン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。
Examples of alkyl (meth)acrylates having an alicyclic (cyclic) alkyl group (cycloalkyl group) include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, Examples include terpene (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.
（メタ）アクリロイル基を有する化合物は、（メタ）アクリロイル基に加えて、ヘテロ環を含む基、ヒドロキシル基、又はカルボキシル基を有する化合物であってもよい。
The compound having a (meth)acryloyl group may be a compound having a heterocycle-containing group, a hydroxyl group, or a carboxyl group in addition to the (meth)acryloyl group.
（メタ）アクリロイル基及びヘテロ環を含む基を有する化合物の例としては、Ｎ－アクリロイルモルホリン（ＡＣＭＯ）、及びテトラヒドロフルフリル（メタ）アクリレートが挙げられる。
Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include N-acryloylmorpholine (ACMO) and tetrahydrofurfuryl (meth)acrylate.
（メタ）アクリロイル基及びヒドロキシル基を有する化合物の例としては、ヒドロキシアルキル（メタ）アクリレート、ヒドロキシアルキルシクロアルカン（メタ）アクリレート等が挙げられる。ヒドロキシアルキル（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート等が挙げられる。ヒドロキシアルキルシクロアルカン（メタ）アクリレートとしては、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等が挙げられる。
Examples of compounds having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylate, hydroxyalkylcycloalkane (meth)acrylate, and the like. Examples of hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples thereof include meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, and 12-hydroxylauryl(meth)acrylate. Examples of the hydroxyalkylcycloalkane (meth)acrylate include (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
（メタ）アクリロイル基及びカルボキシル基を有する化合物の例としては、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、フタル酸モノヒドロキシエチルアクリレート（例えば、東亞合成（株）製「アロニックスＭ５４００」）、及び２－アクリロイルオキシエチルサクシネート（例えば、新中村化学株式会社製「ＮＫエステル Ａ－ＳＡ」）が挙げられる。
Examples of compounds having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and monohydroxyethyl phthalate acrylate (for example, Toagosei Co., Ltd.) "Aronix M5400" manufactured by Shin Nakamura Chemical Co., Ltd.), and 2-acryloyloxyethyl succinate (for example, "NK Ester A-SA" manufactured by Shin Nakamura Chemical Co., Ltd.).
アクリル共重合体は、（メタ）アクリロイル基を有する化合物以外の他の重合性化合物をモノマー単位として含んでいてもよい。アクリル共重合体における他の重合性化合物（モノマー単位）の例としては、アクリロニトリルが挙げられる。
The acrylic copolymer may contain a polymerizable compound other than the compound having a (meth)acryloyl group as a monomer unit. Examples of other polymerizable compounds (monomer units) in the acrylic copolymer include acrylonitrile.
アクリル共重合体の重量平均分子量（Ｍｗ）は、２０万以上、４０万以上、５０万以上、又は６０万以上であってもよく、１２０万以下、１１０万以下、又は１００万以下であってもよい。
The weight average molecular weight (Mw) of the acrylic copolymer may be 200,000 or more, 400,000 or more, 500,000 or more, or 600,000 or more, and is 1.2 million or less, 1.1 million or less, or 1 million or less. Good too.
アクリル共重合体の多分散度（重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ））は、１．１以上、又は１．５以上であってもよく、７．０以下であってもよい。
The polydispersity (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn)) of the acrylic copolymer may be 1.1 or more, or 1.5 or more, and 7 It may be less than .0.
アクリル共重合体のガラス転移温度（Ｔｇ）は、－５０℃以上、又は－４５℃以上であってもよく、－５℃以下、又は－１０℃以下であってもよい。
The glass transition temperature (Tg) of the acrylic copolymer may be -50°C or higher, or -45°C or higher, or -5°C or lower, or -10°C or lower.
アクリル共重合体の酸価は、２０．０ｍｇＫＯＨ／ｇ以上であってよく、３０．０ｍｇＫＯＨ／ｇ以下であってもよい。
The acid value of the acrylic copolymer may be 20.0 mgKOH/g or more and 30.0 mgKOH/g or less.
アクリル共重合体におけるカルボキシル基の濃度は、２．００×１０―４ｍｏｌ／Ｌ以上以上であってもよく、１１．００×１０―４ｍｏｌ／Ｌ以下であってもよい。
The concentration of carboxyl groups in the acrylic copolymer may be 2.00×10 −4 mol/L or more and 11.00×10 −4 mol/L or less.
アクリル共重合体における水酸基の濃度は、１．００×１０―４ｍｏｌ／Ｌ以上であってもよく、５．００×１０―４ｍｏｌ／Ｌ以下であってもよい。
The concentration of hydroxyl groups in the acrylic copolymer may be 1.00×10 −4 mol/L or more and 5.00×10 −4 mol/L or less.
アクリル共重合体の含有量は、粘着層１２の全質量を基準として、７０質量％以上、又は８０質量％以上であってよく、９８質量％以下、又は９５質量％以下であってよい。
The content of the acrylic copolymer may be 70% by mass or more, or 80% by mass or more, and 98% by mass or less, or 95% by mass or less, based on the total mass of the adhesive layer 12.
エポキシ基を有する架橋剤は、エポキシ基を２個以上、３個以上、又は４個以上有していてもよい。エポキシ基を４個有する架橋剤としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－１，３－ビス（アミノメチル）シクロヘキサン（下記式（Ｂ－１）で表される架橋剤）、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（下記式（Ｂ－２）で表される架橋剤）等が挙げられる。また、エポキシ基を２個以上有する架橋剤としては、例えば、ソルビトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル等が挙げられる。
The crosslinking agent having an epoxy group may have 2 or more, 3 or more, or 4 or more epoxy groups. As a crosslinking agent having four epoxy groups, for example, N,N,N',N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane (a crosslinking agent represented by the following formula (B-1) ), N,N,N',N'-tetraglycidyl-m-xylene diamine (crosslinking agent represented by the following formula (B-2)), and the like. Further, examples of the crosslinking agent having two or more epoxy groups include sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, and the like.
エポキシ基を有する架橋剤の含有量は、粘着層１２の全質量を基準として、１質量％以上、又は５質量％以上であってよく、２０質量％以下、又は１５質量％以下であってよい。
The content of the crosslinking agent having an epoxy group may be 1% by mass or more, or 5% by mass or more, and 20% by mass or less, or 15% by mass or less, based on the total mass of the adhesive layer 12. .
粘着層１２は、アクリル共重合体及びエポキシ基を有する架橋剤に加えて、酸化防止剤等の添加剤を更に含んでいてよい。酸化防止剤の例としては、４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミン、ｐ，ｐ’－ジオクチルジフェニルアミン等のフェニルアミン系酸化防止剤が挙げられる。
In addition to the acrylic copolymer and the crosslinking agent having an epoxy group, the adhesive layer 12 may further contain additives such as an antioxidant. Examples of the antioxidant include phenylamine antioxidants such as 4,4-bis(α,α-dimethylbenzyl)diphenylamine and p,p'-dioctyldiphenylamine.
粘着層１２の厚みは、例えば、例えば、５μｍ以上、又は１０μｍ以上であってよく、５０μｍ以下、４０μｍ以下、又は３０μｍ以下であってよい。
The thickness of the adhesive layer 12 may be, for example, 5 μm or more, or 10 μm or more, and 50 μm or less, 40 μm or less, or 30 μm or less.
断熱層１１は、断熱性を有する層であればよい。断熱層１１の２５℃における熱伝導率は、好ましくは、１３０ｍＷ／（ｍ・Ｋ）以下、１００ｍＷ／（ｍ・Ｋ）以下、又は８０ｍＷ／（ｍ・Ｋ）以下である。
The heat insulating layer 11 may be any layer as long as it has heat insulating properties. The thermal conductivity of the heat insulating layer 11 at 25° C. is preferably 130 mW/(m·K) or less, 100 mW/(m·K) or less, or 80 mW/(m·K) or less.
断熱層１１の材質は特に制限されない。断熱層１１は、多孔質材料で構成される層であってよい。多孔質材料は、有機多孔質材料であってよく、無機多孔質材料であってもよい。有機多孔質材料の例としては、樹脂製の多孔質材料が挙げられる。樹脂製の多孔質材料の例としては、メラミン樹脂製の多孔質材料（メラミンスポンジ）が挙げられる。無機多孔質材料の例としては、炭素製の多孔質材料、ガラス製の多孔質材料が挙げられる。炭素製の多孔質材料の例としては、カーボンフェルトが挙げられる。ガラス製の多孔質材料の例としては、ガラス繊維紙、ガラスフェルトが挙げられる。
The material of the heat insulating layer 11 is not particularly limited. The heat insulating layer 11 may be a layer made of porous material. The porous material may be an organic porous material or an inorganic porous material. Examples of organic porous materials include porous materials made of resin. An example of a porous material made of resin is a porous material made of melamine resin (melamine sponge). Examples of inorganic porous materials include carbon porous materials and glass porous materials. An example of a porous material made of carbon is carbon felt. Examples of porous materials made of glass include glass fiber paper and glass felt.
断熱層１１は、中空粒子を含む層であってもよい。断熱層１１は、例えば、中空粒子と、マトリックスポリマーと、を含有していてもよい。
The heat insulating layer 11 may be a layer containing hollow particles. The heat insulating layer 11 may contain, for example, hollow particles and a matrix polymer.
中空粒子は、外殻と中空部とを有する粒子である。中空粒子はその外殻が有機材料により構成されている有機中空粒子であってもよく、その外殻が無機材料により構成されている無機中空粒子であってもよい。中空粒子は、無機中空粒子及び有機中空粒子のいずれか一方を含んでいてよく、両方を含んでいてよい。
A hollow particle is a particle that has an outer shell and a hollow part. The hollow particles may be organic hollow particles whose outer shell is made of an organic material, or may be inorganic hollow particles whose outer shell is made of an inorganic material. The hollow particles may include either inorganic hollow particles or organic hollow particles, or both.
有機中空粒子としては、熱膨張性の有機中空粒子である第一の中空粒子、及び、当該第一の中空粒子以外の有機中空粒子である第二の中空粒子が挙げられる。有機中空粒子は、第一の中空粒子及び第二の中空粒子のいずれか一方又は両方を含んでいてよく、好ましくは第一の中空粒子及び第二の中空粒子の両方を含んでいる。
Examples of the organic hollow particles include first hollow particles that are thermally expandable organic hollow particles, and second hollow particles that are organic hollow particles other than the first hollow particles. The organic hollow particles may include either one or both of the first hollow particles and the second hollow particles, and preferably include both the first hollow particles and the second hollow particles.
第一の中空粒子は、熱により膨張する（熱膨張性の）有機中空粒子である。本明細書における熱膨張性の有機中空粒子とは、２５℃における体積に対する最大体積膨張倍率が１０倍以上である有機中空粒子である。断熱層１１が第一の中空粒子を含有する場合、リフロー工程において、断熱層１１の断熱性を低下させる方向にはたらく現象が生じた場合でも（例えば、後述する第二の中空粒子が収縮して、中空部の体積が減少した場合でも）、第一の中空粒子が熱によって膨張し、断熱層１１の断熱性に寄与する中空部の体積が増加する。そのため、断熱層１１（シート１０）の断熱性の低下を抑制することができる。
The first hollow particles are organic hollow particles that expand due to heat (thermally expandable). The term "thermally expandable organic hollow particles" as used herein refers to organic hollow particles having a maximum volumetric expansion ratio of 10 times or more relative to the volume at 25°C. When the heat insulating layer 11 contains the first hollow particles, even if a phenomenon occurs in the reflow process that reduces the heat insulating properties of the heat insulating layer 11 (for example, the second hollow particles described below shrink). , even if the volume of the hollow part decreases), the first hollow particles expand due to heat, and the volume of the hollow part that contributes to the heat insulating properties of the heat insulating layer 11 increases. Therefore, it is possible to suppress a decrease in the heat insulating properties of the heat insulating layer 11 (sheet 10).
第一の中空粒子の最大体積膨張倍率は、熱機械分析（ＴＭＡ）にて、昇温速度１０℃／分で昇温したときの、第一の中空粒子の最大体積と２５℃における体積との比（最大体積／２５℃における体積）として測定される。第一の中空粒子の最大体積膨張倍率は、例えば、２０倍以上、３０倍以上、又は４０倍以上であってもよく、１２０倍以下であってもよい。
The maximum volumetric expansion ratio of the first hollow particles is determined by thermomechanical analysis (TMA) between the maximum volume of the first hollow particles and the volume at 25°C when the temperature is increased at a temperature increase rate of 10°C/min. It is measured as the ratio (maximum volume/volume at 25°C). The maximum volumetric expansion factor of the first hollow particles may be, for example, 20 times or more, 30 times or more, or 40 times or more, or 120 times or less.
