JP5394607B2 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP5394607B2 JP5394607B2 JP2006322227A JP2006322227A JP5394607B2 JP 5394607 B2 JP5394607 B2 JP 5394607B2 JP 2006322227 A JP2006322227 A JP 2006322227A JP 2006322227 A JP2006322227 A JP 2006322227A JP 5394607 B2 JP5394607 B2 JP 5394607B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- silyl group
- group
- heating
- crosslinkable silyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 77
- 230000001070 adhesive effect Effects 0.000 title claims description 77
- 239000000203 mixture Substances 0.000 title claims description 76
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 54
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 229920000620 organic polymer Polymers 0.000 claims description 35
- 239000003094 microcapsule Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000011810 insulating material Substances 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 22
- 238000010276 construction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 238000005187 foaming Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 28
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 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 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- CBOLARLSGQXRBB-UHFFFAOYSA-N 1-(oxiran-2-yl)-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1OC1)CC1CO1 CBOLARLSGQXRBB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MMGVVYCBXBYXRR-UHFFFAOYSA-L 2-acetyl-3-oxobutanoate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CC(=O)C(C(C)=O)C([O-])=O.CC(=O)C(C(C)=O)C([O-])=O MMGVVYCBXBYXRR-UHFFFAOYSA-L 0.000 description 1
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 description 1
- ZGSJFMIWRLMFBZ-UHFFFAOYSA-N 3-(3-aminopropyl-ethoxy-ethylsilyl)oxybutan-1-amine Chemical compound NCCC(C)O[Si](OCC)(CC)CCCN ZGSJFMIWRLMFBZ-UHFFFAOYSA-N 0.000 description 1
- BNYFUBOZYDQIDU-UHFFFAOYSA-N 3-[diethoxy(ethyl)silyl]propan-1-amine Chemical compound CCO[Si](CC)(OCC)CCCN BNYFUBOZYDQIDU-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- RDIGYBZNNOGMHU-UHFFFAOYSA-N 3-amino-2,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound OC1=CC(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 RDIGYBZNNOGMHU-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108091028140 FREP Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- 238000010538 cationic polymerization reaction Methods 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000005350 fused silica glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 description 1
- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical class 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着剤組成物、接着剤組成物の施工方法および複合材料に関する。 The present invention relates to an adhesive composition, a method for applying the adhesive composition, and a composite material.
従来、建築材料、構造材料、断熱材料として発泡スチロール、発泡ポリエチレン等の各種発泡体が利用されている。
また、エポキシ樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、フェノール樹脂、メラミン樹脂、シリコンエラストマー等の熱硬化性樹脂は、各種構造材料として使用されている。
更に、これらの熱硬化性樹脂は、軽量化、断熱付与、経済的理由により、しばしば発泡体との複合化が行われている（例えば、特許文献１〜４等参照。）。
Conventionally, various foams, such as a polystyrene foam and a polyethylene foam, are utilized as a building material, a structural material, and a heat insulation material.
Thermosetting resins such as epoxy resins, unsaturated polyester resins, polyurethane resins, phenol resins, melamine resins, and silicon elastomers are used as various structural materials.
Furthermore, these thermosetting resins are often combined with foams for light weight, imparting heat insulation, and economical reasons (see, for example, Patent Documents 1 to 4).
具体的には、特許文献１には、「粒径０．０１〜５ｍｍ、発泡倍率３〜１００倍のポリ塩化ビニリデン系多泡質発泡粒子１０〜９９体積％と、熱硬化性樹脂１〜９０体積％からなる複合材料。」が記載され（［請求項１］）、「粒径０．００５〜２ｍｍの、発泡剤を含むポリ塩化ビニリデン系未発泡ビ−ズと熱硬化性樹脂原料とを、ビ−ズ／熱硬化性樹脂原料＝１００／１〜１／３０の重量比で混合し、熱硬化性樹脂の硬化時の反応熱及び、その反応熱と外部からの加熱により、硬化と同時に発泡させることを特徴とする請求項１記載の複合材料の製造方法。」が記載されている（［請求項２］）。
同様に、特許文献２には、「下記（１）、（２）、（３）を主成分とする複合材料。（１）粒径０．０１〜５ｍｍ、発泡倍率３〜１００倍のポリ塩化ビニリデン系多泡質発泡粒子１０〜９９体積％。（２）熱硬化性樹脂１〜９０体積％。（３）（１）及び（２）の合計量１００重量部に対して、１〜２００重量部の補強材。」が記載され（［請求項１］）、「下記（１）、（２）、（３）を主成分とする原料を硬化時の反応熱及び、その反応熱と外部からの加熱により、硬化と同時に発泡させることを特長とする請求項１記載の複合材料の製造方法。
（１）粒径０．００５〜２ｍｍの、発泡剤を含むポリ塩化ビニリデン系未発泡ビーズ。
（２）熱硬化性樹脂原料。ただし、（１）／（２）＝１００／１〜１／３０（重量比）
（３）（１）及び（２）の合計量１００重量部に対して、１〜２００重量部の補強材。」が記載されている（［請求項２］）。
Specifically, Patent Document 1 describes that “polyvinylidene chloride-based foamed foam particles having a particle size of 0.01 to 5 mm and an expansion ratio of 3 to 100 times and 10 to 99% by volume, and thermosetting resins 1 to 90”. Composite material consisting of volume% ”([Claim 1]),“ a polyvinylidene chloride unfoamed bead containing a foaming agent having a particle size of 0.005 to 2 mm and a thermosetting resin raw material. , Bead / thermosetting resin raw material = 100/1 to 1/30 by weight ratio, the reaction heat at the time of curing the thermosetting resin, and the reaction heat and external heating simultaneously with the curing 2. A method for producing a composite material according to claim 1, wherein foaming is performed ([Claim 2]).
