JP6839751B2 - Method of forming a laminated structure and a laminated structure - Google Patents
Method of forming a laminated structure and a laminated structure Download PDFInfo
- Publication number
- JP6839751B2 JP6839751B2 JP2019228969A JP2019228969A JP6839751B2 JP 6839751 B2 JP6839751 B2 JP 6839751B2 JP 2019228969 A JP2019228969 A JP 2019228969A JP 2019228969 A JP2019228969 A JP 2019228969A JP 6839751 B2 JP6839751 B2 JP 6839751B2
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- Prior art keywords
- adhesive
- adhesive layer
- heat
- hydroxyl group
- synthetic resin
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 36
- 239000000463 material Substances 0.000 claims description 119
- 230000001070 adhesive effect Effects 0.000 claims description 110
- 239000000853 adhesive Substances 0.000 claims description 108
- 239000012790 adhesive layer Substances 0.000 claims description 79
- 239000011248 coating agent Substances 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 51
- 229920003002 synthetic resin Polymers 0.000 claims description 51
- 239000000057 synthetic resin Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 43
- 239000005056 polyisocyanate Substances 0.000 claims description 42
- 229920001228 polyisocyanate Polymers 0.000 claims description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000002788 crimping Methods 0.000 claims description 6
- 239000004826 Synthetic adhesive Substances 0.000 claims description 2
- -1 1-methyl-4-hydroxybutyl Chemical group 0.000 description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 230000002265 prevention Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007798 antifreeze agent Substances 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- MEQQGPZLHWVQBZ-UHFFFAOYSA-N 2-methylidene-4-phenylhex-5-enoic acid Chemical compound C(=C)C(C1=CC=CC=C1)CC(C(=O)O)=C MEQQGPZLHWVQBZ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GVRRBIORNFRJPX-UHFFFAOYSA-N 3,3-dibromopropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCC(Br)Br GVRRBIORNFRJPX-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- LQWFHMMEHGQYGB-UHFFFAOYSA-N 4-phenylhexa-2,5-dienoic acid Chemical compound OC(=O)C=CC(C=C)C1=CC=CC=C1 LQWFHMMEHGQYGB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IAANMKMHMYZVOC-UHFFFAOYSA-N aminomethyl dihydrogen phosphate Chemical compound NCOP(O)(O)=O IAANMKMHMYZVOC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- DWPHWVJZBHLVPI-UHFFFAOYSA-N bromophosphonic acid Chemical compound OP(O)(Br)=O DWPHWVJZBHLVPI-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、新規な積層構造体の形成方法に関するものである。本発明で得られる積層構造体は、火災等による温度上昇に際し、基材を保護することができるものである。 The present invention relates to a method for forming a novel laminated structure. The laminated structure obtained in the present invention can protect the base material when the temperature rises due to a fire or the like.
従来より、建築構造物においては、建築物を火災から保護する目的で、柱、梁、床、壁等の主要部位を耐熱構造にすることが求められている。耐熱構造を施す方法の一つとして、主要部位等の基材に熱発泡性被覆材を接着材を介して貼着する方法がある（例えば、特許文献１等）。
Conventionally, in a building structure, for the purpose of protecting the building from a fire, it has been required to make the main parts such as columns, beams, floors, and walls heat-resistant structures. As one of the methods for applying the heat-resistant structure, there is a method of attaching a heat-foamable coating material to a base material such as a main part via an adhesive (for example,
熱発泡性被覆材は、平常時は薄くて軽量であり、火災等による温度上昇には、発泡・炭化して断熱層を形成し、耐熱保護性を発揮する効果を有するものである。このような熱発泡性被覆材は通常、接着材等で貼着することによって施工でき、余分なスペースを必要とせず、厚みを均一にできるといった特徴を有する。 The heat-foamable coating material is thin and lightweight in normal times, and has the effect of foaming and carbonizing to form a heat insulating layer and exhibiting heat-resistant protection against a temperature rise due to a fire or the like. Such a heat-foamable coating material can usually be applied by attaching it with an adhesive or the like, and has a feature that an extra space is not required and the thickness can be made uniform.
しかしながら、上記方法で得られる構造体では、水分等の影響によって十分な接着性を効率良く得ることが困難な場合、あるいは加熱時に形成された断熱層を保持することが困難な場合等がある。このような場合は、熱発泡性被覆材による所望の耐熱保護性能が十分に発揮されないおそれがある。 However, in the structure obtained by the above method, it may be difficult to efficiently obtain sufficient adhesiveness due to the influence of moisture or the like, or it may be difficult to retain the heat insulating layer formed at the time of heating. In such a case, the desired heat-resistant protective performance of the heat-foamable coating material may not be sufficiently exhibited.
本発明は、上記問題に鑑みなされたもので、安定した接着力を有する積層構造体を効率良く得ること、そして当該積層構造体により優れた耐熱保護性を発揮させることを目的とするものである。 The present invention has been made in view of the above problems, and an object of the present invention is to efficiently obtain a laminated structure having a stable adhesive force, and to make the laminated structure exhibit excellent heat-resistant protection. ..
本発明者らは上記問題を解決するために鋭意研究を行った結果、熱発泡性被覆材を基材に貼着する際、特定の構成成分を含む接着材層を用いた形成方法に想到し、本発明の完成に到った。 As a result of diligent research to solve the above problems, the present inventors have come up with a forming method using an adhesive layer containing a specific component when the heat-foamable coating material is attached to a base material. , The present invention has been completed.
すなわち、本発明は以下の特徴を有するものである。
１．基材面に対し、接着材層、及び熱発泡性被覆材が積層された積層構造体の形成方法であって、
前記基材面上に第１接着材層を設ける工程、
前記第１接着材層と、前記熱発泡性被覆材の裏面に設けられた第２接着材層とを圧着する工程を有し、
前記第１接着材層は、水酸基含有合成樹脂を含む（Ｉ）液とポリイソシアネート化合物を含む（ＩＩ）液を、ＮＣＯ／ＯＨ当量比１０／１００〜１２０／１００で含む接着材（Ｍ）より形成されるものであり、前記第２接着材層は、水酸基含有合成樹脂を含む接着材、または水酸基含有合成樹脂及びポリイソシアネート化合物を含む接着材（Ｎ）より形成されるものであり、
前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、前記接着材（Ｍ）におけるＮＣＯ／ＯＨ当量比よりも小さく、
前記接着材（Ｍ）により形成される接着材層の硬化前に、前記第１接着材層と前記第２接着材層とを圧着することを特徴とする積層構造体の形成方法。
２． 前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、１０／１００未満であることを特徴とする１．に記載の積層構造体の形成方法。
３．前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、０／１００であることを特徴とする１．または２．に記載の積層構造体の形成方法。
４．前記接着材（Ｍ）における水酸基含有合成樹脂が、水酸基及びカルボキシル基を含有することを特徴とする１．〜３．のいずれかに記載の積層構造体の形成方法。
５．前記接着材（Ｍ）における水酸基含有合成樹脂が、（メタ）アクリル酸アルキルエステル、カルボキシル基含有単量体、及び水酸基含有単量体を含む単量体群の共重合体であることを特徴とする１．〜４．のいずれかに記載の積層構造体の形成方法。
６．前記ポリイソシアネート化合物が、ビウレット型ポリイソシアネート化合物であることを特徴とする１．〜５．のいずれかに記載の積層構造体の形成方法。
７．基材面に対し、接着材層、及び熱発泡性被覆材が積層された積層構造体であって、
前記接着材層は、基材面に接する第１接着材層と、熱発泡性被覆材に接する第２接着材層を有し、
前記第１接着材層は、水酸基含有合成樹脂を含む（Ｉ）液とポリイソシアネート化合物を含む（ＩＩ）液を、ＮＣＯ／ＯＨ当量比１０／１００〜１２０／１００で含む接着材（Ｍ）より形成されてなり、前記第２接着材層は、水酸基含有合成樹脂を含む接着材、または水酸基含有合成樹脂及びポリイソシアネート化合物を含む接着材（Ｎ）より形成されてなり、
前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、前記接着材（Ｍ）におけるＮＣＯ／ＯＨ当量比よりも小さいことを特徴とする積層構造体。
That is, the present invention has the following features.
1. 1. A method for forming a laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a base material surface.
The step of providing the first adhesive layer on the base material surface,
It has a step of crimping the first adhesive layer and the second adhesive layer provided on the back surface of the heat-foamable coating material.
The first adhesive layer is made from an adhesive (M) containing a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound at an NCO / OH equivalent ratio of 10/100 to 120/100. The second adhesive layer is formed of an adhesive containing a hydroxyl group-containing synthetic resin or an adhesive (N) containing a hydroxyl group-containing synthetic resin and a polyisocyanate compound.
The NCO / OH equivalent ratio in the adhesive (N) is smaller than the NCO / OH equivalent ratio in the adhesive (M).
A method for forming a laminated structure, which comprises crimping the first adhesive layer and the second adhesive layer before curing the adhesive layer formed by the adhesive (M).
2. 2. The NCO / OH equivalent ratio in the adhesive material (N) is 1 and less than 10/100. The method for forming a laminated structure according to.
3. 3. The NCO / OH equivalent ratio in the adhesive (N) is 0/100. Or 2. The method for forming a laminated structure according to.
4. 1. The hydroxyl group-containing synthetic resin in the adhesive (M) contains a hydroxyl group and a carboxyl group. ~ 3. The method for forming a laminated structure according to any one of.