第一の中空粒子の外殻は、好ましくはポリマーで構成されており、更に好ましくは熱可塑性ポリマーで構成されている。この場合、外殻が加熱により軟らかくなるため、中空部に内包されている液体が気化して内圧が上がっても、中空粒子は割れにくく、容易に膨張する。熱可塑性ポリマーは、例えば、アクリロニトリル、塩化ビニリデン等をモノマー単位として含むポリマーであってよい。外殻の厚さは、２μｍ以上であってよく、１５μｍ以下であってよい。
The outer shell of the first hollow particle is preferably made of a polymer, more preferably a thermoplastic polymer. In this case, the outer shell becomes soft due to heating, so even if the liquid contained in the hollow part evaporates and the internal pressure increases, the hollow particle is difficult to break and easily expands. The thermoplastic polymer may be, for example, a polymer containing acrylonitrile, vinylidene chloride, etc. as a monomer unit. The thickness of the outer shell may be greater than or equal to 2 μm and less than or equal to 15 μm.
第一の中空粒子の中空部には、例えば液体が内包されている。第一の中空粒子は、例えば、常温常圧下（例えば、少なくとも大気圧下かつ３０℃）において液体を内包している。当該液体は、例えば、リフロー工程における加熱温度及び後述する第二の中空粒子の収縮開始温度に応じて適宜選択される。当該液体は、例えば、リフロー工程における最高加熱温度以下の温度で気化する液体である。当該液体は、第二の中空粒子の収縮開始温度以下の温度で気化する液体であってもよい。当該液体は、例えば、沸点（大気圧下）が、５０℃以上、１００℃以上、１５０℃以上、又は２００℃以上の炭化水素であってよい。第一の中空粒子の中空部には、上記の液体に加えて、気体が更に内包されていてもよい。
For example, a liquid is contained in the hollow part of the first hollow particle. The first hollow particles, for example, encapsulate a liquid at room temperature and normal pressure (eg, at least atmospheric pressure and 30° C.). The liquid is appropriately selected depending on, for example, the heating temperature in the reflow process and the shrinkage start temperature of the second hollow particles, which will be described later. The liquid is, for example, a liquid that vaporizes at a temperature below the maximum heating temperature in the reflow process. The liquid may be a liquid that vaporizes at a temperature below the contraction start temperature of the second hollow particles. The liquid may be, for example, a hydrocarbon having a boiling point (under atmospheric pressure) of 50°C or higher, 100°C or higher, 150°C or higher, or 200°C or higher. In addition to the above-mentioned liquid, gas may be further included in the hollow portion of the first hollow particle.
第一の中空粒子の中空部に内包されている成分としては、例えば、プロパン、プロピレン、ブテン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ネオペンタン、ノルマルヘキサン、イソヘキサン、ヘプタン、イソオクタン、ノルマルオクタン、イソアルカン（炭素数：１０～１３）、石油エーテル等の炭化水素；メタンのハロゲン化物、テトラアルキルシラン等の低沸点化合物；アゾジカルボンアミド等の熱分解によりガス化する化合物が挙げられる。
The components contained in the hollow part of the first hollow particles include, for example, propane, propylene, butene, normal butane, isobutane, normal pentane, isopentane, neopentane, normal hexane, isohexane, heptane, isooctane, normal octane, isoalkane. (carbon number: 10 to 13), hydrocarbons such as petroleum ether; low-boiling compounds such as halides of methane and tetraalkylsilane; and compounds that are gasified by thermal decomposition such as azodicarbonamide.
第一の中空粒子の平均粒子径は、５μｍ以上、又は１０μｍ以上であってよく、５０μｍ以下、４０μｍ以下、又は３０μｍ以下であってよい。第一の中空粒子の平均粒子径は、レーザー回折・散乱法により（例えば、（株）島津製作所製「ＳＡＬＤ－７５００ｎａｎｏ」を用いて）測定される。
The average particle diameter of the first hollow particles may be 5 μm or more, or 10 μm or more, and may be 50 μm or less, 40 μm or less, or 30 μm or less. The average particle diameter of the first hollow particles is measured by a laser diffraction/scattering method (eg, using "SALD-7500nano" manufactured by Shimadzu Corporation).
シート１０がリフロー工程（一般的に２６０℃まで加熱される）における断熱材としてより好適に用いられる観点から、第一の中空粒子の膨張開始温度は、後述する第二の中空粒子の収縮開始温度以下であることが好ましい。第一の中空粒子の膨張開始温度は、好ましくは、１５０℃以上、又は１８０℃以上であり、好ましくは、２６０℃以下、２４０℃以下、２２０℃以下、又は２００℃以下である。第一の中空粒子の膨張開始温度は、熱機械分析（ＴＭＡ）にて、昇温速度１０℃／分で昇温したときの温度（横軸）－体積変化（縦軸）のプロファイルにおいて、３倍以上／５℃の体積変化が生じる点の接線と、体積変化がゼロ（初期体積）の直線（横軸）との交点の温度を意味する。
From the viewpoint that the sheet 10 is more suitably used as a heat insulating material in a reflow process (generally heated to 260° C.), the expansion start temperature of the first hollow particles is the contraction start temperature of the second hollow particles described later. It is preferable that it is below. The expansion start temperature of the first hollow particles is preferably 150°C or higher, or 180°C or higher, and preferably 260°C or lower, 240°C or lower, 220°C or lower, or 200°C or lower. The expansion start temperature of the first hollow particles was determined by thermomechanical analysis (TMA) to be 3 in the temperature (horizontal axis) - volume change (vertical axis) profile when the temperature was raised at a heating rate of 10°C/min. It means the temperature at the intersection of the tangent at the point where the volume change of 5 times or more/5° C. occurs and the straight line (horizontal axis) where the volume change is zero (initial volume).
シート１０がリフロー工程における断熱材としてより好適に用いられる観点から、第一の中空粒子の最大膨張温度は、好ましくは、１００℃以上、１５０℃以上、２００℃以上、又は２１０℃以上であり、好ましくは、２９０℃以下、２８０℃以下、又は２７０℃以下である。第一の中空粒子の最大膨張温度は、第一の中空粒子が上述した最大体積膨張倍率を示すときの温度を意味する。
From the viewpoint that the sheet 10 is more suitably used as a heat insulating material in a reflow process, the maximum expansion temperature of the first hollow particles is preferably 100° C. or higher, 150° C. or higher, 200° C. or higher, or 210° C. or higher, Preferably, the temperature is 290°C or lower, 280°C or lower, or 270°C or lower. The maximum expansion temperature of the first hollow particles means the temperature at which the first hollow particles exhibit the maximum volumetric expansion magnification described above.
第一の中空粒子の含有量（大気圧下かつ３０℃における含有量。以下同様。）は、シート１０の断熱性の低下を更に抑える観点から、断熱層１１の全質量を基準として、好ましくは１質量％以上、より好ましくは２質量％以上、更に好ましくは４質量％以上、特に好ましくは５質量％以上であり、２０質量％以下、又は１５質量％以下であってよい。
The content of the first hollow particles (the content at 30° C. under atmospheric pressure; the same applies hereinafter) is preferably based on the total mass of the heat insulating layer 11 from the viewpoint of further suppressing the deterioration of the heat insulating property of the sheet 10. The content may be 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, particularly preferably 5% by mass or more, and 20% by mass or less, or 15% by mass or less.
第一の中空粒子の含有量は、シート１０の断熱性の低下を抑える観点から、断熱層１１の全体積を基準として、好ましくは０．５体積％以上、より好ましくは１．０体積％以上、更に好ましくは１．５体積％以上である。シート１０の体積の過度な膨張を抑える観点から、第一の中空粒子の含有量は、断熱層１１の全体積を基準として、１０体積％以下、７体積％以下、５体積％以下、又は４体積％以下であってよい。
The content of the first hollow particles is preferably 0.5% by volume or more, more preferably 1.0% by volume or more, based on the total volume of the heat insulating layer 11, from the viewpoint of suppressing a decrease in the heat insulation properties of the sheet 10. , more preferably 1.5% by volume or more. From the viewpoint of suppressing excessive expansion of the volume of the sheet 10, the content of the first hollow particles is 10 volume% or less, 7 volume% or less, 5 volume% or less, or 4 volume% or less, based on the total volume of the heat insulating layer 11. It may be less than or equal to % by volume.
第二の中空粒子は、第一の中空粒子以外の有機中空粒子である。すなわち、第二の中空粒子は、２５℃における体積に対する最大体積膨張倍率が１０倍未満である有機中空粒子である。第二の中空粒子を用いることにより、断熱層１１の断熱性が向上し、シート１０を断熱材としてより好適に利用することができる。第二の中空粒子の最大体積膨張倍率は、第一の中空粒子の最大体積膨張倍率と同じ方法で測定される。
The second hollow particles are organic hollow particles other than the first hollow particles. That is, the second hollow particles are organic hollow particles having a maximum volumetric expansion ratio of less than 10 times the volume at 25°C. By using the second hollow particles, the heat insulating properties of the heat insulating layer 11 are improved, and the sheet 10 can be more suitably used as a heat insulating material. The maximum volumetric expansion factor of the second hollow particle is measured in the same manner as the maximum volumetric expansion factor of the first hollow particle.
第二の中空粒子の外殻は、有機材料により構成されている。第二の中空粒子の外殻は、好ましくはポリマーで構成されており、より好ましくは熱可塑性ポリマーで構成されている。この場合、中空粒子は加圧されても割れにくく、中空構造を保持できるため、シート１０の断熱性が維持されやすくなる。熱可塑性ポリマーは、例えば、アクリロニトリル、塩化ビニリデン等をモノマー単位として含むポリマーであってよい。外殻の厚さは、０．００５μｍ以上であってよく、１５μｍ以下であってよい。
The outer shell of the second hollow particle is made of an organic material. The outer shell of the second hollow particle is preferably composed of a polymer, more preferably a thermoplastic polymer. In this case, the hollow particles are difficult to break even when pressurized and can maintain their hollow structure, making it easier to maintain the heat insulating properties of the sheet 10. The thermoplastic polymer may be, for example, a polymer containing acrylonitrile, vinylidene chloride, etc. as a monomer unit. The thickness of the outer shell may be greater than or equal to 0.005 μm and less than or equal to 15 μm.
第二の中空粒子の中空部には、例えば気体が内包されている。第二の中空粒子は、例えば、常温常圧下（例えば、少なくとも大気圧下かつ３０℃）において気体を内包している。第二の中空粒子の中空部には、気体に加えて、液体が更に内包されていてもよい。
For example, gas is encapsulated in the hollow part of the second hollow particle. The second hollow particles, for example, encapsulate gas at room temperature and normal pressure (for example, at least at atmospheric pressure and 30° C.). In addition to gas, a liquid may be further included in the hollow part of the second hollow particle.
第二の中空粒子の中空部に内包されている成分としては、例えば、プロパン、プロピレン、ブテン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ネオペンタン、ノルマルヘキサン、イソヘキサン、ヘプタン、イソオクタン、ノルマルオクタン、イソアルカン（炭素数：１０～１３）、石油エーテル等の炭化水素；メタンのハロゲン化物、テトラアルキルシラン等の低沸点化合物；アゾジカルボンアミド等の熱分解によりガス化する化合物の分解生成物が挙げられる。また、第二の中空粒子の中空部に内包されている成分は、空気であってもよい。
Examples of the components contained in the hollow part of the second hollow particle include propane, propylene, butene, normal butane, isobutane, normal pentane, isopentane, neopentane, normal hexane, isohexane, heptane, isooctane, normal octane, and isoalkane. (carbon number: 10 to 13), hydrocarbons such as petroleum ether; low-boiling compounds such as halides of methane and tetraalkylsilane; and decomposition products of compounds that are gasified by thermal decomposition such as azodicarbonamide. Moreover, the component included in the hollow part of the second hollow particle may be air.
第二の中空粒子の平均粒子径は、断熱性を高める観点から、好ましくは１５０μｍ以下であり、より好ましくは１２０μｍ以下であり、更に好ましくは１００μｍ以下であり、例えば、５μｍ以上、１０μｍ以上、２０μｍ以上、又は３０μｍ以上であってよい。第二の中空粒子の平均粒子径は、レーザー回折・散乱法により（例えば、（株）島津製作所製「ＳＡＬＤ－７５００ｎａｎｏ」を用いて）測定される。
The average particle diameter of the second hollow particles is preferably 150 μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, for example, 5 μm or more, 10 μm or more, 20 μm or less, from the viewpoint of improving heat insulation properties. or more, or 30 μm or more. The average particle diameter of the second hollow particles is measured by a laser diffraction/scattering method (eg, using "SALD-7500nano" manufactured by Shimadzu Corporation).