Similarly, Patent Document 2 states that “a composite material mainly composed of the following (1), (2), and (3). (1) Polychlorination having a particle diameter of 0.01 to 5 mm and an expansion ratio of 3 to 100 times. 10 to 99% by volume of vinylidene-based foamed foam particles (2) 1 to 90% by volume of thermosetting resin (3) 1 to 200% by weight with respect to 100 parts by weight of the total amount of (1) and (2) ([Claim 1]), "reaction heat at the time of curing a raw material mainly comprising the following (1), (2), (3), and the reaction heat and the outside from The method for producing a composite material according to claim 1, wherein foaming is performed simultaneously with curing by heating.
(1) Polyvinylidene chloride unfoamed beads containing a foaming agent and having a particle size of 0.005 to 2 mm.
(2) Thermosetting resin raw material. However, (1) / (2) = 100/1 to 1/30 (weight ratio)
(3) A reinforcing material of 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of (1) and (2). Is described ([Claim 2]).
また、特許文献３には、「部分架橋した塩化ビニリデン系樹脂粒子に発泡剤を均一に含有させ、発泡時に架橋構造により安定化された多泡質構造となる発泡性塩化ビニリデン系樹脂粒子あるいはその予備発泡粒子を配合してなることを特徴とする熱膨張性シーリング剤。」が記載され（［請求項１］）、変成シリコーン樹脂を用いた実施例が記載されている（［実施例１］）。 Further, Patent Document 3 states that “a foaming vinylidene chloride resin particle having a foamed agent uniformly contained in partially crosslinked vinylidene chloride resin particles and having a multi-foamed structure stabilized by a crosslinked structure at the time of foaming or its A heat-expandable sealing agent comprising pre-expanded particles ”([Claim 1]) and an example using a modified silicone resin ([Example 1]). ).
一方、特許文献４には、「家屋の床、壁等を形成する断熱性建築用パネルの製造方法であって、枠材を矩形に接合した周囲枠を有する枠組の一面にこの一面を覆う面材が添設されることにより面材を底面とする浅底皿状の凹所が形成されたパネル基体を前記凹所を上に向けて搬送するとともに搬送の間に、搬送されるパネル基体の少なくとも前記凹所を予備加熱するプレヒート工程と、予備加熱された凹所内に断熱用の発泡性樹脂を未発泡状態で塗着させる塗布工程と、塗着された発泡性樹脂を発泡させ発泡断熱層を形成するキュア工程とを含む処理工程を施すことを特徴とする断熱性建築用パネルの製造方法。」が記載されている。 On the other hand, Patent Document 4 states that “a method for manufacturing a heat-insulating building panel that forms a floor, a wall, etc. of a house, and covers this surface on one surface of a frame having a peripheral frame in which frame materials are joined in a rectangular shape. A panel base having a shallow dish-shaped recess having a face material as a bottom surface by the attachment of the material is transported with the recess facing upward, and the panel base that is transported during transport A preheating step of preheating at least the recess; an application step of applying a foaming resin for heat insulation in the preheated recess in an unfoamed state; and a foaming heat insulating layer by foaming the applied foamable resin The manufacturing method of the panel for heat insulation building characterized by performing the process process including the curing process which forms ".
しかしながら、特許文献１および２に記載の複合材料は、被着体への接着性が劣る問題があり、特許文献３に記載の熱膨張性シーリング剤は、被着体への耐水・耐熱接着性が劣る問題があった。
また、特許文献１、２および４に記載の製造方法では、断熱性に優れる材料が得られないという問題があった。
However, the composite materials described in Patent Documents 1 and 2 have a problem of poor adhesion to the adherend, and the thermally expandable sealing agent described in Patent Document 3 is resistant to water and heat on the adherend. There was an inferior problem.
In addition, the production methods described in Patent Documents 1, 2, and 4 have a problem that a material having excellent heat insulation cannot be obtained.
そこで、本発明は、被着体との接着性（被着性）に優れ、断熱性にも優れる複合材料を得ることができる接着剤組成物および接着剤組成物の施工方法ならびに複合材料を提供することを課題とする。 Accordingly, the present invention provides an adhesive composition capable of obtaining a composite material having excellent adhesion (adhesiveness) to an adherend and excellent heat insulation, a method for applying the adhesive composition, and a composite material The task is to do.
本発明者は、上記課題を解決するため鋭意検討した結果、主剤および硬化剤のいずれか一方または両方に未発泡の熱発泡性マイクロカプセルを含有する接着剤組成物が被着体との接着性（被着性）に優れ、断熱性にも優れる複合材料を得ることができる接着剤組成物となることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has found that an adhesive composition containing unfoamed heat-foamable microcapsules in either one or both of the main agent and the curing agent is adhesive to the adherend. The present invention has been completed by finding that it is an adhesive composition capable of obtaining a composite material having excellent (adhesion properties) and excellent heat insulation properties.
即ち、本発明は、下記（１）〜（４）を提供する。
（１）架橋性シリル基含有有機重合体（Ａ）を含有する基材成分と、
接着付与剤（Ｂ）を含有する硬化剤成分とからなり、
上記基材成分および／または上記硬化剤成分に、未発泡の熱発泡性マイクロカプセル（Ｃ）を含有し、
上記熱発泡性マイクロカプセル（Ｃ）の含有量が、上記架橋性シリル基含有有機重合体（Ａ）および上記接着付与剤（Ｂ）の合計１００質量部に対し、０．１〜１０質量部であり、
上記接着付与剤（Ｂ）が、シランカップリング剤であり、
上記シランカップリング剤の含有量が、上記架橋性シリル基含有有機重合体（Ａ）１００質量部に対して、０．１〜５０質量部である、接着剤組成物。
（２）加熱前の体積と加熱により発泡させた後の体積との比（加熱後／加熱前）が、１超１００以下である上記（１）に記載の接着剤組成物。
（３）上記（１）または（２）のいずれかに記載の接着剤組成物の施工方法であって、
上記接着剤組成物を被着体に塗布する塗布工程と、
上記塗布工程により塗布された上記接着剤組成物を加熱する加熱工程とを具備する施工方法。
（４）上記（３）に記載の接着剤組成物の施工方法により得られる、被着体上に該被着体に接着した断熱材が形成された複合材料。
That is, the present invention provides the following (1) to ( 4 ).