5. The hydroxyl group-containing synthetic resin in the adhesive material (M) is a copolymer of a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a monomer group containing a hydroxyl group-containing monomer. 1. ~ 4. The method for forming a laminated structure according to any one of.
6. 1. The polyisocyanate compound is a biuret-type polyisocyanate compound. ~ 5. The method for forming a laminated structure according to any one of.
7. A laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a base material surface.
The adhesive layer has a first adhesive layer in contact with the surface of the base material and a second adhesive layer in contact with the heat-foamable coating material.
The first adhesive layer is made from an adhesive (M) containing a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound at an NCO / OH equivalent ratio of 10/100 to 120/100. is formed becomes in the second adhesive layer, Ri Na is formed from an adhesive containing a hydroxyl group-containing synthetic resin or adhesive containing a hydroxyl group-containing synthetic resins and polyisocyanate compounds (N),
A laminated structure characterized in that the NCO / OH equivalent ratio in the adhesive material (N) is smaller than the NCO / OH equivalent ratio in the adhesive material (M).
本発明によれば、安定した接着力を有する積層構造体を効率良く形成することができる。本発明の積層構造体は、平常時には優れた接着性を十分に保持し、温度上昇時には優れた脱落防止性及びずれ落ち防止性を発揮して、基材の耐熱保護を図ることができるものである。 According to the present invention, a laminated structure having a stable adhesive force can be efficiently formed. The laminated structure of the present invention can sufficiently maintain excellent adhesiveness in normal times, exhibit excellent drop-off prevention property and slip-off prevention property when the temperature rises, and can protect the base material from heat resistance. is there.
１：基材
２：第１接着材層
３：熱発泡性被覆材
４：第２接着材層
５：積層体
６：離型性シート
1: Base material 2: First adhesive layer 3: Heat-foamable coating material 4: Second adhesive layer 5: Laminated body 6: Releasable sheet
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明は、基材面に対し、接着材層、及び熱発泡性被覆材が積層された積層構造体の形成方法に関するものである。 The present invention relates to a method for forming a laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a base material surface.
［基材］
基材としては、主として建築構造物の柱、梁、床、壁等を構成する材料が挙げられ、例えば、金属で形成されているＨ鋼、鉄骨丸柱、鉄骨角柱、あるいは、モルタル、コンクリート、ケイ酸カルシウム板、石膏ボード、炭酸カルシウム発泡板、不燃火山性ガラス質複層板、繊維強化セメント板、軽量セメント板等が挙げられる。このような基材の表面は、錆止め剤や防錆塗料等で処理されていてもよい。
[Base material]
Examples of the base material include materials that mainly constitute pillars, beams, floors, walls, etc. of building structures. For example, H steel, steel round pillars, steel square pillars, or mortar, concrete, or Kay made of metal. Calcium silicate board, gypsum board, calcium carbonate foam board, non-combustible volcanic vitreous multi-layer board, fiber reinforced cement board, lightweight cement board and the like can be mentioned. The surface of such a base material may be treated with a rust inhibitor, a rust preventive paint, or the like.
［接着材層］
本発明の接着材層は、上記基材に熱発泡性被覆材を接着・固定化するために用いられるものであり、基材面に接する第１接着材層と、熱発泡性被覆材に接する第２接着材層を有する（図１）。本発明において、第１接着材層及び第２接着材層のうち、一方は接着材（Ｍ）から形成されるものであり、他方は接着材（Ｎ）から形成されるものである。なお、本発明における接着材には、粘着材も含まれる。
[Adhesive layer]
The adhesive layer of the present invention is used for adhering and immobilizing a heat-foamable coating material to the base material, and is in contact with the first adhesive layer in contact with the base material surface and the heat-foamable coating material. It has a second adhesive layer (Fig. 1). In the present invention, one of the first adhesive layer and the second adhesive layer is formed from the adhesive (M), and the other is formed from the adhesive (N). The adhesive material in the present invention also includes an adhesive material.
・接着材（Ｍ）
本発明では、接着材（Ｍ）として、水酸基含有合成樹脂（ａ）（以下単に「合成樹脂（ａ）」ともいう。）を含む（Ｉ）液とポリイソシアネート化合物（ｂ）を含む（ＩＩ）液を特定比率で含むものを使用する。
・ Adhesive (M)
In the present invention, the adhesive (M) includes a liquid (I) containing a hydroxyl group-containing synthetic resin (a) (hereinafter, also simply referred to as “synthetic resin (a)”) and a polyisocyanate compound (b) (II). Use a liquid containing a specific ratio.
本発明の合成樹脂（ａ）としては、水酸基含有単量体を含む単量体混合物の共重合体であれば特に限定されない。本発明における水酸基含有単量体としては、１級水酸基含有単量体を含むことが望ましい。１級水酸基含有単量体としては、例えば、２‐ヒドロキシエチル（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、４‐ヒドロキシブチル（メタ）アクリレート、１−メチル−４−ヒドロキシブチル（メタ）アクリレート、５−ヒドロキシペンチル（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、７−ヒドロキシヘプチル（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、２−メチル−８−ヒドロキシオクチル（メタ）アクリレート、７−メチル−８−ヒドロキシオクチル（メタ）アクリレート、９−ヒドロキシノニル（メタ）アクリレート、１０−ヒドロキシデシル（メタ）アクリレート等が挙げられ、本発明では特に、２‐ヒドロキシエチル（メタ）アクリレートを含む態様が好適に用いられる。 The synthetic resin (a) of the present invention is not particularly limited as long as it is a copolymer of a monomer mixture containing a hydroxyl group-containing monomer. The hydroxyl group-containing monomer in the present invention preferably contains a primary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1-methyl-4-hydroxybutyl (meth). Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate , 7-Methyl-8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate and the like. The aspect including is preferably used.
また、上記以外の水酸基含有単量体として、３級水酸基含有単量体を含んでもよい。このような３級水酸基含有単量体としては、例えば２‐ヒドロキシ‐２‐メチルプロピル（メタ）アクリレート、３−エチル−３−ヒドロキシヘキシル（メタ）アクリレート等が挙げられる。合成樹脂（ａ）における水酸基含有単量体の比率は、単量体全量に対し好ましくは０．１〜１０重量％（より好ましくは０．５〜８重量％）である。このような場合、より良い接着性を得ることができる。 Further, as the hydroxyl group-containing monomer other than the above, a tertiary hydroxyl group-containing monomer may be contained. Examples of such a tertiary hydroxyl group-containing monomer include 2-hydroxy-2-methylpropyl (meth) acrylate and 3-ethyl-3-hydroxyhexyl (meth) acrylate. The ratio of the hydroxyl group-containing monomer in the synthetic resin (a) is preferably 0.1 to 10% by weight (more preferably 0.5 to 8% by weight) with respect to the total amount of the monomers. In such a case, better adhesiveness can be obtained.
また、本発明の合成樹脂（ａ）としては、カルボキシル基を含有することが好ましく、カルボキシル基含有単量体及び上記水酸基含有単量体を含む単量体群の共重合体が好ましい。カルボキシル基含有単量体としては、例えば、（メタ）アクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸等を挙げることができ、この中でも特に（メタ）アクリル酸が好適である。合成樹脂（ａ）におけるカルボキシル基含有単量体の比率は、単量体全量に対し好ましくは０．５〜２０重量％（より好ましくは１〜１０重量％）である。このような場合、いっそう接着性を向上させることができる。 Further, the synthetic resin (a) of the present invention preferably contains a carboxyl group, and a copolymer of a carboxyl group-containing monomer and a monomer group containing the hydroxyl group-containing monomer is preferable. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid, and among these, (meth) acrylic acid is particularly preferable. The ratio of the carboxyl group-containing monomer in the synthetic resin (a) is preferably 0.5 to 20% by weight (more preferably 1 to 10% by weight) with respect to the total amount of the monomers. In such a case, the adhesiveness can be further improved.
さらに、本発明の合成樹脂（ａ）としては、（メタ）アクリル酸アルキルエステル、カルボキシル基含有単量体、及び水酸基含有単量体を含む単量体群の共重合体であることが好ましい。なお、本発明では、アクリル酸アルキルエステルとメタクリル酸アルキルエステルを合わせて、（メタ）アクリル酸アルキルエステルと表記する。 Further, the synthetic resin (a) of the present invention is preferably a copolymer of a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a monomer group containing a hydroxyl group-containing monomer. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as (meth) acrylic acid alkyl ester.
（メタ）アクリル酸アルキルエステルとしては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。これらは１種または２種以上で使用することができる。本発明では、アルキル基の炭素数が４〜１４（好ましくは４〜１０）の（メタ）アクリル酸エステルを含む態様が好適であり、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートから選ばれる１種以上を含む態様が好適に用いられる。特に、ｎ−ブチルアクリレート、２−エチルヘキシルアクリレートから選ばれる１種以上を含む態様が最も好適に用いられる。合成樹脂（ａ）における（メタ）アクリル酸アルキルエステルの比率は、単量体全量に対し好ましくは７０重量％以上（より好ましくは８０〜９９．９重量％、さらに好ましくは８２〜９９重量％、特に好ましくは８５〜９５重量％）である。 Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-amyl (meth) acrylate. , Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) ) Acrylate and the like can be mentioned. These can be used alone or in combination of two or more. In the present invention, an embodiment containing a (meth) acrylic acid ester having an alkyl group having 4 to 14 (preferably 4 to 10) carbon atoms is preferable, and n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable. A mode containing one or more selected from the above is preferably used. In particular, an embodiment containing one or more selected from n-butyl acrylate and 2-ethylhexyl acrylate is most preferably used. The ratio of the (meth) acrylic acid alkyl ester in the synthetic resin (a) is preferably 70% by weight or more (more preferably 80 to 99.9% by weight, still more preferably 82 to 99% by weight) with respect to the total amount of the monomers. Particularly preferably, it is 85 to 95% by weight).