第二の中空粒子の密度は、５００ｋｇ／ｍ３以下、３００ｋｇ／ｍ３以下、１００ｋｇ／ｍ３以下、５０ｋｇ／ｍ３以下、又は４０ｋｇ／ｍ３以下であってよく、１０ｋｇ／ｍ３以上、又は２０ｋｇ／ｍ３以上であってよい。本明細書における第二の中空粒子の密度は、タップ密度法にて測定される密度を意味する。すなわち、１０ｍＬのメスシリンダーに第二の中空粒子（約５ｇ）を投入し、５０回タッピングし、最上面が安定した時の体積を安定時体積として、以下の式により求められる密度である。
密度＝初期投入量（ｋｇ）／安定時体積（ｍ３） The density of the second hollow particles may be 500 kg/m 3 or less, 300 kg/m 3 or less, 100 kg/m 3 or less, 50 kg/m 3 or less, or 40 kg/m 3 or less, and 10 kg/m 3 or more, Or it may be 20 kg/m 3 or more. The density of the second hollow particle in this specification means the density measured by the tapped density method. That is, the second hollow particles (approximately 5 g) are placed in a 10 mL measuring cylinder, tapped 50 times, and the volume when the top surface becomes stable is defined as the volume at stable time, and the density is determined by the following formula.
Density = initial input amount (kg) / stable volume (m 3 )
密度＝初期投入量（ｋｇ）／安定時体積（ｍ３） The density of the second hollow particles may be 500 kg/m 3 or less, 300 kg/m 3 or less, 100 kg/m 3 or less, 50 kg/m 3 or less, or 40 kg/m 3 or less, and 10 kg/m 3 or more, Or it may be 20 kg/m 3 or more. The density of the second hollow particle in this specification means the density measured by the tapped density method. That is, the second hollow particles (approximately 5 g) are placed in a 10 mL measuring cylinder, tapped 50 times, and the volume when the top surface becomes stable is defined as the volume at stable time, and the density is determined by the following formula.
Density = initial input amount (kg) / stable volume (m 3 )
シート１０がリフロー工程（一般的に２６０℃まで加熱される）における断熱材としてより好適に用いられる観点から、第二の中空粒子の収縮開始温度は、好ましくは、１５０℃以上、１７０℃以上、又は１８０℃以上であり、２６０℃以下、２４０℃以下、２２０℃以下、又は２００℃以下であってもよい。第二の中空粒子の収縮開始温度は、熱機械分析（ＴＭＡ）にて、昇温速度１０℃／分で昇温したときの温度（横軸）－体積変化（縦軸）のプロファイルにおいて、体積変化が極大値となったときの温度を意味する。
From the viewpoint that the sheet 10 is more suitably used as a heat insulating material in a reflow process (generally heated to 260°C), the contraction start temperature of the second hollow particles is preferably 150°C or higher, 170°C or higher, Alternatively, the temperature may be 180°C or higher, and 260°C or lower, 240°C or lower, 220°C or lower, or 200°C or lower. The contraction start temperature of the second hollow particles was determined by thermomechanical analysis (TMA) in the profile of temperature (horizontal axis) - volume change (vertical axis) when the temperature was raised at a heating rate of 10°C/min. It means the temperature when the change reaches the maximum value.
第二の中空粒子の含有量（大気圧下かつ３０℃における含有量。以下同様。）は、シート１０の断熱性を高める観点から、断熱層１１の全質量を基準として、好ましくは１質量％以上であり、より好ましくは３質量％以上であり、更に好ましくは５質量％以上であり、例えば２０質量％以下であってよい。
The content of the second hollow particles (content under atmospheric pressure and at 30°C; the same applies hereinafter) is preferably 1% by mass based on the total mass of the heat insulating layer 11 from the viewpoint of improving the heat insulation properties of the sheet 10. The content is more preferably 3% by mass or more, still more preferably 5% by mass or more, and may be, for example, 20% by mass or less.
第二の中空粒子の含有量は、シート１０の断熱性を高める観点から、断熱層１１の全体積を基準として、好ましくは５０体積％以上であり、より好ましくは６０体積％以上であり、例えば９５体積％以下であってよい。
From the viewpoint of improving the heat insulation properties of the sheet 10, the content of the second hollow particles is preferably 50% by volume or more, more preferably 60% by volume or more, based on the total volume of the heat insulation layer 11, for example. It may be 95% by volume or less.
第一の中空粒子の含有量に対する第二の中空粒子の含有量の質量比（第二の中空粒子の含有量（質量）／第一の中空粒子の含有量（質量））は、好ましくは１／５以上であり、より好ましくは１／３以上である。第一の中空粒子の含有量に対する第二の中空粒子の含有量の質量比は、好ましくは３以下であり、より好ましくは２以下であり、更に好ましくは１以下である。
The mass ratio of the content of the second hollow particles to the content of the first hollow particles (content (mass) of second hollow particles/content (mass) of first hollow particles) is preferably 1 /5 or more, more preferably 1/3 or more. The mass ratio of the content of the second hollow particles to the content of the first hollow particles is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
第一の中空粒子の含有量に対する第二の中空粒子の含有量の体積比（第二の中空粒子の含有量（体積）／第一の中空粒子の含有量（体積））は、好ましくは１０以上であり、より好ましくは１５以上である。第一の中空粒子の含有量に対する第二の中空粒子の含有量の体積比は、好ましくは８０以下であり、より好ましくは６０以下であり、更に好ましくは４５以下である。
The volume ratio of the content of the second hollow particles to the content of the first hollow particles (content (volume) of second hollow particles/content (volume) of first hollow particles) is preferably 10 or more, and more preferably 15 or more. The volume ratio of the content of the second hollow particles to the content of the first hollow particles is preferably 80 or less, more preferably 60 or less, and still more preferably 45 or less.
無機中空粒子の外殻を構成する無機材料は、例えば、ホウケイ酸ガラス（ホウケイ酸ナトリウムガラス等）、アルミノケイ酸ガラス、それらを複合化させたガラス等の無機ガラスであってよい。無機中空粒子の中空部には、例えば気体が内包されている。無機中空粒子は、例えば、常温常圧下（例えば、少なくとも大気圧下かつ３０℃）において気体を内包している。
The inorganic material constituting the outer shell of the inorganic hollow particles may be, for example, an inorganic glass such as borosilicate glass (sodium borosilicate glass, etc.), aluminosilicate glass, or a composite glass thereof. For example, gas is encapsulated in the hollow part of the inorganic hollow particles. The inorganic hollow particles, for example, encapsulate gas at room temperature and normal pressure (eg, at least atmospheric pressure and 30° C.).
中空粒子の合計含有量（大気圧下かつ３０℃における、第一の中空粒子、第二の中空粒子、及び無機中空粒子の合計含有量。以下同様。）は、シート１０の全質量を基準として、例えば、４質量％以上、８質量％以上、又は１０質量％以上であってよく、４０質量％以下、３５質量％以下、又は３０質量％以下であってよい。
The total content of hollow particles (total content of first hollow particles, second hollow particles, and inorganic hollow particles under atmospheric pressure and at 30°C. The same applies hereinafter) is based on the total mass of the sheet 10. , for example, may be 4% by weight or more, 8% by weight or more, or 10% by weight or more, and may be 40% by weight or less, 35% by weight or less, or 30% by weight or less.
中空粒子の合計含有量は、シート１０の全体積を基準として、例えば、５０体積％以上、６０体積％以上、又は７０体積％以上であってよく、９５体積％以下であってよい。
The total content of hollow particles may be, for example, 50 volume % or more, 60 volume % or more, or 70 volume % or more, and 95 volume % or less, based on the total volume of the sheet 10.
マトリックスポリマーは、断熱層１１に含まれる中空粒子等の他の材料を保持するための母体となる（連続相を形成する）ポリマー（バインダーポリマー）である。中空粒子は、マトリックスポリマーに保持されていてよく、マトリックスポリマー中に分散されていてよい。
The matrix polymer is a polymer (binder polymer) that serves as a base (forms a continuous phase) for holding other materials such as hollow particles contained in the heat insulating layer 11. The hollow particles may be retained in the matrix polymer or dispersed within the matrix polymer.
マトリックスポリマーは、下記式（１）で表される化合物をモノマー単位として含んでいてよい。言い換えれば、マトリックスポリマーは、下記式（１）で表される化合物を含む重合性化合物の重合体であってよい。
式（１）中、Ｒ１１及びＲ１２はそれぞれ独立に水素原子又はメチル基を表し、Ｒ１３はポリオキシアルキレン鎖を有する２価の基を表す。
The matrix polymer may contain a compound represented by the following formula (1) as a monomer unit. In other words, the matrix polymer may be a polymer of a polymerizable compound containing a compound represented by the following formula (1).
In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.
マトリックスポリマーが、上記式（１）で表される化合物をモノマー単位として含む場合、断熱層１１が低弾性で伸びに優れるため、シート１０の被着体への追従性を高めることができる。
When the matrix polymer contains the compound represented by the above formula (1) as a monomer unit, the heat insulating layer 11 has low elasticity and excellent elongation, so that the followability of the sheet 10 to the adherend can be improved.
一実施形態において、Ｒ１１及びＲ１２の一方が水素原子であり、かつ他方がメチル基であってよい。他の一実施形態において、Ｒ１１及びＲ１２の両方が水素原子であってよい。他の実施形態において、Ｒ１１及びＲ１２の両方がメチル基であってよい。
In one embodiment, one of R 11 and R 12 may be a hydrogen atom, and the other may be a methyl group. In another embodiment, both R 11 and R 12 may be hydrogen atoms. In other embodiments, both R 11 and R 12 can be methyl groups.
一実施形態において、ポリオキシアルキレン鎖は、下記式（２）で表される構造単位を含む。これにより、断熱層１１の強度を高めることができる。
In one embodiment, the polyoxyalkylene chain includes a structural unit represented by the following formula (2). Thereby, the strength of the heat insulating layer 11 can be increased.
この場合、Ｒ１３はポリオキシエチレン鎖を有する２価の基であってよく、式（１）で表される化合物は、好ましくは下記式（１－２）で表される化合物（ポリエチレングリコールジ（メタ）アクリレート）である。
式（１－２）中、Ｒ１１及びＲ１２は式（１）におけるＲ１１及びＲ１２とそれぞれ同義であり、ｍは２以上の整数である。
In this case, R 13 may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by formula (1-2) below (polyethylene glycol di (meth)acrylate).
In formula (1-2), R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and m is an integer of 2 or more.
他の一実施形態において、ポリオキシアルキレン鎖は、下記式（３）で表される構造単位を含む。
In another embodiment, the polyoxyalkylene chain includes a structural unit represented by the following formula (3).
この場合、Ｒ１３はポリオキシプロピレン鎖を有する２価の基であってよく、式（１）で表される化合物は、好ましくは下記式（１－３）で表される化合物（ポリプロピレングリコールジ（メタ）アクリレート）である。
式（１－３）中、Ｒ１１及びＲ１２は式（１）におけるＲ１１及びＲ１２とそれぞれ同義であり、ｎは２以上の整数である。
In this case, R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di (meth)acrylate).
In formula (1-3), R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and n is an integer of 2 or more.
他の一実施形態において、ポリオキシアルキレン鎖は、好ましくは、上述した、式（２）で表される構造単位、及び式（３）で表される構造単位を含む共重合鎖である。共重合鎖は、交互共重合鎖、ブロック共重合鎖、又はランダム共重合鎖のいずれであってもよい。共重合鎖は、好ましくはランダム共重合鎖である。
In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain containing the above-mentioned structural unit represented by formula (2) and the structural unit represented by formula (3). The copolymer chain may be an alternating copolymer chain, a block copolymer chain, or a random copolymer chain. The copolymer chain is preferably a random copolymer chain.
上述した各実施形態において、ポリオキシアルキレン鎖は、式（２）で表される構造単位及び式（３）で表される構造単位以外に、オキシテトラメチレン基、オキシブチレン基、オキシペンチレン基等の、炭素数４～５のオキシアルキレン基を構造単位として有していてもよい。
In each of the embodiments described above, the polyoxyalkylene chain includes an oxytetramethylene group, an oxybutylene group, an oxypentylene group, in addition to the structural unit represented by formula (2) and the structural unit represented by formula (3). It may have an oxyalkylene group having 4 to 5 carbon atoms as a structural unit.