(1) a base material component containing a crosslinkable silyl group-containing organic polymer (A);
It comprises a curing agent component containing an adhesion promoter (B),
The base component and / or the curing agent component contains unfoamed thermally foamable microcapsules (C),
The content of the thermally foamable microcapsule (C) is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). Oh it is,
The adhesion-imparting agent (B) is a silane coupling agent,
The adhesive composition whose content of the said silane coupling agent is 0.1-50 mass parts with respect to 100 mass parts of said crosslinkable silyl group containing organic polymers (A) .
(2 ) The adhesive composition according to the above (1 ), wherein the ratio (after heating / before heating) of the volume before heating and the volume after foaming by heating is more than 1 and 100 or less.
(3) A construction method of the above (1) or adhesive composition according to any one of (2),
An application step of applying the adhesive composition to an adherend;
A construction method comprising: a heating step of heating the adhesive composition applied in the application step.
( 4 ) A composite material obtained by the method for applying an adhesive composition according to ( 3 ) above, wherein a heat insulating material adhered to the adherend is formed on the adherend.
以下に示すように、本発明によれば、被着体との接着性（被着性）に優れ、断熱性にも優れる複合材料を得ることができる接着剤組成物および接着剤組成物の施工方法ならびに複合材料を提供することができる。
また、本発明の接着剤組成物を用いれば、施工方法（複合材料の製造段階）において、接着剤および断熱材の容積を減少することができ、施工工程の簡略化および施工時間の短縮化も図ることできるため非常に有用である。
更に、本発明の接着剤組成物を用いれば、被着体上に断熱材を形成する際に特別な型も必要としないため、複雑な形状の被着体に対しても断熱材を形成することができるため非常に有用である。
As shown below, according to the present invention, an adhesive composition capable of obtaining a composite material having excellent adhesion (adhesiveness) to an adherend and excellent heat insulation, and construction of the adhesive composition Methods as well as composite materials can be provided.
In addition, if the adhesive composition of the present invention is used, the volume of the adhesive and the heat insulating material can be reduced in the construction method (composite material production stage), and the construction process can be simplified and the construction time can be shortened. It is very useful because it can be planned.
Furthermore, when the adhesive composition of the present invention is used, no special mold is required when forming the heat insulating material on the adherend, and therefore the heat insulating material is formed even on the adherend having a complicated shape. It is very useful because it can.
本発明の接着剤組成物は、架橋性シリル基含有有機重合体（Ａ）を含有する基材成分と、接着付与剤（Ｂ）を含有する硬化剤成分とからなり、
上記基材成分および／または上記硬化剤成分に、未発泡の熱発泡性マイクロカプセル（Ｃ）を含有する接着剤組成物である。
以下に、架橋性シリル基含有有機重合体（Ａ）、接着付与剤（Ｂ）および熱発泡性マイクロカプセル（Ｃ）について詳述する。
The adhesive composition of the present invention comprises a base material component containing a crosslinkable silyl group-containing organic polymer (A) and a curing agent component containing an adhesion promoter (B),
It is an adhesive composition containing unfoamed thermally foamable microcapsules (C) in the base material component and / or the curing agent component.
Hereinafter, the crosslinkable silyl group-containing organic polymer (A), the adhesion-imparting agent (B), and the thermally foamable microcapsule (C) will be described in detail.
＜架橋性シリル基含有有機重合体（Ａ）＞
上記架橋性シリル基含有有機重合体（Ａ）は、以下に示す架橋性シリル基を末端または側鎖に少なくとも１個有する有機重合体である。
ここで、架橋性シリル基とは、例えば、ケイ素原子と結合した加水分解性基を有するケイ素含有基やシラノール基のように湿気や架橋剤の存在下、必要に応じて触媒等を使用することにより縮合反応を起こす基のことであり、代表的なものを示すと、例えば、下記一般式（１）で表される基が挙げられる。
<Crosslinkable silyl group-containing organic polymer (A)>
The crosslinkable silyl group-containing organic polymer (A) is an organic polymer having at least one crosslinkable silyl group shown below at the terminal or side chain.
Here, the crosslinkable silyl group is, for example, using a catalyst or the like as necessary in the presence of moisture or a crosslinking agent such as a silicon-containing group or silanol group having a hydrolyzable group bonded to a silicon atom. As a representative group, for example, a group represented by the following general formula (1) can be mentioned.
式中、Ｒ1およびＲ2は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基または（Ｒ3）3ＳｉＯ−で示されるトリオルガノシロキシ基を示し、Ｒ1またはＲ2が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。
ここで、Ｒ3は炭素数１〜２０の１価の炭化水素基であり、３個のＲ3は同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０、１、２または３を、ｂは０、１または２をそれぞれ示す。
また、ｔ個の下記一般式（２）で表される基におけるｂは異なっていてもよい。ｔは０〜１９の整数を示す。ただし、ａ＋ｔ×ｂ≧１を満足するものとする。
In the formula, R 1 and R 2 are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R 3 ) 3 SiO—. And when two or more R 1 or R 2 are present, they may be the same or different.
Here, R 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R 3 s may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2.
In the t groups represented by the following general formula (2), b may be different. t shows the integer of 0-19. However, it is assumed that a + t × b ≧ 1 is satisfied.
上記Ｙで示される加水分解性基は特に限定されず、従来公知の加水分解性基であればよい。具体的には、例えば、水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられる。これらのうち、水素原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、アミノオキシ基、メルカプト基およびアルケニルオキシ基であることが好ましく、加水分解性が穏やかで取り扱いやすいという理由からメトキシ基等のアルコキシ基が特に好ましい。
架橋性シリル基の中で、下記一般式（３）で表される架橋性シリル基が、入手容易の点から好ましい。下記一般式（３）中、Ｒ2、Ｙ、ａは上述のＲ2、Ｙ、ａと同義である。
The hydrolyzable group represented by Y is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Alkoxy groups such as groups are particularly preferred.
Among the crosslinkable silyl groups, a crosslinkable silyl group represented by the following general formula (3) is preferable from the viewpoint of easy availability. In the following general formula (3), R 2 , Y and a have the same meanings as R 2 , Y and a described above.