また、必要に応じて、その他の単量体を使用することもできる。その他の単量体としては、例えば、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等のアミノ基含有（メタ）アクリル系単量体、
（メタ）アクリルアミド、エチル（メタ）アクリルアミド等のアミド含有（メタ）アクリル系単量体、
アクリロニトリル等のニトリル基含有（メタ）アクリル系単量体、
グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリル系単量体、
γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン等の加水分解性シリル基含有ビニル系単量体、
トリフルオロエチル（メタ）アクリレート、ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート等のフッ素含有（メタ）アクリル系単量体、
フッ化ビニリデン、トリフルオロエチレン、テトラフルオロエチレン、ペンタフルオロエチレン、ヘキサフルオロプロピレン等のフルオロオレフィン、
スチレン、メチルスチレン、クロロスチレン、ビニルトルエン等の芳香族炭化水素系ビニル単量体、
スチレンスルホン酸、ビニルスルホン酸等のスルホン酸含有ビニル単量体、
塩化ビニル、塩化ビニリデン、クロロプレン等の塩素含有単量体、
エチレン、プロピレン、イソブチレン等のα−オレフィン、
酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル等のビニルエステル、
メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテルなどのビニルエーテル、
エチルアリルエーテル、ブチルアリルエーテル等のアリルエーテル、
等を挙げることができ、これらは１種または２種以上で使用できる。
In addition, other monomers can be used if necessary. Examples of other monomers include amino group-containing (meth) acrylic monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate.
Amide-containing (meth) acrylic monomers such as (meth) acrylamide and ethyl (meth) acrylamide,
Nitrile group-containing (meth) acrylic monomers such as acrylonitrile,
Epoxy group-containing (meth) acrylic monomers such as glycidyl (meth) acrylate,
γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxipropylmethyldiethoxysilane, etc. Hydrolytable silyl group-containing vinyl monomer,
Fluorine-containing (meth) acrylic monomers such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and perfluorocyclohexyl (meth) acrylate,
Fluoroolefins such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoroethylene and hexafluoropropylene,
Aromatic hydrocarbon-based vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene, etc.
Sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid,
Chlorine-containing monomers such as vinyl chloride, vinylidene chloride, and chloroprene,
Α-olefins such as ethylene, propylene and isobutylene,
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc.
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether,
Allyl ethers such as ethyl allyl ether and butyl allyl ether,
Etc., and these can be used in one kind or two or more kinds.
本発明の合成樹脂（ａ）のガラス転移温度は、特に限定されないが、好ましくは−６０℃以上３０℃以下（より好ましくは−５５℃以上０℃以下、さらに好ましくは−５０℃以上−５℃以下）である。ガラス転移温度がこのような領域であることにより、本発明の効果を安定して得ることができる。なお、ガラス転移温度は、ＦＯＸの計算式より求められる値である。 The glass transition temperature of the synthetic resin (a) of the present invention is not particularly limited, but is preferably −60 ° C. or higher and 30 ° C. or lower (more preferably −55 ° C. or higher and 0 ° C. or lower, further preferably −50 ° C. or higher and −5 ° C. Below). When the glass transition temperature is in such a region, the effect of the present invention can be stably obtained. The glass transition temperature is a value obtained from the FOX calculation formula.
本発明の合成樹脂（ａ）としては、例えば、上記単量体を含む単量体混合物を、公知の方法で共重合して水媒体中に分散させた水分散型樹脂であることが好ましい。重合方法としては公知の方法を採用すればよく、通常の乳化重合の他、ソープフリー乳化重合、フィード乳化重合、シード乳化重合等を採用することもできる。また、重合時には、乳化剤、開始剤、分散剤、重合禁止剤、重合抑制剤、緩衝剤、連鎖移動剤等を使用することもできる。乳化剤として反応性乳化剤を使用することもできる。 The synthetic resin (a) of the present invention is preferably an aqueous dispersion type resin in which, for example, a monomer mixture containing the above-mentioned monomer is copolymerized by a known method and dispersed in an aqueous medium. As the polymerization method, a known method may be adopted, and in addition to ordinary emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization and the like can also be adopted. Further, at the time of polymerization, an emulsifier, an initiator, a dispersant, a polymerization inhibitor, a polymerization inhibitor, a buffer, a chain transfer agent and the like can also be used. A reactive emulsifier can also be used as the emulsifier.
本発明のポリイソシアネート化合物（ｂ）としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ポリイソシアネート、
テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート、
イソホロンジイソシアネート、水添キシリレンジイソシアネート等の脂環式ポリイソシアネート、
等が挙げられる。本発明のポリイソシアネート化合物（ｂ）としては、例えば、ビウレット構造、イソシアヌレート構造、ウレタン構造、ウレトジオン構造、アロファネート構造、三量体構造等を有するポリイソシアネート化合物を用いることもできる。特に、本発明では、ビウレット構造を有するポリイソシアネート化合物が好ましい。
Examples of the polyisocyanate compound (b) of the present invention include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate.
Aliphatic polyisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate,
Alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated xylylene diisocyanate,
And so on. As the polyisocyanate compound (b) of the present invention, for example, a polyisocyanate compound having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure and the like can be used. In particular, in the present invention, a polyisocyanate compound having a biuret structure is preferable.
さらに、ポリイソシアネート化合物（ｂ）が、水分散性ポリイソシアネート化合物であることが好ましい。水分散性ポリイソシアネート化合物としては、上記ポリイソシアネート化合物に親水性化合物を導入することにより得られるもので、例えば、ポリイソシアネート化合物に乳化剤を加えたもの、ポリイソシアネート化合物にポリオキシアルキレン基含有化合物を付加反応（変性）させたもの、ポリイソシアネート化合物に水溶性樹脂を付加反応（変性）させたもの等が挙げられる。 Further, the polyisocyanate compound (b) is preferably a water-dispersible polyisocyanate compound. The water-dispersible polyisocyanate compound is obtained by introducing a hydrophilic compound into the above-mentioned polyisocyanate compound. For example, a polyisocyanate compound to which an emulsifier is added, or a polyisocyanate compound containing a polyoxyalkylene group-containing compound. Examples thereof include those obtained by addition reaction (modification) and those obtained by adding a water-soluble resin to a polyisocyanate compound (modification).
本発明では特に、ポリイソシアネート化合物にポリオキシアルキレン基含有化合物を付加反応（変性）させたものが好ましく、その製造方法は特に制限されないが、ポリイソシアネート化合物のイソシアネート基と、ポリオキシアルキレン基含有化合物の末端ヒドロキシル基を反応させることにより容易に製造することができる。 In the present invention, a polyisocyanate compound to which a polyoxyalkylene group-containing compound is added (modified) is particularly preferable, and the production method thereof is not particularly limited, but the isocyanate group of the polyisocyanate compound and the polyoxyalkylene group-containing compound are not particularly limited. It can be easily produced by reacting the terminal hydroxyl group of.
ポリオキシアルキレン基含有化合物としては、例えば、ポリオキシエチレングリコール、ポリオキシエチレングリコールモノアルキルエーテル、ポリオキシエチレングリコールモノアリールエーテル、ポリオキシエチレン−プロピレングリコール、ポリオキシエチレン−プロピレングリコールモノアルキルエーテル、ポリオキシエチレン−プロピレングリコールモノアリールエーテル、ポリオキシエチレン−テトラメチレングリコール、ポリオキシエチレン−テトラメチレングリコールモノアルキルエーテル、ポリオキシエチレン−テトラメチレングリコールモノアリールエーテル等が挙げられる。 Examples of the polyoxyalkylene group-containing compound include polyoxyethylene glycol, polyoxyethylene glycol monoalkyl ether, polyoxyethylene glycol monoaryl ether, polyoxyethylene-propylene glycol, polyoxyethylene-propylene glycol monoalkyl ether, and poly. Examples thereof include oxyethylene-propylene glycol monoaryl ether, polyoxyethylene-tetramethylene glycol, polyoxyethylene-tetramethylene glycol monoalkyl ether, and polyoxyethylene-tetramethylene glycol monoaryl ether.
本発明の接着材（Ｍ）は、上記水酸基含有合成樹脂（ａ）を含む（Ｉ）液と上記ポリイソシアネート化合物（ｂ）を含む（ＩＩ）液を、ＮＣＯ／ＯＨ当量比１０／１００〜１２０／１００（好ましくは２０／１００〜１００／１００、より好ましくは４０／１００〜９０／１００）で含むものである。上記範囲となるようにポリイソシアネート化合物（ｂ）を混合することにより、良好なタック性が得られる。その結果、平常時には優れた接着性を十分に保持し、温度上昇時には優れた脱落防止性及びずれ落ち防止性を発揮して、基材保護を図ることができる。一方、ＮＣＯ／ＯＨ当量比が上記の範囲外である場合は、接着性に劣るおそれがある。なお、ＮＣＯ／ＯＨ当量比は、（ｂ）中のイソシアネート基（−ＮＣＯ）の当量数を、（ａ）中の水酸基（−ＯＨ）当量数で除することによって算出される。 The adhesive material (M) of the present invention comprises a solution (I) containing the hydroxyl group-containing synthetic resin (a) and a solution (II) containing the polyisocyanate compound (b) in an NCO / OH equivalent ratio of 10/100 to 120. It is contained in 100/100 (preferably 20/100 to 100/100, more preferably 40/100 to 90/100). Good tackiness can be obtained by mixing the polyisocyanate compound (b) so as to be within the above range. As a result, it is possible to sufficiently maintain excellent adhesiveness in normal times, exhibit excellent drop-off prevention property and slip-off prevention property when the temperature rises, and protect the base material. On the other hand, if the NCO / OH equivalent ratio is out of the above range, the adhesiveness may be inferior. The NCO / OH equivalent ratio is calculated by dividing the equivalent number of isocyanate groups (−NCO) in (b) by the equivalent number of hydroxyl groups (−OH) in (a).