Ｒ１３は、上述したポリオキシアルキレン鎖に加えて、その他の有機基を更に有する２価の基であってもよい。その他の有機基は、ポリオキシアルキレン鎖以外の鎖状の基であってよく、例えば、メチレン鎖（－ＣＨ２－を構造単位とする鎖）、ポリエステル鎖（－ＣＯＯ－を構造単位中に含む鎖）、ポリウレタン鎖（－ＯＣＯＮ－を構造単位中に含む鎖）等であってよい。
In addition to the above-mentioned polyoxyalkylene chain, R 13 may be a divalent group further having another organic group. The other organic group may be a chain group other than a polyoxyalkylene chain, such as a methylene chain (a chain containing -CH 2 - as a structural unit), a polyester chain (a chain containing -COO- in the structural unit), and a polyester chain (a chain containing -COO- in the structural unit). chain), polyurethane chain (chain containing -OCON- in the structural unit), etc.
例えば、式（１）で表される化合物は、下記式（１－４）で表される化合物であってもよい。
式（１－４）中、Ｒ１１及びＲ１２は式（１）におけるＲ１１及びＲ１２とそれぞれ同義であり、Ｒ１４及びＲ１５は、それぞれ独立に炭素数２～５のアルキレン基であり、ｋ１、ｋ２及びｋ３はそれぞれ独立に２以上の整数である。ｋ２は、例えば１６以下の整数であってよい。
For example, the compound represented by formula (1) may be a compound represented by formula (1-4) below.
In formula (1-4), R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), and R 14 and R 15 each independently represent an alkylene group having 2 to 5 carbon atoms. , k1, k2 and k3 are each independently an integer of 2 or more. k2 may be an integer of 16 or less, for example.
複数存在するＲ１４及びＲ１５は、それぞれ、互いに同一であってよく、互いに異なっていてもよい。複数存在するＲ１４及びＲ１５は、それぞれ、好ましくは、エチレン基及びプロピレン基を含む。すなわち、（Ｒ１４Ｏ）ｋ１で表されるポリオキシアルキレン鎖、及び（Ｒ１５Ｏ）ｋ３で表されるポリオキシアルキレン鎖は、それぞれ、好ましくは、オキシエチレン基（上記式（２）で表される構造単位）、及びオキシプロピレン基（上記式（３）で表される構造単位）を含む共重合鎖である。
A plurality of R 14 and R 15 may be the same or different from each other. The plurality of R 14 and R 15 preferably include an ethylene group and a propylene group, respectively. That is, the polyoxyalkylene chain represented by (R 14 O) k1 and the polyoxyalkylene chain represented by (R 15 O) k3 are each preferably an oxyethylene group (represented by the above formula (2)). It is a copolymer chain containing a structural unit represented by the above formula (3)) and an oxypropylene group (a structural unit represented by the above formula (3)).
上述した各実施形態において、ポリオキシアルキレン鎖におけるオキシアルキレン基の数は、好ましくは１００以上である。ポリオキシアルキレン鎖におけるオキシアルキレン基の数が１００以上であると、式（１）で表される化合物の主鎖が長くなることにより、断熱層１１の伸びが更に優れ、断熱層１１の強度も高めることができる。オキシアルキレン基の数は、式（１－２）におけるｍ、式（１－３）におけるｎ、並びに式（１－４）におけるｋ１及びｋ３のそれぞれに相当する。
In each of the embodiments described above, the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 100 or more. When the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more, the main chain of the compound represented by formula (1) becomes longer, so that the elongation of the heat insulating layer 11 is further excellent, and the strength of the heat insulating layer 11 is also improved. can be increased. The number of oxyalkylene groups corresponds to m in formula (1-2), n in formula (1-3), and k1 and k3 in formula (1-4), respectively.
ポリオキシアルキレン鎖におけるオキシアルキレン基の数は、より好ましくは、１３０以上、１８０以上、２００以上、２２０以上、２５０以上、２７０以上、３００以上、又は３２０以上である。ポリオキシアルキレン鎖におけるオキシアルキレン基の数は、６００以下、５７０以下、又は５３０以下であってよい。
The number of oxyalkylene groups in the polyoxyalkylene chain is more preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more. The number of oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.
式（１）で表される化合物の重量平均分子量は、断熱層１１が低弾性で伸びに優れる観点から、好ましくは、５０００以上、６０００以上、７０００以上、８０００以上、９０００以上、１００００以上、１１０００以上、１２０００以上、１３０００以上、１４０００以上、又は１５０００以上である。式（１）で表される化合物の重量平均分子量は、好ましくは、１０００００以下、８００００以下、６００００以下、３４０００以下、３１０００以下、又は２８０００以下である。
The weight average molecular weight of the compound represented by formula (1) is preferably 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, or 11,000 or more, from the viewpoint that the heat insulating layer 11 has low elasticity and excellent elongation. 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more. The weight average molecular weight of the compound represented by formula (1) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less.
マトリックスポリマーは、モノマー単位として式（１）で表される化合物のみを含有してよい。マトリックスポリマーは、式（１）で表される化合物以外の他の重合性化合物（詳細は後述する）をモノマー単位として更に含有してもよい。この場合、式（１）で表される化合物の含有量は、断熱層１１がより低弾性で伸びに優れる観点から、式（１）で表される化合物及び他の重合性化合物の合計（以下、「モノマー単位の含有量の合計」という）１００質量部に対して、好ましくは、２０質量部以上、３０質量部以上、又は４０質量部以上である。式（１）で表される化合物の含有量は、モノマー単位の含有量の合計１００質量部に対して、８０質量部以下、７０質量部以下、又は６０質量部以下であってよい。
The matrix polymer may contain only the compound represented by formula (1) as a monomer unit. The matrix polymer may further contain other polymerizable compounds (details will be described later) other than the compound represented by formula (1) as a monomer unit. In this case, the content of the compound represented by formula (1) is the sum of the compound represented by formula (1) and other polymerizable compounds (hereinafter referred to as , "total monomer unit content") is preferably 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more. The content of the compound represented by formula (1) may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, based on 100 parts by mass of the total content of monomer units.
マトリックスポリマーにおける他の重合性化合物（モノマー単位）は、例えば、（メタ）アクリロイル基を一つ有する化合物であってよい。当該化合物の例としては、上述した、アクリル共重合体がモノマー単位として含み得る、（メタ）アクリロイル基を有する化合物が挙げられる。また、マトリックスポリマーにおける他の重合性化合物は、一つの（メタ）アクリロイル基に加えて、芳香族炭化水素基、ポリオキシアルキレン鎖を含む基、アルコキシ基、フェノキシ基、シラン基を含む基、シロキサン結合を含む基、ハロゲン原子、アミノ基、又はエポキシ基を有する化合物であってもよい。特に、マトリックスポリマーが、（メタ）アクリロイル基に加えて、ヒドロキシル基、カルボキシル基、アミノ基、又はエポキシ基を有する化合物を含有することにより、断熱層１１の他の部材に対する密着性を更に向上できる。
The other polymerizable compound (monomer unit) in the matrix polymer may be, for example, a compound having one (meth)acryloyl group. Examples of such compounds include the above-mentioned compounds having (meth)acryloyl groups that may be included in the acrylic copolymer as a monomer unit. Other polymerizable compounds in the matrix polymer include, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, an alkoxy group, a phenoxy group, a group containing a silane group, and a siloxane group. It may be a compound having a group containing a bond, a halogen atom, an amino group, or an epoxy group. In particular, when the matrix polymer contains a compound having a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in addition to a (meth)acryloyl group, the adhesion of the heat insulating layer 11 to other members can be further improved. .
（メタ）アクリロイル基及び芳香族炭化水素基を有する化合物としては、ベンジル（メタ）アクリレート等が挙げられる。
Examples of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate and the like.
（メタ）アクリロイル基、及びポリオキシアルキレン鎖を含む基を有する化合物としては、ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリブチレングリコール（メタ）アクリレート、メトキシポリブチレングリコール（メタ）アクリレート等が挙げられる。
Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, Examples include polybutylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, and the like.
（メタ）アクリロイル基及びアルコキシ基を有する化合物としては、２－メトキシエチルアクリレート等が挙げられる。
Examples of the compound having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate.
（メタ）アクリロイル基及びフェノキシ基を有する化合物としては、フェノキシエチル（メタ）アクリレート等が挙げられる。
Examples of the compound having a (meth)acryloyl group and a phenoxy group include phenoxyethyl (meth)acrylate.
（メタ）アクリロイル基、及びシラン基を含む基を有する化合物としては、３－アクリロキシプロピルトリエトキシシラン、１０－メタクリロイルオキシデシルトリメトキシシラン、１０－アクリロイルオキシデシルトリメトキシシラン、１０－メタクリロイルオキシデシルトリエトキシシラン、１０－アクリロイルオキシデシルトリエトキシシラン等が挙げられる。
Examples of compounds having a group containing a (meth)acryloyl group and a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyl Examples include triethoxysilane and 10-acryloyloxydecyltriethoxysilane.
（メタ）アクリロイル基、及びシロキサン結合を含む基を有する化合物としては、シリコーン（メタ）アクリレート等が挙げられる。
Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate.
（メタ）アクリロイル基及びハロゲン原子を有する化合物としては、トリフルオロメチル（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、１，１，１，３，３，３－ヘキサフルオロ－２－プロピル（メタ）アクリレート、パーフルオロエチルメチル（メタ）アクリレート、パーフルオロプロピルメチル（メタ）アクリレート、パーフルオロブチルメチル（メタ）アクリレート、パーフルオロペンチルメチル（メタ）アクリレート、パーフルオロヘキシルメチル（メタ）アクリレート、パーフルオロヘプチルメチル（メタ）アクリレート、パーフルオロオクチルメチル（メタ）アクリレート、パーフルオロノニルメチル（メタ）アクリレート、パーフルオロデシルメチル（メタ）アクリレート、パーフルオロウンデシルメチル（メタ）アクリレート、パーフルオロドデシルメチル（メタ）アクリレート、パーフルオロトリデシルメチル（メタ）アクリレート、パーフルオロテトラデシルメチル（メタ）アクリレート、２－（トリフルオロメチル）エチル（メタ）アクリレート、２－（パーフルオロエチル）エチル（メタ）アクリレート、２－（パーフルオロプロピル）エチル（メタ）アクリレート、２－（パーフルオロブチル）エチル（メタ）アクリレート、２－（パーフルオロペンチル）エチル（メタ）アクリレート、２－（パーフルオロヘキシル）エチル（メタ）アクリレート、２－（パーフルオロヘプチル）エチル（メタ）アクリレート、２－（パーフルオロオクチル）エチル（メタ）アクリレート、２－（パーフルオロノニル）エチル（メタ）アクリレート、２－（パーフルオロトリデシル）エチル（メタ）アクリレート、２－（パーフルオロテトラデシル）エチル（メタ）アクリレート等のフッ素原子を有する（メタ）アクリレートなどが挙げられる。
Examples of compounds having a (meth)acryloyl group and a halogen atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro -2-Propyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, perfluoropentylmethyl (meth)acrylate, perfluorohexylmethyl ( meth)acrylate, perfluoroheptylmethyl(meth)acrylate, perfluorooctylmethyl(meth)acrylate, perfluorononylmethyl(meth)acrylate, perfluorodecylmethyl(meth)acrylate, perfluoroundecylmethyl(meth)acrylate, Perfluorododecylmethyl (meth)acrylate, perfluorotridecylmethyl (meth)acrylate, perfluorotetradecylmethyl (meth)acrylate, 2-(trifluoromethyl)ethyl (meth)acrylate, 2-(perfluoroethyl)ethyl (meth)acrylate, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluoropentyl)ethyl (meth)acrylate, 2-(perfluorohexyl) ) Ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorononyl)ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, Examples include (meth)acrylates having a fluorine atom, such as fluorotridecyl)ethyl (meth)acrylate and 2-(perfluorotetradecyl)ethyl (meth)acrylate.
（メタ）アクリロイル基及びアミノ基を有する化合物としては、例えば、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート等が挙げられる。
Examples of compounds having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. , N,N-diethylaminopropyl (meth)acrylate, and the like.