上記一般式（１）におけるＲ1およびＲ2の具体例としては、例えば、メチル基、エチル基などのアルキル基；シクロヘキシル基などの脂環式炭化水素基；フェニル基などのアリール基；ベンジル基などのアラルキル基；Ｒ3がメチル基やフェニル基などである（Ｒ3）3ＳｉＯ−で示されるトリオルガノシロキシ基；等が挙げられる。Ｒ1、Ｒ2、Ｒ3としてはメチル基が特に好ましい。 Specific examples of R 1 and R 2 in the general formula (1) include, for example, alkyl groups such as methyl group and ethyl group; alicyclic hydrocarbon groups such as cyclohexyl group; aryl groups such as phenyl group; benzyl group And a triorganosiloxy group represented by (R 3 ) 3 SiO— in which R 3 is a methyl group or a phenyl group. R 1 , R 2 and R 3 are particularly preferably methyl groups.
したがって、上記架橋性シリル基含有有機重合体（Ａ）は、末端または側鎖に、上記一般式（１）で表される架橋性シリル基を少なくとも１個有する有機重合体であれば特に限定されず、具体的には、例えば、シリル基含有ポリエーテル、シリル基含有ポリエステル、シリル基含有ビニル系重合体、シリル基含有ポリエステル変性ビニル系重合体、シリル基含有ジアリルフタレート系重合体、シリル基含有ジアリールフタレート系重合体、シリル基含有ポリイソブチレン、シリル基含有エチレン・α−オレフィン系共重合体、これらの混合物およびこれらの共重合体（ブロック共重合体、グラフト共重合体）のシリル基含有有機重合体等が挙げられる。 Therefore, the crosslinkable silyl group-containing organic polymer (A) is particularly limited as long as it is an organic polymer having at least one crosslinkable silyl group represented by the general formula (1) at the terminal or side chain. Specifically, for example, silyl group-containing polyether, silyl group-containing polyester, silyl group-containing vinyl polymer, silyl group-containing polyester modified vinyl polymer, silyl group-containing diallyl phthalate polymer, silyl group-containing Diaryl phthalate polymers, silyl group-containing polyisobutylenes, silyl group-containing ethylene / α-olefin copolymers, mixtures thereof and silyl group-containing organics of these copolymers (block copolymers, graft copolymers) A polymer etc. are mentioned.
これらのうち、上記架橋性シリル基含有有機重合体（Ａ）がシリル基含有ポリエーテルである場合、主鎖のポリエーテルとしては、エチレンオキサイド、プロピレンオキサイド、ブテンオキシド、テトラヒドロフランなどを原料物質として、カチオン重合、アニオン重合の方法を用いて製造されるもの等が好適に例示される。 Among these, when the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyether, as the main chain polyether, ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran and the like are used as raw materials. Preferred examples include those produced using cationic polymerization and anionic polymerization methods.
上記架橋性シリル基含有有機重合体（Ａ）がシリル基含有ポリエステルである場合には、主鎖のポリエステルとしては、マレイン酸、コハク酸、グルタル酸、アジピン酸、フタル酸などのカルボン酸、その無水物、そのエステルまたはハロゲン化物と、化学量論的過剰のエチレングリコール、プロピレングリコール、グリセリンなどのポリオールと、を反応させることにより調整されるポリエステルポリオール類、または、ラクトン類の開環重合により得られるラクトンポリオール類等が好適に例示される。 When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyester, examples of the main chain polyester include carboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid, and phthalic acid, Obtained by ring-opening polymerization of polyester polyols or lactones prepared by reacting anhydrides, esters or halides thereof with a stoichiometric excess of polyols such as ethylene glycol, propylene glycol, and glycerin. Preferred examples include lactone polyols and the like.
上記架橋性シリル基含有有機重合体（Ａ）がシリル基含有ビニル系重合体である場合、ビニルモノマーとしてアクリルモノマーを主成分に用いることが、得られる架橋性シリル基含有有機重合体（Ａ）を含有する本発明の接着剤組成物の耐候性および物性（モジュラス）が向上する理由から好ましい。
上記ビニルモノマーの具体例としては、特開２００２−９７４４９号公報に記載されているシクロヘキシルアクリレートおよび／またはブチルアクリレートを主成分とするビニルモノマーが挙げられる。また、上記公報では、上記ビニルモノマーとアルコキシシリル基含有モノマーとを共重合させることによって、シリル基含有ビニル系重合体が得られることが記載されている。更に、重合方法は、通常のラジカル重合に加え、特開昭５７−５０２１７１号公報および特開昭５９−６２０７号公報に記載されている高温連続重合を用いることもできる。
When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing vinyl polymer, it is possible to use an acrylic monomer as a vinyl monomer as a main component, and the resulting crosslinkable silyl group-containing organic polymer (A) This is preferable because the weather resistance and physical properties (modulus) of the adhesive composition of the present invention containing the above are improved.
Specific examples of the vinyl monomer include vinyl monomers mainly composed of cyclohexyl acrylate and / or butyl acrylate described in JP-A No. 2002-97449. Further, the above publication describes that a silyl group-containing vinyl polymer can be obtained by copolymerizing the vinyl monomer and an alkoxysilyl group-containing monomer. Furthermore, as a polymerization method, high-temperature continuous polymerization described in JP-A-57-502171 and JP-A-59-6207 can be used in addition to normal radical polymerization.
上記架橋性シリル基含有有機重合体（Ａ）が、シリル基含有ポリイソブチレンやシリル基含有エチレン・α−オレフィン系共重合体である場合、主鎖としては、それぞれ、特開平４−１５４８１６号公報および特開２００１−３１７１９号公報に記載された方法により製造されたものが用いられる。 When the crosslinkable silyl group-containing organic polymer (A) is a silyl group-containing polyisobutylene or a silyl group-containing ethylene / α-olefin copolymer, the main chain is disclosed in JP-A-4-154816, respectively. And what was manufactured by the method described in Unexamined-Japanese-Patent No. 2001-31719 is used.