本発明で用いる接着材（Ｍ）の、上記合成樹脂（ａ）を含む（Ｉ）液、上記ポリイソシアネート化合物（ｂ）を含む（ＩＩ）液には、公知の添加剤が含まれていてもよい。添加剤としては、例えば、充填剤、着色剤、希釈剤、粘接着付与剤、増粘剤、分散剤、湿潤剤、消泡剤、可塑剤、造膜助剤、凍結防止剤、防腐剤、防黴剤、防藻剤、紫外線吸収剤、光安定剤等が挙げられる。 Even if the liquid (I) containing the synthetic resin (a) and the liquid (II) containing the polyisocyanate compound (b) of the adhesive (M) used in the present invention contain known additives. Good. Additives include, for example, fillers, colorants, diluents, sticky adhesives, thickeners, dispersants, wetting agents, defoamers, plasticizers, film-forming aids, antifreeze agents, preservatives. , Antifungal agents, anti-algae agents, ultraviolet absorbers, light stabilizers and the like.
・接着材（Ｎ）
本発明では、接着材（Ｎ）として、水酸基含有合成樹脂（ａ’）「（以下単に「合成樹脂（ａ’）」ともいう。）を含むものを使用する。合成樹脂（ａ’）としては、水酸基を含有する合成樹脂であれば特に限定されずに使用することができる。例えば、水酸基含有単量体を含む単量体混合物の共重合体が好ましい。
・ Adhesive (N)
In the present invention, as the adhesive (N), a material containing a hydroxyl group-containing synthetic resin (a') "(hereinafter, also simply referred to as" synthetic resin (a') ") is used. The synthetic resin (a') can be used without particular limitation as long as it is a synthetic resin containing a hydroxyl group. For example, a copolymer of a monomer mixture containing a hydroxyl group-containing monomer is preferable.
また、本発明の合成樹脂（ａ’）としては、カルボキシル基を含有することが好ましく、カルボキシル基含有単量体及び上記水酸基含有単量体を含む単量体群の共重合体が好ましい。さらには、本発明の合成樹脂（ａ’）としては、（メタ）アクリル酸アルキルエステル、カルボキシル基含有単量体、及び水酸基含有単量体を含む単量体群の共重合体であることが好ましい。本発明の合成樹脂（ａ’）のガラス転移温度は、特に限定されないが、好ましくは−６０℃以上３０℃以下（より好ましくは−５５℃以上０℃以下、さらに好ましくは−５０℃以上−５℃以下）である。また、本発明の合成樹脂（ａ’）は水分散型樹脂であることが好ましい。なお、合成樹脂（ａ’）における水酸基含有単量体、カルボキシル基含有単量体、及び（メタ）アクリル酸アルキルエステルとしては、上述のものを使用することができる。本発明の合成樹脂（ａ’）としては、上記接着材（Ｍ）の（Ｉ）液と同様の合成樹脂（ａ）を使用することが好ましい。合成樹脂（ａ）と合成樹脂（ａ’）が（メタ）アクリル酸アルキルエステルとして同一のものを含む場合、さらには同一組成の場合、いっそう接着性を向上させることができる。 Further, the synthetic resin (a') of the present invention preferably contains a carboxyl group, and a copolymer of a carboxyl group-containing monomer and a monomer group containing the hydroxyl group-containing monomer is preferable. Furthermore, the synthetic resin (a') of the present invention may be a copolymer of a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a monomer group containing a hydroxyl group-containing monomer. preferable. The glass transition temperature of the synthetic resin (a') of the present invention is not particularly limited, but is preferably −60 ° C. or higher and 30 ° C. or lower (more preferably −55 ° C. or higher and 0 ° C. or lower, still more preferably −50 ° C. or higher and −5 ° C. ℃ or less). Further, the synthetic resin (a') of the present invention is preferably a water-dispersible resin. As the hydroxyl group-containing monomer, the carboxyl group-containing monomer, and the (meth) acrylic acid alkyl ester in the synthetic resin (a'), the above-mentioned ones can be used. As the synthetic resin (a') of the present invention, it is preferable to use the same synthetic resin (a) as the liquid (I) of the adhesive (M). When the synthetic resin (a) and the synthetic resin (a') contain the same (meth) acrylic acid alkyl ester, and when they have the same composition, the adhesiveness can be further improved.
さらに、本発明の接着材（Ｎ）として、ポリイソシアネート化合物を混合することもできる。ポリイソシアネート化合物は、合成樹脂（ａ’）の水酸基が残存するようにＮＣＯ／ＯＨの当量比を設定して混合することが好ましい。さらには接着材（Ｎ）におけるＮＣＯ／ＯＨの当量比は、接着材（Ｍ）におけるＮＣＯ／ＯＨの当量比よりも小さいことが好ましく、具体的には、好ましくは４０／１００未満（より好ましくは２０／１００未満、さらに好ましくは１０／１００未満、最も好ましくは０／１００以上８／１００以下）であり、ＮＣＯ（ポリイソシアネート化合物）を含まない態様も好適である。ポリイソシアネート化合物としては、上述のものと同様のものを使用できる。 Further, a polyisocyanate compound can be mixed as the adhesive (N) of the present invention. The polyisocyanate compound is preferably mixed by setting the equivalent ratio of NCO / OH so that the hydroxyl group of the synthetic resin (a') remains. Furthermore, the equivalent ratio of NCO / OH in the adhesive (N) is preferably smaller than the equivalent ratio of NCO / OH in the adhesive (M), specifically, preferably less than 40/100 (more preferably). It is less than 20/100, more preferably less than 10/100, most preferably 0/100 or more and 8/100 or less), and an NCO (polyisocyanate compound) -free embodiment is also preferable. As the polyisocyanate compound, the same compounds as those described above can be used.
本発明で用いる接着材（Ｎ）には、公知の添加剤が含まれていてもよい。添加剤としては、例えば、充填剤、着色剤、希釈剤、粘接着付与剤、増粘剤、分散剤、湿潤剤、消泡剤、可塑剤、造膜助剤、凍結防止剤、防腐剤、防黴剤、防藻剤、紫外線吸収剤、光安定剤等が挙げられる。 The adhesive (N) used in the present invention may contain a known additive. Additives include, for example, fillers, colorants, diluents, sticky adhesives, thickeners, dispersants, wetting agents, defoamers, plasticizers, film-forming aids, antifreeze agents, preservatives. , Antifungal agents, anti-algae agents, ultraviolet absorbers, light stabilizers and the like.
［熱発泡性被覆材］
本発明における熱発泡性被覆材としては、温度上昇時に発泡・炭化して断熱層を形成するものが使用できる。好適な熱発泡性被覆材としては、例えば、合成樹脂、難燃剤、発泡剤、炭化剤等を含有するシート状のものが挙げられる。
[Thermal foaming coating material]
As the heat-foamable coating material in the present invention, a material that foams and carbonizes when the temperature rises to form a heat insulating layer can be used. Suitable heat-foamable coating materials include, for example, sheet-like materials containing synthetic resins, flame retardants, foaming agents, carbonizing agents and the like.
熱発泡性被覆材における合成樹脂としては、熱可塑性樹脂が好ましく用いられる。このような熱可塑性樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブテン樹脂、ポリペンテン樹脂、ポリスチレン樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリフェニレンエーテル樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、フェノール樹脂、ポリウレタン樹脂、クロロプレン樹脂、ポリブタジエン、ポリイソブチレン、ニトリルゴム、ブチルゴム、ビニルトルエン−ブタジエン共重合体、ビニルトルエン−アクリル酸エステル共重合体、ビニルトルエン−メタクリル酸エステル共重合体、スチレン−ブタジエン共重合体、エチレン−メタクリル酸エステル共重合体、エチレン−酢酸ビニル共重合体等が挙げられる。 As the synthetic resin in the heat-foamable coating material, a thermoplastic resin is preferably used. Examples of such thermoplastic resins include polyethylene resin, polypropylene resin, polybutene resin, polypentene resin, polystyrene resin, polycarbonate resin, acrylic resin, polyphenylene ether resin, polyamide resin, polyvinyl chloride resin, phenol resin, and polyurethane resin. Chloroprene resin, polybutadiene, polyisobutylene, nitrile rubber, butyl rubber, vinyl toluene-butadiene copolymer, vinyl toluene-acrylic acid ester copolymer, vinyl toluene-methacrylic acid ester copolymer, styrene-butadiene copolymer, ethylene- Examples thereof include a methacrylic acid ester copolymer and an ethylene-vinyl acetate copolymer.