（メタ）アクリロイル基及びエポキシ基を有する化合物としては、例えば、（メタ）アクリル酸グリシジル、α－エチル（メタ）アクリル酸グリシジル、α－ｎ－プロピル（メタ）アクリル酸グリシジル、α－ｎ－ブチル（メタ）アクリル酸グリシジル、（メタ）アクリル酸－３，４－エポキシブチル、（メタ）アクリル酸－４，５－エポキシペンチル、（メタ）アクリル酸－６，７－エポキシヘプチル、α－エチル（メタ）アクリル酸－６，７－エポキシヘプチル、（メタ）アクリル酸－３－メチル－３，４－エポキシブチル、（メタ）アクリル酸－４－メチル－４，５－エポキシペンチル、（メタ）アクリル酸－５－メチル－５，６－エポキシヘキシル、（メタ）アクリル酸－β－メチルグリシジル、α－エチル（メタ）アクリル酸－β－メチルグリシジル等が挙げられる。
Examples of compounds having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, α-ethyl (meth)glycidyl acrylate, α-n-propyl (meth)glycidyl acrylate, α-n-butyl Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl ( 6,7-epoxyheptyl meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, (meth)acrylic Examples include 5-methyl-5,6-epoxyhexyl acid, β-methylglycidyl (meth)acrylate, and β-methylglycidyl α-ethyl (meth)acrylate.
マトリックスポリマーは、モノマー単位として、上記他の重合性化合物のうちの１種を含有してもよく、２種以上を含有してもよい。また、式（１）で表される化合物を更に含有してもよく、含有しなくてもよい。
The matrix polymer may contain one or more of the above other polymerizable compounds as a monomer unit. Moreover, the compound represented by formula (1) may or may not be further contained.
マトリックスポリマーの含有量は、断熱層１１の全質量を基準として、例えば、４０質量％以上、５０質量％以上、６０質量％以上、又は７０質量％以上であってよく、９５質量％以下、又は９０質量％以下であってよい。
The content of the matrix polymer may be, for example, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 95% by mass or less, based on the total mass of the heat insulating layer 11. It may be 90% by mass or less.
断熱層１１は、必要に応じて、その他の添加剤を更に含有することができる。その他の添加剤としては、例えば、可塑剤、酸化防止剤（例えばフェノール系酸化防止剤）、表面調整剤（例えばシランカップリング剤）、分散剤、硬化促進剤、着色剤、結晶核剤、熱安定剤、発泡剤、難燃剤、制振剤、脱水剤、難燃助剤（例えば金属酸化物）等が挙げられる。その他の添加剤の含有量は、断熱層１１の全質量を基準として、０．１質量％以上であってよく、３０質量％以下であってよい。
The heat insulating layer 11 can further contain other additives as necessary. Other additives include, for example, plasticizers, antioxidants (e.g. phenolic antioxidants), surface conditioners (e.g. silane coupling agents), dispersants, curing accelerators, colorants, crystal nucleating agents, thermal Stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, flame retardant aids (for example, metal oxides) and the like can be mentioned. The content of other additives may be 0.1% by mass or more and 30% by mass or less based on the total mass of the heat insulating layer 11.
断熱層１１の厚みは、例えば、１００μｍ以上、２００μｍ以上、又は５００μｍ以上であってよく、１０ｍｍ以下、５ｍｍ以下、又は２ｍｍ以下であってよい。
The thickness of the heat insulating layer 11 may be, for example, 100 μm or more, 200 μm or more, or 500 μm or more, and may be 10 mm or less, 5 mm or less, or 2 mm or less.
シート１０は、図１に示す一実施形態のように、断熱層１１及び粘着層１２のみからなっていてよい。他の一実施形態において、シートは、断熱層及び粘着層以外の他の層を更に備えていてもよい。この場合、シートにおいて、断熱層と粘着層とは互いに接していてよく（他の層を介さず積層されていてよく）、断熱層と粘着層とは他の層を介して積層されていてもよい。他の層の例としては、表面保護層、接着層、及び支持層が挙げられる。
The sheet 10 may consist only of a heat insulating layer 11 and an adhesive layer 12, as in the embodiment shown in FIG. In another embodiment, the sheet may further include layers other than the heat insulating layer and the adhesive layer. In this case, in the sheet, the heat insulating layer and the adhesive layer may be in contact with each other (they may be laminated without intervening another layer), and the heat insulating layer and the adhesive layer may be laminated with another layer in between. good. Examples of other layers include a surface protection layer, an adhesive layer, and a support layer.
他の層を備えるシートは、一実施形態において、表面保護層（第一の表面保護層）と、断熱層と、接着層（第一の接着層）と、支持層（第一の支持層）と、接着層（第二の接着層）と、支持層（第二の支持層）と、粘着層と、表面保護層（第二の表面保護層）と、を備えるシートであってよい。表面保護層は、例えば、断熱層又は粘着層と接する面が易剥離処理された樹脂フィルム（ＰＥＴフィルム等）で構成されていてよい。接着層は、例えば、アクリル系接着剤、エポキシ系接着剤等を含有していてよい。支持層は、例えば、樹脂フィルム（ポリイミドフィルム等）で構成されていてよい。
In one embodiment, the sheet including other layers includes a surface protection layer (first surface protection layer), a heat insulating layer, an adhesive layer (first adhesive layer), and a support layer (first support layer). The sheet may include an adhesive layer (second adhesive layer), a support layer (second support layer), an adhesive layer, and a surface protection layer (second surface protection layer). The surface protective layer may be composed of, for example, a resin film (such as a PET film) whose surface in contact with the heat insulating layer or the adhesive layer has been subjected to easy-peel treatment. The adhesive layer may contain, for example, an acrylic adhesive, an epoxy adhesive, or the like. The support layer may be made of, for example, a resin film (such as a polyimide film).
シート１０の厚みは、例えば、１００μｍ以上、２００μｍ以上、又は５００μｍ以上であってよく、１１ｍｍ以下、５ｍｍ以下、３ｍｍ以下、又は２ｍｍ以下であってよい。
The thickness of the sheet 10 may be, for example, 100 μm or more, 200 μm or more, or 500 μm or more, and may be 11 mm or less, 5 mm or less, 3 mm or less, or 2 mm or less.
シート１０は、例えば、断熱層１１及び粘着層１２をそれぞれ作製し、断熱層１１と粘着層１２とを、貼り合わせることにより作製することができる。例えば、上記の他の層を備えるシートの製造方法は、表面保護層（第一の表面保護層）及び断熱層の積層体Ａと、接着層（第一の接着層）、支持層（第一の支持層）、及び接着層（第二の接着層）の積層体Ｂと、支持層（第二の支持層）、粘着層、及び表面保護層（第二の表面保護層）の積層体Ｃとをそれぞれ準備する工程と、積層体Ａの断熱層と積層体Ｂの接着層（第一の接着層）とを貼り合わせると共に、積層体Ｂの接着層（第二の接着層）と積層体Ｃの支持層（第二の支持層）とを貼り合わせる工程とを備えていてよい。
The sheet 10 can be produced, for example, by separately producing the heat insulating layer 11 and the adhesive layer 12, and then bonding the heat insulating layer 11 and the adhesive layer 12 together. For example, a method for producing a sheet including the other layers described above includes a laminate A of a surface protection layer (first surface protection layer) and a heat insulating layer, an adhesive layer (first adhesive layer), a support layer (first A laminate B of a support layer (supporting layer) and an adhesive layer (second adhesive layer), and a laminate C of a support layer (second support layer), an adhesive layer, and a surface protection layer (second surface protection layer) a process of preparing the laminate A and the adhesive layer (first adhesive layer) of the laminate B, and bonding the adhesive layer (second adhesive layer) of the laminate B and the laminate It may also include a step of bonding the support layer (second support layer) of C.
積層体Ａは、例えば、上述した第一の中空粒子、第二の中空粒子及び重合性化合物を含む混合物を準備した後、表面保護層（第一の表面保護層）上で当該混合物中の重合性化合物を重合させてマトリックスポリマーを形成することにより得られる。積層体Ｂとしては、例えば、支持層（第一の支持層）と、支持層の両面それぞれに設けられた接着層（第一の接着層）及び接着層（第二の接着層）とを備える両面接着テープを用いることができる。積層体Ｃは、例えば、アクリル系粘着剤等の材料を混合して得た粘着剤組成物を、表面保護層（第二の表面保護層）上に塗工し、粘着剤組成物の乾燥及び／又は粘着剤組成物中の硬化性成分の硬化を進行させて粘着層を形成した後、粘着層の表面保護層（第二の表面保護層）と反対側の面に支持層（第二の支持層）を設けることにより得られる。積層体Ａ、積層体Ｂ、及び積層体Ｃを貼り合わせる工程では、例えば、ロールラミネーターを用いることができる。
Laminated body A is produced, for example, by preparing a mixture containing the first hollow particles, second hollow particles, and a polymerizable compound described above, and then applying polymerization in the mixture on a surface protective layer (first surface protective layer). It is obtained by polymerizing a compound to form a matrix polymer. The laminate B includes, for example, a support layer (first support layer), and an adhesive layer (first adhesive layer) and an adhesive layer (second adhesive layer) provided on both surfaces of the support layer, respectively. Double-sided adhesive tape can be used. The laminate C is produced by coating a pressure-sensitive adhesive composition obtained by mixing materials such as an acrylic pressure-sensitive adhesive on a surface protective layer (second surface protective layer), drying the pressure-sensitive adhesive composition, and drying the pressure-sensitive adhesive composition. / Or after the curing of the curable component in the adhesive composition is progressed to form an adhesive layer, a support layer (second support layer). In the step of bonding the laminate A, the laminate B, and the laminate C together, a roll laminator can be used, for example.
以下、実施例に基づいて本発明を更に具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples in any way.
＜粘着層＞
［粘着層の作製］
粘着層を作製するために、以下の各成分を用いた。
（アクリル共重合体）
Ａ－１：ブチルアクリレート（ＢＡ）、エチルアクリレート（ＥＡ）、アクリロニトリル（ＡＮ）、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）、及びアクリル酸（ＡＡ）の共重合体（モノマー比：ＢＡ／ＥＡ／ＡＮ／ＨＥＭＡ／ＡＡ＝６１／１９／１５／２．５／２．５、カルボキシル基の濃度：２．７７×１０―４ｍｏｌ／Ｌ、水酸基の濃度：２．０５×１０―４ｍｏｌ／Ｌ、Ｔｇ：－２８℃。）
Ａ－２：ＢＡ及びＮ－アクリロイルモルホリン（ＡＣＭＯ）の共重合体（モノマー単位の含有比率（質量比）：ＢＡ／ＡＣＭＯ＝９９．９／０．１、多分散度：Ｍｗ／Ｍｎ＝１．７、酸価：２３．３ｍｇＫＯＨ／ｇ。）
Ａ－３：ＢＡ、ＡＮ及びＡＡの共重合体（モノマー単位の含有比率（質量比）：ＢＡ／ＡＮ／ＡＡ＝８５／７．５／７．５、Ｍｗ＝６７万～９５万、多分散度：Ｍｗ／Ｍｎ＝３．８～６．５、カルボキシル基の濃度：１０．４１×１０―４ｍｏｌ／Ｌ、Ｔｇ：－４４℃。）
（架橋剤）
Ｂ－１：下記式（Ｂ－１）で表される架橋剤
Ｂ－２：下記式（Ｂ－２）で表される架橋剤（三菱ガス化学（株）製「テトラッドＸ」）
ｂ－１：３個のイソシアネート基を有する（エポキシ基を有さない）架橋剤（東ソー（株）製「コロネートＬ３８ＥＴ」）
（酸化防止剤）
Ｃ：４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミン（精工化学（株）製「ノンフレックスＤＣＤ」） <Adhesive layer>
[Preparation of adhesive layer]
The following components were used to prepare the adhesive layer.
(acrylic copolymer)
A-1: Copolymer of butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), 2-hydroxyethyl methacrylate (HEMA), and acrylic acid (AA) (monomer ratio: BA/EA/AN/ HEMA/AA=61/19/15/2.5/2.5, concentration of carboxyl group: 2.77×10 −4 mol/L, concentration of hydroxyl group: 2.05×10 −4 mol/L, Tg :-28℃.)
A-2: Copolymer of BA and N-acryloylmorpholine (ACMO) (monomer unit content ratio (mass ratio): BA/ACMO=99.9/0.1, polydispersity: Mw/Mn=1. 7. Acid value: 23.3mgKOH/g.)
A-3: Copolymer of BA, AN and AA (monomer unit content ratio (mass ratio): BA/AN/AA=85/7.5/7.5, Mw=670,000 to 950,000, polydispersity degree: Mw/Mn = 3.8 to 6.5, concentration of carboxyl group: 10.41 x 10 -4 mol/L, Tg: -44°C.)