また、架橋性シリル基含有有機重合体（Ａ）の数平均分子量は１０００以上であることが好ましく、６０００〜３００００であることがより好ましい。数平均分子量がこの範囲であると、架橋性シリル基含有有機重合体（Ａ）を含有する本発明の接着剤組成物の硬化前の粘度が低くなるため取り扱い易く、硬化後の強度、伸び、モジュラス等の物性が良好となる理由から好ましい。 Moreover, it is preferable that the number average molecular weights of a crosslinkable silyl group containing organic polymer (A) are 1000 or more, and it is more preferable that it is 6000-30000. When the number average molecular weight is within this range, the adhesive composition of the present invention containing the crosslinkable silyl group-containing organic polymer (A) is easy to handle because the viscosity before curing is low, and the strength, elongation after curing, It is preferable because the physical properties such as modulus are good.
本発明においては、以上で説明するもののうち、主鎖が本質的にポリエーテルで、分子中に末端としてまたは側鎖に少なくとも１個のメチルジメトキシシリル基を有するポリエーテルオリゴマー、または、該ポリエーテルオリゴマーとメチルジメトキシシリル基を有するアクリルオリゴマーとの混合物を含む架橋性シリル基含有有機重合体を用いることが好ましい。
また、得られる本発明の接着剤組成物を用いて被着体上に形成される断熱材の硬度を高くする観点からは、架橋性シリル基を３個有する有機重合体であるのが好ましく、また、該断熱材の硬度を低くする観点からは、架橋性シリル基を２個有する有機重合体であるのが好ましい。
In the present invention, among those described above, a polyether is essentially a polyether, a polyether oligomer having at least one methyldimethoxysilyl group as a terminal or a side chain in the molecule, or the polyether It is preferable to use a crosslinkable silyl group-containing organic polymer containing a mixture of an oligomer and an acrylic oligomer having a methyldimethoxysilyl group.
Further, from the viewpoint of increasing the hardness of the heat insulating material formed on the adherend using the adhesive composition of the present invention obtained, it is preferably an organic polymer having three crosslinkable silyl groups, Further, from the viewpoint of lowering the hardness of the heat insulating material, an organic polymer having two crosslinkable silyl groups is preferable.
また、本発明においては、架橋性シリル基含有有機重合体（Ａ）として、鐘淵化学工業社製のＭＳポリマーやサイリル、エピオン、旭硝子社製のエクセスター等の市販品を用いることができる。 In the present invention, as the crosslinkable silyl group-containing organic polymer (A), commercially available products such as MS polymer manufactured by Kaneka Chemical Industry Co., Ltd., Silyl, Epion, Exastar manufactured by Asahi Glass Co., Ltd. can be used.
＜接着付与剤（Ｂ）＞
上記接着付与剤（Ｂ）は、従来公知の接着性付与剤であれば特に限定されず、その具体例としては、シランカップリング剤、テルペン樹脂、フェノール樹脂、テルペン−フェノール樹脂、ロジン樹脂、キシレン樹脂等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
これらのうち、シランカップリング剤であるのが、得られる本発明の接着剤組成物の被着体に対する接着性がより向上する理由から好ましい。
<Adhesion imparting agent (B)>
The adhesion imparting agent (B) is not particularly limited as long as it is a conventionally known adhesion imparting agent. Specific examples thereof include a silane coupling agent, a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and xylene. Resin etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
Among these, the silane coupling agent is preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.
上記シランカップリング剤は、接着付与剤として従来公知のシランカップリング剤であれば特に限定されず、その具体例としては、アミノシラン、メルカプトシラン、ビニルシラン、エポキシシラン、メタクリルシラン、イソシアネートシラン、ケチミンシランもしくはこれらの混合物もしくは反応物、または、これらとポリイソシアネートとの反応により得られる化合物等が挙げられる。
これらのうち、アミノシラン、メルカプトシランであるのが、得られる本発明の接着剤組成物の被着体に対する接着性が更に向上する理由から好ましい。
The silane coupling agent is not particularly limited as long as it is a conventionally known silane coupling agent as an adhesion-imparting agent, and specific examples thereof include aminosilane, mercaptosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or These mixtures or reactants, or compounds obtained by reacting these with polyisocyanates, and the like can be mentioned.
Among these, aminosilane and mercaptosilane are preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.
アミノシランは、アミノ基またはイミノ基と加水分解性のケイ素含有基とを有する化合物であれば特に限定されず、その具体例としては、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルエチルジエトキシシラン、ビストリメトキシシリルプロピルアミン、ビストリエトキシシリルプロピルアミン、ビスメトキシジメトキシシリルプロピルアミン、ビスエトキシジエトキシシリルプロピルアミン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルエチルジエトキシシラン等が挙げられる。 The aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- ( Aminoethyl -3-aminopropyl ethyldiethoxysilane and the like.
メルカプトシランとしては、具体的には、例えば、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン、γ−メルカプトプロピルエチルジエトキシシラン等が挙げられる。 Specific examples of the mercaptosilane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-mercaptopropylethyl. Examples include diethoxysilane.
ビニルシランとしては、具体的には、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、トリス−（２−メトキシエトキシ）ビニルシラン等が挙げられる。
エポキシシランとしては、具体的には、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルジメチルエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルメチルジメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。
メタクリルシランとしては、具体的には、例えば、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン等が挙げられる。
イソシアネートシランとしては、具体的には、例えば、イソシアネートプロピルトリエトキシシラン、イソシアネートプロピルトリメトキシシランが挙げられる。
ケチミンシランとしては、具体的には、例えば、ケチミン化プロピルトリメトキシシラン、ケチミン化プロピルトリエトキシシランが挙げられる。
Specific examples of vinylsilane include vinyltrimethoxysilane, vinyltriethoxysilane, and tris- (2-methoxyethoxy) vinylsilane.
Specific examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4- Epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Specific examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Can be mentioned.
Specific examples of the isocyanate silane include isocyanate propyl triethoxy silane and isocyanate propyl trimethoxy silane.
Specific examples of the ketimine silane include ketiminated propyltrimethoxysilane and ketiminated propyltriethoxysilane.