難燃剤は、一般に、火災時に脱水冷却効果、不燃性ガス発生効果、バインダー炭化促進効果等の少なくとも一つの効果を発揮し、樹脂成分の燃焼を防止ないし抑制する作用を有する。難燃剤としては、例えば、トリクレジルホスフェート、ジフェニルクレジルフォスフェート、ジフェニルオクチルフォスフェート、トリ（β−クロロエチル）フォスフェート、トリブチルフォスフェート、トリ（ジクロロプロピル）フォスフェート、トリフェニルフォスフェート、トリ（ジブロモプロピル）フォスフェート、クロロフォスフォネート、ブロモフォスフォネート、ジエチル−Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノメチルフォスフェート、ジ（ポリオキシエチレン）ヒドロキシメチルフォスフォネート等の有機リン系化合物；塩素化ポリフェニル、塩素化ポリエチレン、塩化ジフェニル、塩化トリフェニル、五塩化脂肪酸エステル、パークロロペンタシクロデカン、塩素化ナフタレン、テトラクロル無水フタル酸等の塩素化合物；三酸化アンチモン、五塩化アンチモン等のアンチモン化合物；三塩化リン、五塩化リン、リン酸アンモニウム、ポリリン酸アンモニウム等のリン化合物；その他ホウ酸亜鉛、ホウ酸ソーダ等の無機質化合物等が挙げられる。これらは、単独で又は２種以上で使用することができる。本発明では、特にポリリン酸アンモニウムが好ましい。ポリリン酸アンモニウムを使用する場合には、脱水冷却効果と不燃性ガス発生効果とをより効果的に発揮できるので難燃効果が高く、しかも発泡剤の含有量を削減できる効果もある。 The flame retardant generally exerts at least one effect such as a dehydration cooling effect, a nonflammable gas generating effect, and a binder carbonization promoting effect in the event of a fire, and has an effect of preventing or suppressing combustion of a resin component. Examples of the flame retardant include tricredyl phosphate, diphenyl cresil phosphate, diphenyloctyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, and tri. Organophosphorus such as (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphate, di (polyoxyethylene) hydroxymethylphosphonate, etc. System compounds; Chlorine compounds such as chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride; Antimony compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate and the like; other inorganic compounds such as zinc borate, sodium borate and the like can be mentioned. These can be used alone or in combination of two or more. In the present invention, ammonium polyphosphate is particularly preferable. When ammonium polyphosphate is used, the dehydration cooling effect and the nonflammable gas generation effect can be more effectively exhibited, so that the flame retardant effect is high and the content of the foaming agent can be reduced.
発泡剤は、一般に、火災時に不燃性ガスを発生させて、炭化していく樹脂成分及び炭化剤を発泡させ、気孔を有する炭化断熱層を形成させる役割を果たす。発泡剤としては、例えば、メラミン及びその誘導体、ジシアンジアミド及びその誘導体、アゾジカーボンアミド、尿素、チオ尿素等の含窒素化合物が挙げられる。また、これらは単独で又は２種以上で使用することができる。これらの中では、メラミン、ジシアンジアミド、アゾジカーボンアミド等が不燃性ガスの発生効率に優れていることから好ましい。 The foaming agent generally plays a role of generating a nonflammable gas in the event of a fire to foam a carbonizing resin component and a carbonizing agent to form a carbonized heat insulating layer having pores. Examples of the foaming agent include nitrogen-containing compounds such as melamine and its derivatives, dicyandiamide and its derivatives, azodicarbonamide, urea, and thiourea. In addition, these can be used alone or in combination of two or more. Among these, melamine, dicyandiamide, azodicarbonamide and the like are preferable because they are excellent in the generation efficiency of nonflammable gas.
炭化剤は、一般に、火災による樹脂成分の炭化とともにそれ自体も脱水炭化していくことにより、断熱性により優れた厚みのある炭化断熱層を形成する作用を有する。炭化剤としては、例えば、ジペンタエリスリトール、ペンタエリスリトール、トリメチロールプロパン等の多価アルコールのほか、デンプン、カゼイン等が挙げられる。これらは、単独で又は２種以上で使用することができる。 In general, a carbonizing agent has an action of forming a thick carbonized heat insulating layer having better heat insulating properties by dehydrating and carbonizing itself together with carbonization of a resin component due to a fire. Examples of the carbonizing agent include polyhydric alcohols such as dipentaerythritol, pentaerythritol and trimethylolpropane, as well as starch and casein. These can be used alone or in combination of two or more.
熱発泡性被覆材における各成分の構成比率は、樹脂成分の固形分１００重量部に対し、難燃剤２００重量部以上６００重量部以下（好ましくは２５０重量部以上５００重量部以下）、発泡剤１０重量部以上２００重量部以下（好ましくは２０重量部以上１５０重量部以下）、炭化剤１０重量部以上２００重量部以下（好ましくは３０重量部以上１５０重量部以下）であることが好ましい。 The composition ratio of each component in the heat-foamable coating material is 200 parts by weight or more and 600 parts by weight or less (preferably 250 parts by weight or more and 500 parts by weight or less) of the flame retardant and the foaming agent 10 with respect to 100 parts by weight of the solid content of the resin component. It is preferably 2 parts by weight or more and 200 parts by weight or less (preferably 20 parts by weight or more and 150 parts by weight or less), and 10 parts by weight or more and 200 parts by weight or less (preferably 30 parts by weight or more and 150 parts by weight or less).
熱発泡性被覆材は、上記成分の他、さらに充填剤、顔料、繊維、湿潤剤、可塑剤、滑剤、防腐剤、防黴剤、防藻剤、抗菌剤、増粘剤、レベリング剤、分散剤、消泡剤、架橋剤、紫外線吸収剤、酸化防止剤、触媒等を含有することもできる。 In addition to the above components, the heat-foamable coating material further includes fillers, pigments, fibers, wetting agents, plasticizers, lubricants, preservatives, fungicides, algae-proofing agents, antibacterial agents, thickeners, leveling agents, and dispersions. It can also contain agents, antifoaming agents, cross-linking agents, UV absorbers, antioxidants, catalysts and the like.
このうち充填剤は、一般に、炭化断熱層の強度を改善し、かつ、耐熱保護性を高める作用を有する。充填剤は、かかる作用を有する限り特に制限されず、公知の熱発泡性被覆材における充填剤と同様のものが使用できる。例えば、タルク等の珪酸塩；炭酸カルシウム、炭酸ナトリウム等の炭酸塩；酸化アルミニウム、二酸化チタン、酸化亜鉛等の金属酸化物；粘土、クレー、シラス、マイカ等の天然鉱物類等が挙げられる。これらは、単独で又は２種以上で使用することができる。これらの充填剤中では二酸化チタンがより好ましい。 Of these, the filler generally has the effect of improving the strength of the carbonized heat insulating layer and enhancing the heat resistance. The filler is not particularly limited as long as it has such an action, and the same filler as the filler in the known heat-foamable coating material can be used. For example, silicates such as talc; carbonates such as calcium carbonate and sodium carbonate; metal oxides such as aluminum oxide, titanium dioxide and zinc oxide; natural minerals such as clay, clay, silas and mica can be mentioned. These can be used alone or in combination of two or more. Of these fillers, titanium dioxide is more preferred.
顔料としては、一般の着色顔料（有機顔料・無機顔料）が使用できる。本発明では、特にベンガラ、黄鉛、黄色酸化鉄、チタンイエロー、クロムグリーン、群青、コバルトブルー、カドミウムレッド等の無機顔料が好ましい。さらに、耐熱保護性をより高めるために膨張性黒鉛、未膨張バーミキュライト等を配合しても良い。 As the pigment, general coloring pigments (organic pigments / inorganic pigments) can be used. In the present invention, inorganic pigments such as red iron oxide, chrome yellow, yellow iron oxide, titanium yellow, chrome green, ultramarine blue, cobalt blue and cadmium red are particularly preferable. Further, expandable graphite, unexpanded vermiculite and the like may be blended in order to further enhance the heat resistance.
本発明で用いる熱発泡性被覆材は、公知の方法で製造することができる。例えば、前述の合成樹脂、難燃剤、発泡剤、炭化剤等を適量配合した組成物に、必要に応じて適当な溶媒を加えて型枠内に流し込み、乾燥後に脱型する方法；前記組成物を加温塗工機によって離型紙に塗付した後に巻き取る方法；ニーダーによって混練した前記組成物を押し出し成型機によってシート状に加工する方法；ニーダーによって混練した前記組成物を対ロールの間に供給してシート状に加工する方法；前記組成物をペレット状にした後に押し出し成型機によってシート状に加工する方法；バンバリーミキサー、ミキシングロール等で混練した前記組成物を複数の熱ロールからなるカレンダによって圧延してシート状に加工する方法等が挙げられる。 The heat-foamable coating material used in the present invention can be produced by a known method. For example, a method in which an appropriate amount of the above-mentioned synthetic resin, flame retardant, foaming agent, carbonizing agent, etc. is blended, an appropriate solvent is added as necessary, poured into a mold, dried, and then demolded; Is applied to the release paper by a heating coating machine and then wound up; a method of processing the composition kneaded by a kneader into a sheet shape by an extrusion molding machine; a method of kneading the composition by a kneader between rolls. A method of supplying and processing into a sheet; a method of pelletizing the composition and then processing it into a sheet by an extrusion molding machine; a calendar composed of a plurality of heat rolls of the composition kneaded with a Banbury mixer, a mixing roll or the like. Examples thereof include a method of rolling and processing into a sheet.