(Crosslinking agent)
B-1: Crosslinking agent represented by the following formula (B-1)
B-2: Crosslinking agent represented by the following formula (B-2) (“Tetrad X” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
b-1: Crosslinking agent having 3 isocyanate groups (not having epoxy groups) (“Coronate L38ET” manufactured by Tosoh Corporation)
(Antioxidant)
C: 4,4-bis(α,α-dimethylbenzyl)diphenylamine (“Nonflex DCD” manufactured by Seiko Chemical Co., Ltd.)
［粘着層の作製］
粘着層を作製するために、以下の各成分を用いた。
（アクリル共重合体）
Ａ－１：ブチルアクリレート（ＢＡ）、エチルアクリレート（ＥＡ）、アクリロニトリル（ＡＮ）、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）、及びアクリル酸（ＡＡ）の共重合体（モノマー比：ＢＡ／ＥＡ／ＡＮ／ＨＥＭＡ／ＡＡ＝６１／１９／１５／２．５／２．５、カルボキシル基の濃度：２．７７×１０―４ｍｏｌ／Ｌ、水酸基の濃度：２．０５×１０―４ｍｏｌ／Ｌ、Ｔｇ：－２８℃。）
Ａ－２：ＢＡ及びＮ－アクリロイルモルホリン（ＡＣＭＯ）の共重合体（モノマー単位の含有比率（質量比）：ＢＡ／ＡＣＭＯ＝９９．９／０．１、多分散度：Ｍｗ／Ｍｎ＝１．７、酸価：２３．３ｍｇＫＯＨ／ｇ。）
Ａ－３：ＢＡ、ＡＮ及びＡＡの共重合体（モノマー単位の含有比率（質量比）：ＢＡ／ＡＮ／ＡＡ＝８５／７．５／７．５、Ｍｗ＝６７万～９５万、多分散度：Ｍｗ／Ｍｎ＝３．８～６．５、カルボキシル基の濃度：１０．４１×１０―４ｍｏｌ／Ｌ、Ｔｇ：－４４℃。）
（架橋剤）
Ｂ－１：下記式（Ｂ－１）で表される架橋剤
（酸化防止剤）
Ｃ：４，４－ビス（α，α－ジメチルベンジル）ジフェニルアミン（精工化学（株）製「ノンフレックスＤＣＤ」） <Adhesive layer>
[Preparation of adhesive layer]
The following components were used to prepare the adhesive layer.
(acrylic copolymer)
A-1: Copolymer of butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), 2-hydroxyethyl methacrylate (HEMA), and acrylic acid (AA) (monomer ratio: BA/EA/AN/ HEMA/AA=61/19/15/2.5/2.5, concentration of carboxyl group: 2.77×10 −4 mol/L, concentration of hydroxyl group: 2.05×10 −4 mol/L, Tg :-28℃.)
A-2: Copolymer of BA and N-acryloylmorpholine (ACMO) (monomer unit content ratio (mass ratio): BA/ACMO=99.9/0.1, polydispersity: Mw/Mn=1. 7. Acid value: 23.3mgKOH/g.)
A-3: Copolymer of BA, AN and AA (monomer unit content ratio (mass ratio): BA/AN/AA=85/7.5/7.5, Mw=670,000 to 950,000, polydispersity degree: Mw/Mn = 3.8 to 6.5, concentration of carboxyl group: 10.41 x 10 -4 mol/L, Tg: -44°C.)
(Crosslinking agent)
B-1: Crosslinking agent represented by the following formula (B-1)
(Antioxidant)
C: 4,4-bis(α,α-dimethylbenzyl)diphenylamine (“Nonflex DCD” manufactured by Seiko Chemical Co., Ltd.)
表１に示す量の各成分と、下記の溶媒とを混合し、自公転ミキサーにて回転数１０００ｒｐｍで５分間撹拌した後、常温で気泡がなくなるまで放置することにより粘着剤組成物を得た。各例で用いた溶媒の種類及び量は下記のとおりである。なお、下記の溶媒の量は、表１に示す各成分の合計１００質量部に対する量を意味する。
（比較例１）トルエン：メチルエチルケトン＝４：１の混合溶媒３７質量部
（実施例１）トルエン：メチルエチルケトン＝４：１の混合溶媒３７質量部
（実施例２）酢酸エチル１２１質量部
（実施例３）トルエン：メチルエチルケトン＝４：１の混合溶媒１１．５質量部 A pressure-sensitive adhesive composition was obtained by mixing each component in the amounts shown in Table 1 and the following solvent, stirring for 5 minutes at a rotational speed of 1000 rpm using a rotational revolution mixer, and then leaving it at room temperature until there were no air bubbles. . The types and amounts of solvents used in each example are as follows. In addition, the amount of the following solvent means the amount with respect to the total of 100 parts by mass of each component shown in Table 1.
(Comparative Example 1) 37 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1 (Example 1) 37 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1 (Example 2) 121 parts by mass of ethyl acetate (Example 3) ) 11.5 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1
（比較例１）トルエン：メチルエチルケトン＝４：１の混合溶媒３７質量部
（実施例１）トルエン：メチルエチルケトン＝４：１の混合溶媒３７質量部
（実施例２）酢酸エチル１２１質量部
（実施例３）トルエン：メチルエチルケトン＝４：１の混合溶媒１１．５質量部 A pressure-sensitive adhesive composition was obtained by mixing each component in the amounts shown in Table 1 and the following solvent, stirring for 5 minutes at a rotational speed of 1000 rpm using a rotational revolution mixer, and then leaving it at room temperature until there were no air bubbles. . The types and amounts of solvents used in each example are as follows. In addition, the amount of the following solvent means the amount with respect to the total of 100 parts by mass of each component shown in Table 1.
(Comparative Example 1) 37 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1 (Example 1) 37 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1 (Example 2) 121 parts by mass of ethyl acetate (Example 3) ) 11.5 parts by mass of a mixed solvent of toluene: methyl ethyl ketone = 4:1
得られた粘着剤組成物を、片面にシリコーン系剥離剤による易剥離処理が施されている厚さ３８μｍのポリエステルフィルム（商品名：ピューレックスＡ３１、東洋紡(株)製）の易剥離処理面上に塗工した後、乾燥オーブンにより１００℃で２分間乾燥し、厚さ１０μｍの粘着層を形成した。次いで、室温（２５℃）にて、形成した粘着層の露出面上に、厚さ２５μｍのポリイミドフィルム基材（商品名：カプトン１００Ｈ、東レ・デュポン社製）をラミネートすることにより、表面保護層（ポリエステルフィルム）、各実施例及び比較例の粘着層、及び支持層（ポリイミドフィルム基材）がこの順に積層された積層体（積層体Ｃ）を作製した。また、積層体Ｃの表面保護層を剥離することにより、支持層付き粘着層を得た。
The obtained adhesive composition was applied onto the easily peelable surface of a 38 μm thick polyester film (trade name: Purex A31, manufactured by Toyobo Co., Ltd.), which had been treated with a silicone release agent on one side for easy peeling. After coating, it was dried in a drying oven at 100° C. for 2 minutes to form an adhesive layer with a thickness of 10 μm. Next, a 25 μm thick polyimide film base material (trade name: Kapton 100H, manufactured by DuPont Toray) is laminated on the exposed surface of the formed adhesive layer at room temperature (25° C.) to form a surface protective layer. (polyester film), the adhesive layer of each example and comparative example, and the support layer (polyimide film base material) were laminated in this order to produce a laminate (laminate C). Further, by peeling off the surface protective layer of the laminate C, an adhesive layer with a support layer was obtained.
［粘着層のピール強度］
各粘着層の９０°ピール強度を、下記の手順で測定した。縦２５ｍｍ×横７０ｍｍのＳｉウエハと縦２０ｍｍ×横６０ｍｍにカットした支持層付き粘着層を準備した。粘着層とＳｉウエハとが接し、かつ両者の間に気泡が入らないように、Ｓｉウエハ上に支持層付き粘着層を設置した。支持層付き粘着層が設置されたＳｉウエハを縦３８０ｍｍ×横５００ｍｍ×厚み０．５ｍｍのステンレス板の上に乗せ、ロールラミネーター（大成ラミネーター（株）製「ＶＡ－７７０Ｈ特殊型ラミネーター」）により圧力６ｋｇｆ／ｃｍ２、回転速度０．２ｒｐｍ、温度４０℃の条件で粘着層とＳｉウエハとを貼り付けて、サンプルを作製した。得られたサンプルの支持層付き粘着層を幅５ｍｍでカットし、長さ方向の片側１０ｍｍをＳｉウエハから剥がし、引っ張り試験機（（株）島津製作所製「Ａｕｔｏｇｒａｐｈ ＥＺ－ＴＥＳＴ ＥＺ－Ｓ」）により、９０°ピール強度（初期９０°ピール強度）を測定した。また、作製したサンプルをリフロー炉(タムラ製作所製ＴＮＰ２５－３３７ＥＭシリーズ Ｎ２リフロー装置)に通して熱履歴を加え、放冷した後、同様に９０°ピール強度（加熱後９０°ピール強度）を測定した。熱履歴は、具体的には、リフロー炉において、昇温速度４７℃／分で室温（２５℃）から２００℃まで昇温した後、昇温速度３８℃／分で２００℃から２６０℃まで昇温することにより加えられた。また、放冷は、具体的には、リフロー炉内で６０℃まで冷却し、リフロー炉からとり出して２５℃まで冷却するというものであった。結果を表１に示す。 [Peel strength of adhesive layer]
The 90° peel strength of each adhesive layer was measured according to the following procedure. A Si wafer with a length of 25 mm and a width of 70 mm and an adhesive layer with a support layer cut into a size of 20 mm in length and 60 mm in width were prepared. The adhesive layer with a support layer was placed on the Si wafer so that the adhesive layer and the Si wafer were in contact with each other and no air bubbles were present between the two. The Si wafer on which the adhesive layer with support layer has been installed is placed on a stainless steel plate measuring 380 mm long x 500 mm wide x 0.5 mm thick, and pressure is applied using a roll laminator (“VA-770H special laminator” manufactured by Taisei Laminator Co., Ltd.). A sample was prepared by pasting the adhesive layer and the Si wafer under the conditions of 6 kgf/cm 2 , rotation speed of 0.2 rpm, and temperature of 40°C. The adhesive layer with support layer of the obtained sample was cut to a width of 5 mm, 10 mm of one side in the length direction was peeled off from the Si wafer, and tested using a tensile tester ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation). , 90° peel strength (initial 90° peel strength) was measured. In addition, the prepared sample was passed through a reflow oven (TNP25-337EM series N2 reflow device manufactured by Tamura Seisakusho) to add a thermal history, and after cooling, the 90° peel strength (90° peel strength after heating) was measured in the same manner. . Specifically, the thermal history was determined by raising the temperature from room temperature (25°C) to 200°C at a heating rate of 47°C/min in a reflow oven, and then from 200°C to 260°C at a heating rate of 38°C/min. Added by heating. Moreover, specifically, the cooling was performed by cooling to 60°C in a reflow oven, taking it out from the reflow oven, and cooling it to 25°C. The results are shown in Table 1.