本発明においては、このような接着付与剤（Ｂ）を含有することにより、得られる本発明の接着剤組成物を用いて被着体上に形成される断熱材と該被着体との接着性が良好なものとなる。
また、このような接着付与剤（Ｂ）を含有することにより、現行の施工方法、即ち、被着体上に接着剤を塗布し、断熱材を圧着させる施工方法において使用する接着剤を用いる必要がなく、施工工程の簡略化および施工時間の短縮化も図ることできる。これは、上記架橋性シリル基含有有機重合体（Ａ）および上記接着付与剤（Ｂ）とともに後述する未発泡の熱発泡性マイクロカプセル（Ｃ）を含有する本発明の接着剤組成物を被着体上に塗布し、加熱することにより、接着剤組成物そのものが被着体に接着した断熱材となるためである。
In the present invention, by containing such an adhesion-imparting agent (B), the heat-insulating material formed on the adherend by using the obtained adhesive composition of the present invention and the adherend are bonded. The property is good.
Moreover, it is necessary to use the adhesive used in the current construction method, that is, the construction method in which the adhesive is applied onto the adherend and the heat insulating material is pressure-bonded by containing such an adhesion-imparting agent (B). Therefore, it is possible to simplify the construction process and shorten the construction time. This is applied to the adhesive composition of the present invention containing unfoamed thermally foamable microcapsules (C) to be described later together with the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). This is because the adhesive composition itself becomes a heat insulating material adhered to the adherend by applying and heating on the body.
また、本発明においては、接着付与剤（Ｂ）としてシランカップリング剤を使用する場合、その含有量は、基材成分に含有する上記架橋性シリル基含有有機重合体（Ａ）１００質量部に対して、０．１〜５０質量部であるのが好ましく、０．５〜５質量部であるのがより好ましい。シランカップリン剤の含有量がこの範囲であると、得られる本発明の接着剤組成物を用いて被着体上に形成される断熱材と該被着体との接着性がより良好なものとなる。 Moreover, in this invention, when using a silane coupling agent as an adhesion | attachment imparting agent (B), the content is 100 mass parts of said crosslinkable silyl group containing organic polymers (A) contained in a base material component. On the other hand, it is preferable that it is 0.1-50 mass parts, and it is more preferable that it is 0.5-5 mass parts. When the content of the silane coupling agent is in this range, the adhesive between the heat insulating material formed on the adherend using the adhesive composition of the present invention obtained and the adherend is better. It becomes.
＜熱発泡性マイクロカプセル（Ｃ）＞
上記熱発泡性マイクロカプセル（Ｃ）は、加熱により発泡するマイクロカプセルであり、本発明においては、基材成分および硬化剤成分のいずれか一方または両方に、未発泡の状態で含有するものである。
<Heat-foaming microcapsule (C)>
The thermally foamable microcapsule (C) is a microcapsule that foams by heating, and in the present invention, it is contained in one or both of the base material component and the curing agent component in an unfoamed state. .
上記熱発泡性マイクロカプセル（Ｃ）は、従来公知のものを用いることができ、その具体例としては、低沸点溶剤とそれを内包する熱可塑性ポリマー壁材とからなる熱発泡性マイクロカプセルが好適に挙げられる。 A conventionally well-known thing can be used for the said thermally foamable microcapsule (C), As the specific example, the thermally foamable microcapsule which consists of a low-boiling-point solvent and the thermoplastic polymer wall material which includes it is suitable. It is mentioned in.
ここで、熱可塑性ポリマー壁材に用いられる熱可塑性ポリマーとしては、例えば、アクリロニトリル、アクリルアミド、アクリル酸、アクリル酸エステル、メタクリロニトリル、メタクリルアミド、メタクリル酸、メタクリル酸エステル、塩化ビニル、塩化ビニリデン、酢酸ビニル等の単独重合体または共重合体が挙げられる。また、これらに、架橋剤、例えば、ジビニルベンゼン、（ポリ）エチレングリコール（ジ）メタアクリレート、トリアリルイソシアヌレート（ＴＡＩＣ）、トリメチロールプロパントリメタクリレート（ＴＭＰ）、トリアクリルホルマール（ＴＡＦ）を少量加えて用いることもできる。更に、これらは樹脂の種類、用途等に基づいて適宜選択することができる。
これらのうち、より低温で発泡する観点から、塩化ビニリデンの重合体であるのが好ましい。
Here, as the thermoplastic polymer used for the thermoplastic polymer wall material, for example, acrylonitrile, acrylamide, acrylic acid, acrylic ester, methacrylonitrile, methacrylamide, methacrylic acid, methacrylic ester, vinyl chloride, vinylidene chloride, A homopolymer or copolymer such as vinyl acetate can be used. Also, a small amount of a crosslinking agent such as divinylbenzene, (poly) ethylene glycol (di) methacrylate, triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMP), triacryl formal (TAF) is added to these. Can also be used. Furthermore, these can be selected as appropriate based on the type and use of the resin.
Among these, from the viewpoint of foaming at a lower temperature, a vinylidene chloride polymer is preferable.
次に、内包される低沸点溶剤としては、沸点が−２０〜２００℃の炭化水素型の溶剤が好適に用いられる。このような溶剤としては、具体的には、例えば、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ネオペンタン、ｎ−ヘキサン、イソヘキサン、ｎ−ヘプタン、石油エーテル等の石油分留成分が挙げられる。 Next, as the low boiling point solvent to be included, a hydrocarbon type solvent having a boiling point of -20 to 200 ° C. is preferably used. Specific examples of such a solvent include petroleum fractionation components such as n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, and petroleum ether.
また、上記熱発泡性マイクロカプセル（Ｃ）は、粒径が、通常、２〜１００μｍ程度であるのが好ましく、５〜５０μｍ程度であるのがより好ましい。 Moreover, it is preferable that the said heat-foamable microcapsule (C) is about 2-100 micrometers normally, and, as for a particle size, it is more preferable that it is about 5-50 micrometers.