また、熱発泡性被覆材には、補強シートを積層することもできる。補強シートとしては、例えば、織布、不織布、メッシュ、あるいはこれらの複合体等が挙げられる。補強シートは、少なくとも熱発泡性被覆材の裏面側に積層することが望ましい。このような補強シートを有する熱発泡性被覆材は、接着性、脱落防止性、ずれ落ち防止性等の効果向上の点で好適である。 Further, a reinforcing sheet can be laminated on the heat-foamable coating material. Examples of the reinforcing sheet include woven fabrics, non-woven fabrics, meshes, and composites thereof. It is desirable that the reinforcing sheet is laminated at least on the back surface side of the heat-foamable coating material. A heat-foamable coating material having such a reinforcing sheet is suitable in terms of improving effects such as adhesiveness, falling-off prevention property, and slip-off prevention property.
熱発泡性被覆材の厚さは、特に限定されないが、好ましくは０．２ｍｍ以上１０ｍｍ以下、より好ましくは０．５ｍｍ以上６ｍｍ以下である。 The thickness of the heat-foamable coating material is not particularly limited, but is preferably 0.2 mm or more and 10 mm or less, and more preferably 0.5 mm or more and 6 mm or less.
・積層体
本発明では、上記熱発泡性被覆材と第２接着材層を有する積層体を用いることができる。このような積層体は、熱発泡性被覆材の裏面に接着材を塗付し、第２接着材層を形成することで得られる。さらに、第２接着材層の表面は、離型性シートで覆うことができる。図３は、積層体の一例で、熱発泡性被覆材の裏面に、第２接着材層と、離型性シートを有するものである。このような積層体を用いることで、作業効率を高めることができる。
-Laminated body In the present invention, a laminated body having the above-mentioned heat-foamable coating material and a second adhesive layer can be used. Such a laminate can be obtained by applying an adhesive to the back surface of the heat-foamable coating material to form a second adhesive layer. Further, the surface of the second adhesive layer can be covered with a releasable sheet. FIG. 3 shows an example of a laminated body having a second adhesive layer and a releasable sheet on the back surface of the heat-foamable coating material. By using such a laminated body, work efficiency can be improved.
離型性シートは、熱発泡性被覆材の保管中もしくは運搬中等において、第２接着材層を保護し、熱発泡性被覆材を使用する際には第２接着材層から容易に剥離できるものである。このような離型性シートとしては、公知のものを使用することができ、例えば、シリコン、ワックス、弗素樹脂等の離型剤を塗布もしくは含浸した紙あるいはフィルム、または該離型剤を含まずそれ自体離型性を有するポリプロピレン、ポリエチレン等の合成樹脂フィルム等が挙げられる。 The releasable sheet protects the second adhesive layer during storage or transportation of the heat-foamable coating material, and can be easily peeled off from the second adhesive layer when the heat-foamable coating material is used. Is. As such a releasable sheet, a known one can be used, and for example, a paper or film coated or impregnated with a releasing agent such as silicone, wax, or fluororesin, or the releasable agent is not included. Examples thereof include synthetic resin films such as polypropylene and polyethylene which have releasability by themselves.
積層体の製造方法は、特に限定されないが、図３の積層体については、例えば、熱発泡性被覆材の一面に接着材を塗付け、その上に離型性シートを積層する方法、あるいは、離型性シートの上に接着材を塗付け、その上に熱発泡性被覆材を積層する方法等が挙げられる。このような積層体において、第２接着材層を形成する接着材としては、上記接着材（Ｍ）、上記接着材（Ｎ）のいずれであってもよいが、本発明では、上記接着材（Ｎ）を用いることが好ましい。上記接着材（Ｎ）を用いた積層体は、長期保管した場合であっても接着性を保持することができ、安定した接着力を有する積層構造体を形成することができる。接着材の塗付け量（固形分）は、好ましくは２５ｇ／ｍ２以上３００ｇ／ｍ２以下であり、第２接着材層の塗付厚みは、好ましくは１２〜１５０μｍ（より好ましくは２５〜１００μｍ）である。また、接着材は、塗付け後、乾燥させておくことが望ましい。ただし、接着材（Ｍ）は硬化前までとする。接着材（Ｍ）の乾燥は、常温（例えば、５〜４０℃）下、接着材（Ｎ）の乾燥は、常温下、または加温（例えば、５０〜１００℃）下で行うことが望ましい。 The method for producing the laminate is not particularly limited, but for the laminate in FIG. 3, for example, a method in which an adhesive is applied to one surface of a heat-foamable coating material and a releasable sheet is laminated on the adhesive, or Examples thereof include a method in which an adhesive is applied on a releasable sheet and a heat-foamable coating material is laminated on the adhesive. In such a laminated body, the adhesive material forming the second adhesive layer may be either the above-mentioned adhesive material (M) or the above-mentioned adhesive material (N), but in the present invention, the above-mentioned adhesive material ( It is preferable to use N). The laminated body using the adhesive material (N) can maintain the adhesiveness even when stored for a long period of time, and can form a laminated structure having a stable adhesive force. The amount (solid content) of the adhesive applied is preferably 25 g / m 2 or more and 300 g / m 2 or less, and the coating thickness of the second adhesive layer is preferably 12 to 150 μm (more preferably 25 to 100 μm). ). Further, it is desirable that the adhesive is dried after being applied. However, the adhesive (M) is used until it is cured. It is desirable that the adhesive (M) is dried at room temperature (for example, 5 to 40 ° C.), and the adhesive material (N) is dried at room temperature or warmed (for example, 50 to 100 ° C.).
［積層構造体の形成方法］
本発明の積層構造体は、基材面上に第１接着材層、熱発泡性被覆材の裏面に第２接着材層を設け、基材面上の第１接着材層と、熱発泡性被覆材の裏面の第２接着材層とを圧着することで形成できる（図２）。具体的には、裏面に第２接着材層を設けた熱発泡性被覆材（積層体）を用意しておく。一方、基材表面に接着材を塗付して、第１接着材層を形成し、積層体（第２接着材層側）を貼り付け、圧着することを特徴とする。積層体が離型性シートを有する場合は、離型性シートを剥離し、第２接着材層を露出させて貼り付ければよい。
[Method of forming a laminated structure]
In the laminated structure of the present invention, a first adhesive layer is provided on the base material surface and a second adhesive layer is provided on the back surface of the heat-foamable coating material, and the first adhesive layer on the base material surface and heat-foamability It can be formed by crimping the second adhesive layer on the back surface of the covering material (FIG. 2). Specifically, a heat-foamable coating material (laminate) having a second adhesive layer on the back surface is prepared. On the other hand, the surface of the base material is coated with an adhesive to form a first adhesive layer, and a laminate (second adhesive layer side) is attached and crimped. When the laminate has a releasable sheet, the releasable sheet may be peeled off to expose the second adhesive layer and attached.
本発明では、前記第１接着材層及び前記第２接着材層のうち、一方は、上記接着材（Ｍ）より形成されるものであり、他方は、上記接着材（Ｎ）より形成されるものである。本発明では、第１接着材層が接着材（Ｍ）、第２接着材層が接着材（Ｎ）より形成される接着材層であることが好ましい。また、積層体の貼り付けは、接着材（Ｍ）の硬化前に行なうことを特徴とする。これにより、基材面と接着材（Ｍ）の界面において優れた接着性を有するとともに、第１接着材層と第２接着層の界面で架橋反応を生じるため、安定した接着力を有する積層構造体を効率よく形成することができると考えられる。 In the present invention, one of the first adhesive layer and the second adhesive layer is formed of the adhesive (M), and the other is formed of the adhesive (N). It is a thing. In the present invention, it is preferable that the first adhesive layer is an adhesive layer (M) and the second adhesive layer is an adhesive layer formed of an adhesive (N). Further, the laminated body is attached before the adhesive (M) is cured. As a result, it has excellent adhesiveness at the interface between the base material surface and the adhesive (M), and a cross-linking reaction occurs at the interface between the first adhesive layer and the second adhesive layer, so that the laminated structure has stable adhesive force. It is thought that the body can be formed efficiently.
なお、接着材（Ｍ）の硬化前とは、接着材（Ｍ）に含まれるポリイソシアネート化合物（ｂ）のイソシアネート基（−ＮＣＯ）が残存する状態のことをいう。例えば、接着材（Ｍ）は、上記（Ｉ）液と上記（ＩＩ）液を混合後、２５℃下で好ましくは４時間以内（より好ましくは３時間以内）に基材または熱発泡性被覆材の裏面に塗付し、塗付後、好ましくは１０時間以内（より好ましくは１０分以上６時間以内）に、第１接着材層と第２接着材層が接するように積層体を貼り付ける。なお、イソシアネート基（−ＮＣＯ）が残存する状態は、赤外分光光度計（ＦＴ−ＩＲ）により確認することができる。また、圧着する際には、必要に応じ、ローラー、コテ等の押圧具を用いることができる。 The term "before curing" of the adhesive (M) means a state in which the isocyanate group (-NCO) of the polyisocyanate compound (b) contained in the adhesive (M) remains. For example, the adhesive (M) is a base material or a heat-foamable coating material, preferably within 4 hours (more preferably within 3 hours) at 25 ° C. after mixing the above solution (I) and the above solution (II). The laminate is applied to the back surface of the above material, and the laminate is attached so that the first adhesive layer and the second adhesive layer are in contact with each other, preferably within 10 hours (more preferably 10 minutes or more and 6 hours or less) after the application. The state in which the isocyanate group (-NCO) remains can be confirmed by an infrared spectrophotometer (FT-IR). Further, when crimping, a pressing tool such as a roller or a trowel can be used if necessary.