各粘着層の９０°ピール強度を、下記の手順で測定した。縦２５ｍｍ×横７０ｍｍのＳｉウエハと縦２０ｍｍ×横６０ｍｍにカットした支持層付き粘着層を準備した。粘着層とＳｉウエハとが接し、かつ両者の間に気泡が入らないように、Ｓｉウエハ上に支持層付き粘着層を設置した。支持層付き粘着層が設置されたＳｉウエハを縦３８０ｍｍ×横５００ｍｍ×厚み０．５ｍｍのステンレス板の上に乗せ、ロールラミネーター（大成ラミネーター（株）製「ＶＡ－７７０Ｈ特殊型ラミネーター」）により圧力６ｋｇｆ／ｃｍ２、回転速度０．２ｒｐｍ、温度４０℃の条件で粘着層とＳｉウエハとを貼り付けて、サンプルを作製した。得られたサンプルの支持層付き粘着層を幅５ｍｍでカットし、長さ方向の片側１０ｍｍをＳｉウエハから剥がし、引っ張り試験機（（株）島津製作所製「Ａｕｔｏｇｒａｐｈ ＥＺ－ＴＥＳＴ ＥＺ－Ｓ」）により、９０°ピール強度（初期９０°ピール強度）を測定した。また、作製したサンプルをリフロー炉(タムラ製作所製ＴＮＰ２５－３３７ＥＭシリーズ Ｎ２リフロー装置)に通して熱履歴を加え、放冷した後、同様に９０°ピール強度（加熱後９０°ピール強度）を測定した。熱履歴は、具体的には、リフロー炉において、昇温速度４７℃／分で室温（２５℃）から２００℃まで昇温した後、昇温速度３８℃／分で２００℃から２６０℃まで昇温することにより加えられた。また、放冷は、具体的には、リフロー炉内で６０℃まで冷却し、リフロー炉からとり出して２５℃まで冷却するというものであった。結果を表１に示す。 [Peel strength of adhesive layer]
The 90° peel strength of each adhesive layer was measured according to the following procedure. A Si wafer with a length of 25 mm and a width of 70 mm and an adhesive layer with a support layer cut into a size of 20 mm in length and 60 mm in width were prepared. The adhesive layer with a support layer was placed on the Si wafer so that the adhesive layer and the Si wafer were in contact with each other and no air bubbles were present between the two. The Si wafer on which the adhesive layer with support layer has been installed is placed on a stainless steel plate measuring 380 mm long x 500 mm wide x 0.5 mm thick, and pressure is applied using a roll laminator (“VA-770H special laminator” manufactured by Taisei Laminator Co., Ltd.). A sample was prepared by pasting the adhesive layer and the Si wafer under the conditions of 6 kgf/cm 2 , rotation speed of 0.2 rpm, and temperature of 40°C. The adhesive layer with support layer of the obtained sample was cut to a width of 5 mm, 10 mm of one side in the length direction was peeled off from the Si wafer, and tested using a tensile tester ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation). , 90° peel strength (initial 90° peel strength) was measured. In addition, the prepared sample was passed through a reflow oven (TNP25-337EM series N2 reflow device manufactured by Tamura Seisakusho) to add a thermal history, and after cooling, the 90° peel strength (90° peel strength after heating) was measured in the same manner. . Specifically, the thermal history was determined by raising the temperature from room temperature (25°C) to 200°C at a heating rate of 47°C/min in a reflow oven, and then from 200°C to 260°C at a heating rate of 38°C/min. Added by heating. Moreover, specifically, the cooling was performed by cooling to 60°C in a reflow oven, taking it out from the reflow oven, and cooling it to 25°C. The results are shown in Table 1.
＜断熱層＞
［式（１－５）で表される化合物の合成］
撹拌機、温度計、窒素ガス導入管、排出管及び加熱ジャケットから構成された５００ｍＬフラスコを反応器とし、ポリオキシアルキレン鎖を有するグリコール（三洋化成（株）製「ニューポール７５Ｈ－９００００」）２２５ｇ、トルエン３００ｇを反応器に加え、４５℃、撹拌回転数２５０回／分で撹拌し、窒素を１００ｍＬ／分で流し、３０分撹拌した。その後、２５℃に降温し、降温完了後、塩化アクリロイル２．９ｇを反応器に滴下し、３０分撹拌した。その後、トリエチルアミン３．８ｇを滴下し、２時間撹拌した。その後、４５℃に昇温し、２時間反応させた。反応液を濾過し、濾液を脱溶し、式（１－５）で表される化合物（重量平均分子量：１５０００、式（１－５）中のｍ１＋ｍ２が概ね２５２±５、ｎ１＋ｎ２が概ね６３±５の整数（ただし、ｍ１、ｍ２、ｎ１及びｎ２はそれぞれ２以上の整数であり、ｍ１＋ｎ１≧１００、ｍ２＋ｎ２≧１００）である混合物、２５℃における粘度：５０Ｐａ・ｓ）を得た。
［式（１－５）中、－ｒ－はランダム共重合を表す符号である。］
<Insulating layer>
[Synthesis of compound represented by formula (1-5)]
A 500 mL flask consisting of a stirrer, a thermometer, a nitrogen gas inlet pipe, an outlet pipe, and a heating jacket was used as a reactor, and 225 g of glycol having a polyoxyalkylene chain ("Newport 75H-90000" manufactured by Sanyo Kasei Co., Ltd.) was used as a reactor. , 300 g of toluene was added to the reactor, and the mixture was stirred at 45° C. and at a stirring rotation speed of 250 times/min, nitrogen was flowed at 100 mL/min, and the mixture was stirred for 30 minutes. Thereafter, the temperature was lowered to 25°C, and after the temperature was lowered, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Then, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. Thereafter, the temperature was raised to 45° C., and the mixture was reacted for 2 hours. The reaction solution was filtered, the filtrate was desoluted, and a compound represented by formula (1-5) (weight average molecular weight: 15000, m1+m2 in formula (1-5) was approximately 252±5, n1+n2 was approximately 63± A mixture having an integer of 5 (where m1, m2, n1 and n2 are each integers of 2 or more, m1+n1≧100, m2+n2≧100) and a viscosity at 25° C.: 50 Pa·s) was obtained.
[In formula (1-5), -r- is a code representing random copolymerization. ]
［式（１－５）で表される化合物の合成］
撹拌機、温度計、窒素ガス導入管、排出管及び加熱ジャケットから構成された５００ｍＬフラスコを反応器とし、ポリオキシアルキレン鎖を有するグリコール（三洋化成（株）製「ニューポール７５Ｈ－９００００」）２２５ｇ、トルエン３００ｇを反応器に加え、４５℃、撹拌回転数２５０回／分で撹拌し、窒素を１００ｍＬ／分で流し、３０分撹拌した。その後、２５℃に降温し、降温完了後、塩化アクリロイル２．９ｇを反応器に滴下し、３０分撹拌した。その後、トリエチルアミン３．８ｇを滴下し、２時間撹拌した。その後、４５℃に昇温し、２時間反応させた。反応液を濾過し、濾液を脱溶し、式（１－５）で表される化合物（重量平均分子量：１５０００、式（１－５）中のｍ１＋ｍ２が概ね２５２±５、ｎ１＋ｎ２が概ね６３±５の整数（ただし、ｍ１、ｍ２、ｎ１及びｎ２はそれぞれ２以上の整数であり、ｍ１＋ｎ１≧１００、ｍ２＋ｎ２≧１００）である混合物、２５℃における粘度：５０Ｐａ・ｓ）を得た。
[Synthesis of compound represented by formula (1-5)]
A 500 mL flask consisting of a stirrer, a thermometer, a nitrogen gas inlet pipe, an outlet pipe, and a heating jacket was used as a reactor, and 225 g of glycol having a polyoxyalkylene chain ("Newport 75H-90000" manufactured by Sanyo Kasei Co., Ltd.) was used as a reactor. , 300 g of toluene was added to the reactor, and the mixture was stirred at 45° C. and at a stirring rotation speed of 250 times/min, nitrogen was flowed at 100 mL/min, and the mixture was stirred for 30 minutes. Thereafter, the temperature was lowered to 25°C, and after the temperature was lowered, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Then, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. Thereafter, the temperature was raised to 45° C., and the mixture was reacted for 2 hours. The reaction solution was filtered, the filtrate was desoluted, and a compound represented by formula (1-5) (weight average molecular weight: 15000, m1+m2 in formula (1-5) was approximately 252±5, n1+n2 was approximately 63± A mixture having an integer of 5 (where m1, m2, n1 and n2 are each integers of 2 or more, m1+n1≧100, m2+n2≧100) and a viscosity at 25° C.: 50 Pa·s) was obtained.
［断熱層の作製］
式（１－５）で表される化合物３９．２質量％、ジシクロペンタニルアクリレ－ト（昭和電工マテリアルズ（株）製「ファンクリル（登録商標） ＦＡ－５１３Ａ」）２３．５質量％、４－ヒドロキシブチルアクリレート（大阪有機化学工業（株）製）１５．７質量％、第一の中空粒子（松本油脂製薬（株）製「マツモトマイクロスフェアー（登録商標） ＦＮ－１９０ＳＳＤ」、平均粒子径：１０～１５μｍ、最大体積膨張倍率：５０倍以上、膨張開始温度：１９０℃、最大膨張温度：２１０～２２０℃）１１．０質量％、第二の中空粒子（日本フィライト（株）製「Ｅｘｐａｎｃｅｌ（登録商標） ９２０ＤＥ８０ｄ３０」、平均粒子径６０～９０μｍ、密度３０±３ｋｇ／ｍ３、最大体積膨張倍率：５倍未満）５．８質量％、重合開始剤（パーブチルオキサイド、日油（株）製「パーブチル（登録商標）Ｏ」）０．９質量％、フェノール系酸化防止剤（ＢＡＳＦジャパン（株）製「Ｉｒｇａｎｏｘ１０１０」）３．１質量％、及び表面調整剤（ＢＹＫ（株）製「ＢＹＫ（登録商標）３５０」）０．８質量％を混合し、断熱層作製用組成物を得た。なお、該断熱層作製用組成物全量を基準として、第一の中空粒子の配合量は３．８体積％であり、第二の中空粒子の配合量は６７．３体積％であった。 [Preparation of heat insulating layer]
39.2% by mass of the compound represented by formula (1-5), 23.5% by mass of dicyclopentanyl acrylate (“Fancryl (registered trademark) FA-513A” manufactured by Showa Denko Materials Co., Ltd.) %, 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 15.7% by mass, first hollow particles (“Matsumoto Microsphere (registered trademark) FN-190SSD” manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Average particle diameter: 10 to 15 μm, maximum volumetric expansion ratio: 50 times or more, expansion start temperature: 190°C, maximum expansion temperature: 210 to 220°C) 11.0% by mass, second hollow particles (Nippon Philite Co., Ltd.) "Expancel (registered trademark) 920DE80d30", average particle diameter 60-90 μm, density 30±3 kg/m 3 , maximum volumetric expansion ratio: less than 5 times) 5.8% by mass, polymerization initiator (perbutyl oxide, NOF) Co., Ltd. "Perbutyl (registered trademark) O") 0.9% by mass, phenolic antioxidant (BASF Japan Co., Ltd. "Irganox 1010") 3.1% by mass, and surface conditioner (BYK Co., Ltd.) "BYK (registered trademark) 350") was mixed with 0.8% by mass to obtain a composition for preparing a heat insulating layer. Note that, based on the total amount of the composition for producing a heat insulating layer, the amount of the first hollow particles was 3.8% by volume, and the amount of the second hollow particles was 67.3% by volume.
式（１－５）で表される化合物３９．２質量％、ジシクロペンタニルアクリレ－ト（昭和電工マテリアルズ（株）製「ファンクリル（登録商標） ＦＡ－５１３Ａ」）２３．５質量％、４－ヒドロキシブチルアクリレート（大阪有機化学工業（株）製）１５．７質量％、第一の中空粒子（松本油脂製薬（株）製「マツモトマイクロスフェアー（登録商標） ＦＮ－１９０ＳＳＤ」、平均粒子径：１０～１５μｍ、最大体積膨張倍率：５０倍以上、膨張開始温度：１９０℃、最大膨張温度：２１０～２２０℃）１１．０質量％、第二の中空粒子（日本フィライト（株）製「Ｅｘｐａｎｃｅｌ（登録商標） ９２０ＤＥ８０ｄ３０」、平均粒子径６０～９０μｍ、密度３０±３ｋｇ／ｍ３、最大体積膨張倍率：５倍未満）５．８質量％、重合開始剤（パーブチルオキサイド、日油（株）製「パーブチル（登録商標）Ｏ」）０．９質量％、フェノール系酸化防止剤（ＢＡＳＦジャパン（株）製「Ｉｒｇａｎｏｘ１０１０」）３．１質量％、及び表面調整剤（ＢＹＫ（株）製「ＢＹＫ（登録商標）３５０」）０．８質量％を混合し、断熱層作製用組成物を得た。なお、該断熱層作製用組成物全量を基準として、第一の中空粒子の配合量は３．８体積％であり、第二の中空粒子の配合量は６７．３体積％であった。 [Preparation of heat insulating layer]
39.2% by mass of the compound represented by formula (1-5), 23.5% by mass of dicyclopentanyl acrylate (“Fancryl (registered trademark) FA-513A” manufactured by Showa Denko Materials Co., Ltd.) %, 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 15.7% by mass, first hollow particles (“Matsumoto Microsphere (registered trademark) FN-190SSD” manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Average particle diameter: 10 to 15 μm, maximum volumetric expansion ratio: 50 times or more, expansion start temperature: 190°C, maximum expansion temperature: 210 to 220°C) 11.0% by mass, second hollow particles (Nippon Philite Co., Ltd.) "Expancel (registered trademark) 920DE80d30", average particle diameter 60-90 μm, density 30±3 kg/m 3 , maximum volumetric expansion ratio: less than 5 times) 5.8% by mass, polymerization initiator (perbutyl oxide, NOF) Co., Ltd. "Perbutyl (registered trademark) O") 0.9% by mass, phenolic antioxidant (BASF Japan Co., Ltd. "Irganox 1010") 3.1% by mass, and surface conditioner (BYK Co., Ltd.) "BYK (registered trademark) 350") was mixed with 0.8% by mass to obtain a composition for preparing a heat insulating layer. Note that, based on the total amount of the composition for producing a heat insulating layer, the amount of the first hollow particles was 3.8% by volume, and the amount of the second hollow particles was 67.3% by volume.