更に、上記熱発泡性マイクロカプセル（Ｃ）は、従来公知の方法により製造することができる。具体的には、例えば、特公昭４２−２６５２４号公報に記載されている方法を用いることができる。 Further, the thermally foamable microcapsule (C) can be produced by a conventionally known method. Specifically, for example, a method described in Japanese Patent Publication No. 42-26524 can be used.
本発明においては、このような熱発泡性マイクロカプセル（Ｃ）を含有することにより、得られる本発明の接着剤組成物を用いて得られる複合材料の断熱性が良好となり、その容積も減少することができる。これは、本発明の接着剤組成物が未発泡の状態で熱発泡性マイクロカプセル（Ｃ）を含有するため、本発明の接着剤組成物を用いて基板上に形成される断熱材が独立発泡体になりやすく、即ち、断熱材内部に存する発泡部分が非連続となりやすく、熱伝導率が低くなるためであると考えられる。
また、このような熱発泡性マイクロカプセル（Ｃ）を含有することにより、得られる本発明の接着剤組成物を用いて被着体上に断熱材を形成する際に特別な型も必要としないため、複雑な形状の被着体に対しても断熱材を形成することができる。
In the present invention, by containing such a heat-foamable microcapsule (C), the heat insulating property of the composite material obtained using the obtained adhesive composition of the present invention is improved, and the volume thereof is also reduced. be able to. This is because the heat-insulating material formed on the substrate using the adhesive composition of the present invention is independently foamed because the adhesive composition of the present invention contains the thermally foamable microcapsules (C) in an unfoamed state. This is considered to be because the foamed portion existing inside the heat insulating material tends to be discontinuous and the thermal conductivity is lowered.
Further, by containing such a heat-foamable microcapsule (C), no special mold is required when forming a heat insulating material on an adherend using the adhesive composition of the present invention obtained. Therefore, a heat insulating material can be formed even on an adherend having a complicated shape.
また、本発明においては、上記熱発泡性マイクロカプセル（Ｃ）の含有量が、架橋性シリル基含有有機重合体（Ａ）および接着付与剤（Ｂ）の合計１００質量部に対し、０．１〜１０質量部であるのが好ましく、１〜５質量部であるのがより好ましい。上記熱発泡性マイクロカプセル（Ｃ）の含有量がこの範囲であると、本発明の接着剤組成物の被着体との接着性がより良好となる。 Moreover, in this invention, content of the said heat-foamable microcapsule (C) is 0.1 with respect to a total of 100 mass parts of a crosslinkable silyl group containing organic polymer (A) and an adhesion | attachment imparting agent (B). It is preferable that it is -10 mass parts, and it is more preferable that it is 1-5 mass parts. Adhesiveness with the to-be-adhered body of the adhesive composition of this invention becomes it that content of the said heat-foamable microcapsule (C) is this range.
本発明の接着剤組成物は、加熱前の体積と加熱により発泡させた後の体積との比（加熱後／加熱前）が、１超１００以下であるのが好ましく、１〜５０であるのがより好ましく、１〜１０であるのが更に好ましい。体積比がこの範囲であると、本発明の接着剤組成物の被着体との接着性がより良好となる。 In the adhesive composition of the present invention, the ratio of the volume before heating to the volume after foaming by heating (after heating / before heating) is preferably more than 1 and 100 or less, and preferably 1 to 50. Is more preferable, and it is still more preferable that it is 1-10. When the volume ratio is within this range, the adhesiveness of the adhesive composition of the present invention to the adherend becomes better.
本発明の接着剤組成物は、更に、スズ触媒、亜鉛触媒、チタン触媒等の金属触媒を含有するのが好ましい。
スズ触媒としては、具体的には、例えば、ジブチルスズジラウレート、ジブチルスズマレエート、ジブチルスズジアセテート、オクチル酸スズ、ナフテン酸スズ等のスズカルボン酸塩類；ジブチルスズオキサイドとフタル酸エステルとの反応物；ジブチルスズジアセチルアセトナートが挙げられる。
亜鉛触媒としては、具体的には、例えば、オクチル酸亜鉛等が挙げられる。
チタン触媒としては、具体的には、例えば、テトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル類が挙げられる。
本発明においては、これらの触媒を１種単独で用いてもよく、２種以上を併用してもよい。
The adhesive composition of the present invention preferably further contains a metal catalyst such as a tin catalyst, a zinc catalyst, or a titanium catalyst.
Specific examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; a reaction product of dibutyltin oxide and phthalate; dibutyltin diacetylacetate Naruto.
Specific examples of the zinc catalyst include zinc octylate.
Specific examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
In the present invention, these catalysts may be used alone or in combination of two or more.
本発明の接着剤組成物は、被着体上に形成される断熱材の硬度を調整する観点から、更に、エポキシ樹脂を含有することができる。
このようなエポキシ樹脂としては、従来公知のエポキシ樹脂を用いることができる。
具体的には、例えば、ビスフェノールＡ型、ビスフェノールＦ型、臭素化ビスフェノールＡ型、水添ビスフェノールＡ型、ビスフェノールＳ型、ビスフェノールＡＦ型、ビフェニル型等のビスフェニル基を有するエポキシ化合物や、ポリアルキレングリコール型、アルキレングリコール型のエポキシ化合物や、ナフタレン環を有するエポキシ化合物や、フルオレン基を有するエポキシ化合物等の二官能型のグリシジルエーテル系エポキシ樹脂；
フェノールノボラック型、オルソクレゾールノボラック型、トリスヒドロキシフェニルメタン型、テトラフェニロールエタン型等の多官能型のグリシジルエーテル系エポキシ樹脂；
ダイマー酸等の合成脂肪酸のグリシジルエステル系エポキシ樹脂；
下記式（４）で表されるＮ，Ｎ，Ｎ′，Ｎ′−テトラグリシジルジアミノジフェニルメタン（ＴＧＤＤＭ）、テトラグリシジルジアミノジフェニルスルホン（ＴＧＤＤＳ）、テトラグリシジル−ｍ−キシリレンジアミン（ＴＧＭＸＤＡ）、下記式（５）で表されるトリグリシジル−ｐ−アミノフェノール、トリグリシジル−ｍ−アミノフェノール、Ｎ，Ｎ−ジグリシジルアニリン、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（ＴＧ１，３−ＢＡＣ）、トリグリシジルイソシアヌレート（ＴＧＩＣ）等のグリシジルアミン系エポキシ樹脂；
The adhesive composition of the present invention can further contain an epoxy resin from the viewpoint of adjusting the hardness of the heat insulating material formed on the adherend.