基材に第１接着材を塗付する際には、例えば刷毛、ローラー、コテ、へら、スプレー等の器具を用いることができる。第１接着材の塗付け量（固形分）は、好ましくは２５ｇ／ｍ２以上３００ｇ／ｍ２以下であり、第１接着材層の塗付厚みは、好ましくは１２〜１５０μｍ（より好ましくは２５〜１００μｍ）である。第１接着材は、塗付け後、乾燥させておくことが望ましい。ただし、接着材（Ｍ）は硬化前までとする。接着材（Ｍ）の乾燥は、常温（例えば、５〜４０℃）下、接着材（Ｎ）の乾燥は、常温下、または加温（例えば、５０〜１００℃）下で行うことが望ましい。 When applying the first adhesive to the base material, for example, an instrument such as a brush, a roller, a trowel, a spatula, or a spray can be used. The coating amount (solid content) of the first adhesive is preferably 25 g / m 2 or more and 300 g / m 2 or less, and the coating thickness of the first adhesive layer is preferably 12 to 150 μm (more preferably 25). ~ 100 μm). It is desirable that the first adhesive is dried after being applied. However, the adhesive (M) is used until it is cured. It is desirable that the adhesive (M) is dried at room temperature (for example, 5 to 40 ° C.), and the adhesive material (N) is dried at room temperature or warmed (for example, 50 to 100 ° C.).
本発明の積層構造体は、上記熱発泡性被覆材を２枚以上積層して使用することができる。熱発泡性被覆材を２枚以上積層する場合は、予め接着材等で積層した熱発泡性被覆材を用いることもできる。 In the laminated structure of the present invention, two or more heat-foamable coating materials can be laminated and used. When two or more heat-foamable coating materials are laminated, a heat-foamable coating material previously laminated with an adhesive or the like can also be used.
本発明では、熱発泡性被覆材の表面に化粧層を形成させることもできる。化粧層は公知の方法で形成すればよく、例えば各種塗料を塗装したり、あるいは化粧フィルム、化粧シート等を積層したりすることができる。化粧層は、複数の材料が積層されたものであってもよい。 In the present invention, a decorative layer can also be formed on the surface of the heat-foamable coating material. The decorative layer may be formed by a known method, and for example, various paints may be applied, or a decorative film, a decorative sheet, or the like may be laminated. The decorative layer may be a laminate of a plurality of materials.
以下、実施例を示し、本発明の特徴をより明確にする。 Hereinafter, examples will be shown to further clarify the features of the present invention.
（合成樹脂エマルション１〜６）
反応容器に、脱イオン水を仕込み、攪拌及び窒素置換を行いながら８０℃まで昇温した。これに、別途用意した乳化モノマー（脱イオン水にドデシル硫酸ナトリウムを溶解させた水溶液に、表１に示すモノマーを乳化分散させたもの）、開始剤水溶液（脱イオン水に過硫酸アンモニウムを溶解させた水溶液）をそれぞれ３時間かけて連続的に滴下した。
滴下終了後３時間熟成し、３０℃まで冷却した後、アンモニア水を添加してｐＨを８に調製することにより、合成樹脂エマルション１〜５を得た。この合成樹脂エマルション１〜５の樹脂固形分は５０重量％であった。
(
Deionized water was charged into the reaction vessel, and the temperature was raised to 80 ° C. while stirring and nitrogen substitution. To this, a separately prepared emulsified monomer (an aqueous solution in which sodium dodecyl sulfate was dissolved in deionized water and the monomer shown in Table 1 was emulsified and dispersed) and an initiator aqueous solution (ammonium persulfate was dissolved in deionized water). Aqueous solution) was continuously added dropwise over 3 hours.
After completion of the dropping, the mixture was aged for 3 hours, cooled to 30 ° C., and then aqueous ammonia was added to adjust the pH to 8, to obtain
（接着材１〜１５の製造）
合成樹脂エマルション１００重量部に、添加剤（顔料、湿潤剤、増粘剤、消泡剤、防腐剤等）４重量部を配合し（Ｉ）液を製造した。次いで、ポリイソシアネート化合物からなる（ＩＩ）液を用意し、上記（Ｉ）液と混合し接着剤１〜１５を製造した。この接着材１〜１５は水を適量添加し固形分を５０重量％に調製した。なお、各接着材に使用した合成樹脂エマルション、ポリイソシアネート化合物、及びＮＣＯ／ＯＨ当量比を表２に示す。
また、ポリイソシアネート化合物としては、以下を使用した。
・ポリイソシアネート化合物１：ビウレット型水分散型イソシアネート（固形分：８０重量％、ＮＣＯ％：１３．４重量％）
・ポリイソシアネート化合物２：イソシアヌレート型水分散型イソシアネート（固形分：１００重量％、ＮＣＯ％：１４．３重量％）
(Manufacturing of
4 parts by weight of additives (pigments, wetting agents, thickeners, defoamers, preservatives, etc.) were added to 100 parts by weight of the synthetic resin emulsion to produce the liquid (I). Next, the solution (II) composed of the polyisocyanate compound was prepared and mixed with the solution (I) to produce
The following were used as the polyisocyanate compound.
-Polyisocyanate compound 1: Biuret type water-dispersed isocyanate (solid content: 80% by weight, NCO%: 13.4% by weight)
-Polyisocyanate compound 2: Isocyanurate type water-dispersed isocyanate (solid content: 100% by weight, NCO%: 14.3% by weight)
（熱発泡性被覆材１の製造）
アクリル樹脂１００重量部、メラミン７５重量部、ジペンタエリスリトール７５重量部、ポリリン酸アンモニウム３７０重量部及び酸化チタン１０５重量部を含む原料混合物を、ニーダーを用いて充分に混練後、押出し成形機によってシート状に加工し、膜厚１ｍｍの熱発泡性被覆材１を作製した。
(Manufacturing of heat-foamable coating material 1)
A raw material mixture containing 100 parts by weight of acrylic resin, 75 parts by weight of melamine, 75 parts by weight of dipentaerythritol, 370 parts by weight of ammonium polyphosphate and 105 parts by weight of titanium oxide is sufficiently kneaded using a kneader and then sheeted by an extrusion molding machine. It was processed into a shape to prepare a heat-
（熱発泡性被覆材２の製造）
エチレン−酢酸ビニル樹脂１００重量部、メラミン７５重量部、ジペンタエリスリトール７５重量部、ポリリン酸アンモニウム３７０重量部及び酸化チタン１０５重量部を含む原料混合物を、ニーダーを用いて充分に混練後、押出し成形機によってシート状に加工し、膜厚１ｍｍの熱発泡性被覆材２を作製した。
(Manufacturing of heat-foamable coating material 2)
A raw material mixture containing 100 parts by weight of ethylene-vinyl acetate resin, 75 parts by weight of melamine, 75 parts by weight of dipentaerythritol, 370 parts by weight of ammonium polyphosphate and 105 parts by weight of titanium oxide is sufficiently kneaded using a kneader and then extruded. It was processed into a sheet by a machine to prepare a heat-
（実施例１）
＜接着性評価＞
熱発泡性被覆材１（２５ｍｍ×５０ｍｍ）の片面の半面（２５ｍｍ×２５ｍｍ）に接着材１を１００ｇ／ｍ２塗付け、２５℃で３時間乾燥させ熱発泡性被覆材の裏面に第２接着材層を設けた積層体１を製造した。
一方、鋼板（１５０ｍｍ×７０ｍｍ×１．６ｍｍ）の片面に接着材２を１００ｇ／ｍ２塗付け第１接着材層を形成した。なお、接着材１、接着材２はいずれも、（Ｉ）液と（ＩＩ）液を混合後３時間以内のものを使用した。
次いで、鋼板の第１接着材層（接着材２塗付け面）の硬化前（塗付後２５℃で２時間乾燥）に、鋼板の第１接着材層と、積層体１の第２接着材層とを圧着して貼り合わせ、試験体Ａを得た。（なお、この試験体は、熱発泡性被覆材１の半面が鋼板に接着していない（非接着部分を有する）態様である。）
接着性試験では、上記試験体Ａを熱発泡性被覆材１が下側となるように水平に設置し、該熱発泡性被覆材１の非接着部分を９０°に折り曲げ、熱発泡性被覆材１折り曲げ部分の先端に２００ｇの重りを吊り下げ、鋼板から熱発泡性被覆材１が剥がれ落ちるまでの時間を測定した。評価は次の５段階で行った。結果は表３に示す。
Ａ：２時間以上
Ｂ：１時間以上２時間未満
Ｃ：３０分以上１時間未満
Ｄ：１５分以上３０分未満
Ｅ：１５分未満
(Example 1)
<Adhesiveness evaluation>
100 g / m 2 of adhesive 1 is applied to one side (25 mm x 25 mm) of the heat-foamable dressing 1 (25 mm x 50 mm), dried at 25 ° C. for 3 hours, and secondly adhered to the back surface of the heat-foamable dressing. A
On the other hand, 100 g / m 2 of the adhesive 2 was applied to one side of the steel plate (150 mm × 70 mm × 1.6 mm) to form the first adhesive layer. As the
Next, before the first adhesive layer (adhesive 2 coated surface) of the steel sheet is cured (dried at 25 ° C. for 2 hours after coating), the first adhesive layer of the steel sheet and the second adhesive of the
In the adhesiveness test, the test piece A is horizontally installed so that the heat-
A: 2 hours or more B: 1 hour or more and less than 2 hours C: 30 minutes or more and less than 1 hour D: 15 minutes or more and less than 30 minutes E: less than 15 minutes
＜耐水性評価＞
熱発泡性被覆材１（１５０ｍｍ×７０ｍｍ）の片面の全面に接着材１を１００ｇ／ｍ２塗付け、２５℃で３時間乾燥させ熱発泡性被覆材の裏面に第２接着材層を設けた積層体２を製造した。
一方、鋼板（１５０ｍｍ×７０ｍｍ×１．６ｍｍ）の片面に接着材２を１００ｇ／ｍ２塗付け第１接着材層を形成した。なお、接着材１、接着材２はいずれも、（Ｉ）液と（ＩＩ）液を混合後３時間以内のものを使用した。
次いで、鋼板の第１接着材層（接着材２塗付け面）の硬化前（塗付後２５℃で２時間乾燥）に、鋼板の第１接着材層と、積層体２の第２接着材層とを圧着して貼り合わせた。
さらに熱発泡性被覆材１の表面に化粧層（ウレタン樹脂塗料層）を積層し試験体Ｂを得た。
得られた試験体Ｂを、２５℃の水に４日間浸漬（耐水性評価１）し、積層体の外観を評価した。評価基準は、評価は次の４段階で行った。
さらに、耐水性評価１で良好な結果（◎）であったものについて、試験体Ｂを２５℃の水に７日間浸漬（耐水性評価２）し、同様の評価を実施した。結果は表３に示す。
◎：全く変化がない
○：ほぼ変化がない
△：やや剥がれが生じた
×：剥がれが生じた
<Water resistance evaluation>
100 g / m 2 of the adhesive 1 was applied to the entire surface of one side of the heat-foamable coating material 1 (150 mm × 70 mm) and dried at 25 ° C. for 3 hours to provide a second adhesive layer on the back surface of the heat-foamable coating material. The
On the other hand, 100 g / m 2 of the adhesive 2 was applied to one side of the steel plate (150 mm × 70 mm × 1.6 mm) to form the first adhesive layer. As the
Next, before the first adhesive layer (adhesive 2 coated surface) of the steel sheet is cured (dried at 25 ° C. for 2 hours after coating), the first adhesive layer of the steel sheet and the second adhesive of the
Further, a decorative layer (urethane resin paint layer) was laminated on the surface of the heat-
The obtained test body B was immersed in water at 25 ° C. for 4 days (water resistance evaluation 1) to evaluate the appearance of the laminated body. As for the evaluation criteria, the evaluation was performed in the following four stages.