縦２００ｍｍ×横２００ｍｍ×厚さ５ｍｍのガラス板の上に、縦２００ｍｍ×横２００ｍｍ×厚さ０．１ｍｍの離型処理されたポリエステルシート（東洋紡（株）製「Ａ３１」）の離型処理面を上向きにのせた成形板を２組準備した。一方の成形板の離型処理面上に、１２０ｍｍ×１２０ｍｍ×２．０ｍｍの穴が形成されているシリコーンゴム製型枠（２００ｍｍ×２００ｍｍ）を設置し、当該型枠の内側に断熱層作製用組成物を充填した。さらに、他方の成形板の離型処理面を組成物側にして、上蓋をした後に、１３５℃の条件で４０分間加熱した。その後、一方の成形板と、シリコーンゴム製型枠と、他方の成形板におけるガラス板とを取り除き、表面保護層（ポリエステルシート）と断熱層（厚さ２．０ｍｍ）との積層体（積層体Ａ）を作製した。また、積層体Ａの表面保護層を剥離することにより、断熱層を得た。
A release-treated surface of a polyester sheet ("A31" manufactured by Toyobo Co., Ltd.) measuring 200 mm long x 200 mm wide x 0.1 mm thick was placed on a glass plate measuring 200 mm long x 200 mm wide x 5 mm thick. Two sets of molded plates were prepared, on which the molded plates were placed facing upward. A silicone rubber mold (200 mm x 200 mm) with holes of 120 mm x 120 mm x 2.0 mm is installed on the release-treated surface of one of the molding plates, and a heat insulating layer is prepared inside the mold. Filled with composition. Furthermore, the other molded plate was heated at 135° C. for 40 minutes after the release-treated surface was placed on the composition side and the top lid was placed. After that, one molded plate, the silicone rubber mold, and the glass plate of the other molded plate were removed, and a laminate (laminate) of a surface protection layer (polyester sheet) and a heat insulating layer (thickness 2.0 mm) was removed. A) was produced. Further, by peeling off the surface protective layer of the laminate A, a heat insulating layer was obtained.
［断熱層の熱伝導率］
作製した断熱層の熱伝導率を、下記の手順で測定した。断熱層を、８ｃｍ×１３ｃｍ×２．０ｍｍに切断し、レファレンスプレートと測定プローブで挟み込み、迅速熱伝導率計（京都電子工業（株）製「ＱＴＭ－７１０」、測定プローブＰＤ－１１Ｎ、薄膜測定モード）にて２５℃の条件で熱伝導率（初期熱伝導率）を測定した。また、断熱層を幅２０ｍｍ×長さ５０ｍｍに切断して断熱層の試験片を作製し、試験片に対し、上記［粘着層のピール強度］と同様に熱履歴を加え、放冷した後、上記と同様に熱伝導率（加熱後熱伝導率）を測定した。レファレンスは、離型処理されたポリエステルシート（東洋紡（株）製「Ａ３１」）を２枚重ねてレファレンスプレートと測定プローブで挟みこみ測定した。その結果、初期熱伝導率は６４ｍＷ／（ｍ・Ｋ）であり、加熱後熱伝導率は、６７ｍＷ／（ｍ・Ｋ）であった。 [Thermal conductivity of heat insulation layer]
The thermal conductivity of the produced heat insulating layer was measured according to the following procedure. The heat insulating layer was cut into 8 cm x 13 cm x 2.0 mm, sandwiched between a reference plate and a measurement probe, and a quick thermal conductivity meter (Kyoto Electronics Co., Ltd. "QTM-710", measurement probe PD-11N, thin film measurement) was used. The thermal conductivity (initial thermal conductivity) was measured under the condition of 25° C. (mode). In addition, a test piece of the heat insulating layer was prepared by cutting the heat insulating layer into 20 mm width x 50 mm length, and the test piece was subjected to heat history in the same manner as described above for [Peel strength of adhesive layer], and after being left to cool, The thermal conductivity (thermal conductivity after heating) was measured in the same manner as above. The reference was measured by stacking two release-treated polyester sheets ("A31" manufactured by Toyobo Co., Ltd.) and sandwiching them between a reference plate and a measurement probe. As a result, the initial thermal conductivity was 64 mW/(m·K), and the thermal conductivity after heating was 67 mW/(m·K).
作製した断熱層の熱伝導率を、下記の手順で測定した。断熱層を、８ｃｍ×１３ｃｍ×２．０ｍｍに切断し、レファレンスプレートと測定プローブで挟み込み、迅速熱伝導率計（京都電子工業（株）製「ＱＴＭ－７１０」、測定プローブＰＤ－１１Ｎ、薄膜測定モード）にて２５℃の条件で熱伝導率（初期熱伝導率）を測定した。また、断熱層を幅２０ｍｍ×長さ５０ｍｍに切断して断熱層の試験片を作製し、試験片に対し、上記［粘着層のピール強度］と同様に熱履歴を加え、放冷した後、上記と同様に熱伝導率（加熱後熱伝導率）を測定した。レファレンスは、離型処理されたポリエステルシート（東洋紡（株）製「Ａ３１」）を２枚重ねてレファレンスプレートと測定プローブで挟みこみ測定した。その結果、初期熱伝導率は６４ｍＷ／（ｍ・Ｋ）であり、加熱後熱伝導率は、６７ｍＷ／（ｍ・Ｋ）であった。 [Thermal conductivity of heat insulation layer]
The thermal conductivity of the produced heat insulating layer was measured according to the following procedure. The heat insulating layer was cut into 8 cm x 13 cm x 2.0 mm, sandwiched between a reference plate and a measurement probe, and a quick thermal conductivity meter (Kyoto Electronics Co., Ltd. "QTM-710", measurement probe PD-11N, thin film measurement) was used. The thermal conductivity (initial thermal conductivity) was measured under the condition of 25° C. (mode). In addition, a test piece of the heat insulating layer was prepared by cutting the heat insulating layer into 20 mm width x 50 mm length, and the test piece was subjected to heat history in the same manner as described above for [Peel strength of adhesive layer], and after being left to cool, The thermal conductivity (thermal conductivity after heating) was measured in the same manner as above. The reference was measured by stacking two release-treated polyester sheets ("A31" manufactured by Toyobo Co., Ltd.) and sandwiching them between a reference plate and a measurement probe. As a result, the initial thermal conductivity was 64 mW/(m·K), and the thermal conductivity after heating was 67 mW/(m·K).
＜シート＞
［シートの作製］
ロールラミネーター（（株）ラミーコーポレーション製 ホットドック ＬＭＰ－３５０ＥＸ）を用いて、各粘着層を備える積層体Ｃの支持層側に接着テープ（支持層と、該支持層の両面に設けられた接着層とを備えるテープ。昭和電工マテリアルズ（株）製、ハイボン１１－６５２。）をラミネートした。さらに、上記ロールラミネーターを用いて、当該テープ上に、積層体Ａをテープと断熱層とが接するようにラミネートして、比較例１及び実施例１～３に係るシートを得た。シートの厚みは、２１３５μｍであった。 <Sheet>
[Preparation of sheet]
Using a roll laminator (Hot Dog LMP-350EX manufactured by Lamy Corporation), apply adhesive tape (the supporting layer and the adhesive layers provided on both sides of the supporting layer) to the supporting layer side of the laminate C having each adhesive layer. (Hybon 11-652, manufactured by Showa Denko Materials Co., Ltd.) was laminated. Furthermore, using the roll laminator described above, laminate A was laminated onto the tape so that the tape and the heat insulating layer were in contact with each other to obtain sheets according to Comparative Example 1 and Examples 1 to 3. The thickness of the sheet was 2135 μm.
［シートの作製］
ロールラミネーター（（株）ラミーコーポレーション製 ホットドック ＬＭＰ－３５０ＥＸ）を用いて、各粘着層を備える積層体Ｃの支持層側に接着テープ（支持層と、該支持層の両面に設けられた接着層とを備えるテープ。昭和電工マテリアルズ（株）製、ハイボン１１－６５２。）をラミネートした。さらに、上記ロールラミネーターを用いて、当該テープ上に、積層体Ａをテープと断熱層とが接するようにラミネートして、比較例１及び実施例１～３に係るシートを得た。シートの厚みは、２１３５μｍであった。 <Sheet>
[Preparation of sheet]
Using a roll laminator (Hot Dog LMP-350EX manufactured by Lamy Corporation), apply adhesive tape (the supporting layer and the adhesive layers provided on both sides of the supporting layer) to the supporting layer side of the laminate C having each adhesive layer. (Hybon 11-652, manufactured by Showa Denko Materials Co., Ltd.) was laminated. Furthermore, using the roll laminator described above, laminate A was laminated onto the tape so that the tape and the heat insulating layer were in contact with each other to obtain sheets according to Comparative Example 1 and Examples 1 to 3. The thickness of the sheet was 2135 μm.
１０…シート、１１…断熱層、１２…粘着層。
10... Sheet, 11... Heat insulation layer, 12... Adhesive layer.
Claims (5)
- 断熱層と、粘着層と、を備え、
前記粘着層が、アクリル共重合体と、エポキシ基を有する架橋剤と、を含む、シート。 Equipped with a heat insulating layer and an adhesive layer,
A sheet in which the adhesive layer includes an acrylic copolymer and a crosslinking agent having an epoxy group. - 前記断熱層が、中空粒子と、マトリックスポリマーと、を含有する、請求項１に記載のシート。 The sheet according to claim 1, wherein the heat insulating layer contains hollow particles and a matrix polymer.
- 前記マトリックスポリマーが、下記式（１）で表される化合物をモノマー単位として含む、請求項２に記載のシート。
- 前記中空粒子が、有機中空粒子を含む、請求項２又は３に記載のシート。 The sheet according to claim 2 or 3, wherein the hollow particles include organic hollow particles.
- 前記有機中空粒子が、熱膨張性の有機中空粒子である第一の中空粒子と、第一の中空粒子以外の有機中空粒子である第二の中空粒子と、を含む、請求項４に記載のシート。 5. The organic hollow particles according to claim 4, wherein the organic hollow particles include first hollow particles that are thermally expandable organic hollow particles and second hollow particles that are organic hollow particles other than the first hollow particles. sheet.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2022099816 | 2022-06-21 | ||
| JP2022-099816 | 2022-06-21 |
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| WO2023248906A1 true WO2023248906A1 (en) | 2023-12-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/022127 WO2023248906A1 (en) | 2022-06-21 | 2023-06-14 | Sheet provided with heat insulating layer and adhesive layer |
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| TW (1) | TW202406744A (en) |
| WO (1) | WO2023248906A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11116644A (en) * | 1997-08-11 | 1999-04-27 | Nippon Shokubai Co Ltd | Block copolymer and its polymerization |
| JPH11293208A (en) * | 1998-04-10 | 1999-10-26 | Nhk Spring Co Ltd | Foam coated with pressure-sensitive adhesive and its production |
| WO2016117646A1 (en) * | 2015-01-21 | 2016-07-28 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, adhesive sheet, and method for producing same |
| WO2018235217A1 (en) * | 2017-06-22 | 2018-12-27 | 株式会社寺岡製作所 | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
| WO2020246351A1 (en) * | 2019-06-04 | 2020-12-10 | Dic株式会社 | Double-sided adhesive tape and electronic device |
-
2023
- 2023-06-14 WO PCT/JP2023/022127 patent/WO2023248906A1/en unknown
- 2023-06-16 TW TW112122584A patent/TW202406744A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11116644A (en) * | 1997-08-11 | 1999-04-27 | Nippon Shokubai Co Ltd | Block copolymer and its polymerization |
| JPH11293208A (en) * | 1998-04-10 | 1999-10-26 | Nhk Spring Co Ltd | Foam coated with pressure-sensitive adhesive and its production |
| WO2016117646A1 (en) * | 2015-01-21 | 2016-07-28 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, adhesive sheet, and method for producing same |
| WO2018235217A1 (en) * | 2017-06-22 | 2018-12-27 | 株式会社寺岡製作所 | Acrylic resin composition, adhesive agent composition, base for adhesive sheet, and adhesive sheet |
| WO2020246351A1 (en) * | 2019-06-04 | 2020-12-10 | Dic株式会社 | Double-sided adhesive tape and electronic device |
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| Publication number | Publication date |
|---|---|
| TW202406744A (en) | 2024-02-16 |
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