Further, for those having a good result (⊚) in the
⊚: No change at all ○: Almost no change △: Slight peeling occurred ×: Peeling occurred
＜脱落防止性評価＞
熱発泡性被覆材１（７０ｍｍ×７０ｍｍ）の片面の全面に接着材１を１００ｇ／ｍ２塗付け、２５℃で３時間乾燥させ熱発泡性被覆材の裏面に第２接着材層を設けた積層体３を製造した。
一方、鋼板（１５０ｍｍ×７０ｍｍ×１．６ｍｍ）の片面に接着材２を１００ｇ／ｍ２塗付け第１接着材層を形成した。なお、接着材１、接着材２はいずれも、（Ｉ）液と（ＩＩ）液を混合後３時間以内のものを使用した。
次いで、鋼板の第１接着材層（接着材２塗付け面）の硬化前（塗付後２５℃で２時間乾燥）に、鋼板の第１接着材層と、積層体３の第２接着材層とを圧着して貼り合わせ、試験体Ｃを得た。
脱落防止性試験では、熱発泡性被覆材１が下側となるように水平に設置し、該試験体の上側２５ｍｍの位置にヒーター（ヒーター温度６８０℃）を設置し、ヒーターにより試験体を加熱し、鋼板から熱発泡性被覆材１が脱落したときの鋼板と熱発泡性被覆材１の境界面温度を測定した。評価は次の４段階で行った。結果は表３に示す。
◎：脱落温度３２０℃以上
○：脱落温度３００℃以上３２０℃未満
△：脱落温度２８０以上３００℃未満
×：脱落温度２８０℃未満
<Evaluation of dropout prevention>
100 g / m 2 of adhesive 1 was applied to the entire surface of one side of the heat-foamable coating material 1 (70 mm × 70 mm), dried at 25 ° C. for 3 hours, and a second adhesive layer was provided on the back surface of the heat-foamable coating material. The
On the other hand, 100 g / m 2 of the adhesive 2 was applied to one side of the steel plate (150 mm × 70 mm × 1.6 mm) to form the first adhesive layer. As the
Next, before the first adhesive layer (adhesive 2 coated surface) of the steel sheet is cured (dried at 25 ° C. for 2 hours after coating), the first adhesive layer of the steel sheet and the second adhesive of the
In the dropout prevention test, the heat-
⊚: Dropping temperature 320 ° C or higher ○: Dropping temperature 300 ° C or higher and lower than 320 ° C Δ: Dropping temperature 280 or higher and lower than 300 ° C ×: Dropping temperature less than 280 ° C
（実施例２〜１２、１４〜１６、比較例１〜２、参考例１３、１７）
実施例２〜１２、１４〜１６、比較例１〜２、参考例１３、１７で使用した接着材の種類、使用した熱発泡性被覆材の種類を表３に示す通りとした。
熱発泡性被覆材（２５ｍｍ×５０ｍｍ）の片面の半面（２５ｍｍ×２５ｍｍ）に接着材を１００ｇ／ｍ ２ 塗付け、２５℃で３時間または２４時間乾燥させ熱発泡性被覆材の裏面に第２接着材層を設けた積層体を製造した。
それ以外は、実施例１と同様の方法で、試験体を作製し、各試験を行った。結果は表３に示す。
( Examples 2 to 12, 14 to 16, Comparative Examples 1 to 2, Reference Examples 13 and 17 )
The types of adhesives used in Examples 2 to 12, 14 to 16, Comparative Examples 1 to 2, and Reference Examples 13 and 17 and the types of heat-foamable coating materials used were as shown in Table 3.
100 g / m 2 of adhesive is applied to one side (25 mm x 25 mm) of the heat-foamable dressing (25 mm x 50 mm) and dried at 25 ° C. for 3 hours or 24 hours to cover the back surface of the heat-foamable dressing. A laminate provided with an adhesive layer was manufactured.
Except for the above, a test body was prepared in the same manner as in Example 1, and each test was performed. The results are shown in Table 3.
Claims (7)
前記基材面上に第１接着材層を設ける工程、
前記第１接着材層と、前記熱発泡性被覆材の裏面に設けられた第２接着材層とを圧着する工程を有し、
前記第１接着材層は、水酸基含有合成樹脂を含む（Ｉ）液とポリイソシアネート化合物を含む（ＩＩ）液を、ＮＣＯ／ＯＨ当量比１０／１００〜１２０／１００で含む接着材（Ｍ）より形成されるものであり、前記第２接着材層は、水酸基含有合成樹脂を含む接着材、または水酸基含有合成樹脂及びポリイソシアネート化合物を含む接着材（Ｎ）より形成されるものであり、
前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、前記接着材（Ｍ）におけるＮＣＯ／ＯＨ当量比よりも小さく、
前記接着材（Ｍ）により形成される接着材層の硬化前に、前記第１接着材層と前記第２接着材層とを圧着することを特徴とする積層構造体の形成方法。 A method for forming a laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a base material surface.
The step of providing the first adhesive layer on the base material surface,
It has a step of crimping the first adhesive layer and the second adhesive layer provided on the back surface of the heat-foamable coating material.
The first adhesive layer is made from an adhesive (M) containing a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound at an NCO / OH equivalent ratio of 10/100 to 120/100. The second adhesive layer is formed of an adhesive containing a hydroxyl group-containing synthetic resin or an adhesive (N) containing a hydroxyl group-containing synthetic resin and a polyisocyanate compound.
The NCO / OH equivalent ratio in the adhesive (N) is smaller than the NCO / OH equivalent ratio in the adhesive (M).
A method for forming a laminated structure, which comprises crimping the first adhesive layer and the second adhesive layer before curing the adhesive layer formed by the adhesive (M).
前記接着材層は、基材面に接する第１接着材層と、熱発泡性被覆材に接する第２接着材層を有し、
前記第１接着材層は、水酸基含有合成樹脂を含む（Ｉ）液とポリイソシアネート化合物を含む（ＩＩ）液を、ＮＣＯ／ＯＨ当量比１０／１００〜１２０／１００で含む接着材（Ｍ）より形成されてなり、前記第２接着材層は、水酸基含有合成樹脂を含む接着材、または水酸基含有合成樹脂及びポリイソシアネート化合物を含む接着材（Ｎ）より形成されてなり、
前記接着材（Ｎ）におけるＮＣＯ／ＯＨ当量比は、前記接着材（Ｍ）におけるＮＣＯ／ＯＨ当量比よりも小さいことを特徴とする積層構造体。
A laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a base material surface.
The adhesive layer has a first adhesive layer in contact with the surface of the base material and a second adhesive layer in contact with the heat-foamable coating material.
The first adhesive layer is made from an adhesive (M) containing a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound at an NCO / OH equivalent ratio of 10/100 to 120/100. is formed becomes in the second adhesive layer, Ri Na is formed from an adhesive containing a hydroxyl group-containing synthetic resin or adhesive containing a hydroxyl group-containing synthetic resins and polyisocyanate compounds (N),
A laminated structure characterized in that the NCO / OH equivalent ratio in the adhesive material (N) is smaller than the NCO / OH equivalent ratio in the adhesive material (M).
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