A conventionally well-known epoxy resin can be used as such an epoxy resin.
Specifically, for example, epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, and polyalkylene Bifunctional glycidyl ether type epoxy resins such as glycol type, alkylene glycol type epoxy compounds, epoxy compounds having a naphthalene ring, and epoxy compounds having a fluorene group;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type;
Glycidyl ester epoxy resins of synthetic fatty acids such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyldiaminodiphenylsulfone (TGDDS), tetraglycidyl-m-xylylenediamine (TGMXDA) represented by the following formula (4), (5) represented by triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, N, N-diglycidylaniline, tetraglycidyl 1,3-bisaminomethylcyclohexane (TG1,3-BAC), tri Glycidylamine epoxy resin such as glycidyl isocyanurate (TGIC);
下記式（６）で表されるトリシクロ〔５，２，１，０2,6〕デカン環を有するエポキシ化合物、具体的には、例えば、ジシクロペンタジエンとメタクレゾール等のクレゾール類またはフェノール類を重合させた後、エピクロルヒドリンを反応させる公知の製造方法によって得ることができるエポキシ化合物； Following epoxy compound having a tricyclo [5,2,1,0 2,6] decane ring represented by (6), specifically, for example, cresol or phenols, such as dicyclopentadiene and cresol An epoxy compound which can be obtained by a known production method of reacting epichlorohydrin after polymerization;
（式中、ｍは、０〜１５の整数を示す。）
(In the formula, m represents an integer of 0 to 15.)
脂環型エポキシ樹脂；東レチオコール社製のフレップ１０に代表されるエポキシ樹脂主鎖に硫黄原子を有するエポキシ樹脂；ウレタン結合を有するウレタン変性エポキシ樹脂；ポリブタジエン、液状ポリアクリロニトリル−ブタジエンゴムまたはアクリロニトリルブタジエンゴム（ＮＢＲ）を含有するゴム変性エポキシ樹脂等が挙げられる。
これらは１種単独で用いても、２種以上を併用してもよい。
Cycloaliphatic epoxy resin; epoxy resin represented by Toraythiol Co., Ltd. Frep 10 epoxy resin main chain having sulfur atom; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR).
These may be used alone or in combination of two or more.
これらのエポキシ樹脂のうち、ビスフェノールＡ型であるのが、得られる本発明の接着剤組成物の被着体に対する接着性がより向上する理由から好ましい。 Among these epoxy resins, the bisphenol A type is preferable because the adhesiveness of the obtained adhesive composition of the present invention to the adherend is further improved.
本発明の接着剤組成物は、本発明の目的を損なわない範囲で、上記各種成分以外に、必要に応じて、各種の添加剤を含有することができる。添加剤としては、例えば、充填剤、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、分散剤、揺変性付与剤が挙げられる。 The adhesive composition of the present invention can contain various additives as required in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of the additive include a filler, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, a dispersant, and a thixotropic agent.
充填剤としては、例えば、ろう石クレー、カオリンクレー、焼成クレー；ヒュームドシリカ、焼成シリカ、沈降シリカ、粉砕シリカ、溶融シリカ；けいそう土；酸化鉄、酸化亜鉛、酸化チタン、酸化バリウム、酸化マグネシウム；炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛；カーボンブラック等の有機または無機充填剤；これらの脂肪酸、樹脂酸、脂肪酸エステル処理物、脂肪酸エステルウレタン化合物処理物が挙げられる。 Examples of the filler include wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, oxidized Magnesium; calcium carbonate, magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.
老化防止剤としては、例えば、ヒンダードフェノール系化合物、ヒンダードアミン系化合物が挙げられる。
酸化防止剤としては、例えば、ブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）が挙げられる。
帯電防止剤としては、例えば、第四級アンモニウム塩；ポリグリコール、エチレンオキサイド誘導体等の親水性化合物が挙げられる。
Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.
難燃剤としては、例えば、クロロアルキルホスフェート、ジメチル・メチルホスホネート、臭素・リン化合物、アンモニウムポリホスフェート、ネオペンチルブロマイド−ポリエーテル、臭素化ポリエーテルが挙げられる。
揺変性付与剤としては、例えば、水添ヒマシ油、シリカ、タルク等が挙げられる。
上記の各添加剤は適宜、組み合わせて用いることができる。
Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the thixotropic agent include hydrogenated castor oil, silica, and talc.
The above additives can be used in combination as appropriate.
本発明においては、上記架橋性シリル基含有有機重合体（Ａ）を含有する基材成分は、上記架橋性シリル基含有有機重合体（Ａ）および上記熱発泡性マイクロカプセル（Ｃ）のみを含有する成分であってもよく、上記熱発泡性マイクロカプセル（Ｃ）を含有しない場合は、上記架橋性シリル基含有有機重合体（Ａ）のみを含有する成分であってもよいが、必要に応じて、上述した各種の添加剤（金属触媒、エポキシ樹脂を含む。以下同様。）を含有していてもよい。
同様に、上記接着付与剤（Ｂ）を含有する硬化剤成分は、上記接着付与剤（Ｂ）および上記熱発泡性マイクロカプセル（Ｃ）のみを含有する成分であってもよく、上記熱発泡性マイクロカプセル（Ｃ）を含有しない場合は、上記接着付与剤（Ｂ）のみを含有する成分であってもよいが、必要に応じて、上述した各種の添加剤を含有していてもよい。
In the present invention, the substrate component containing the crosslinkable silyl group-containing organic polymer (A) contains only the crosslinkable silyl group-containing organic polymer (A) and the thermally foamable microcapsule (C). In the case where the thermally foamable microcapsule (C) is not contained, it may be a component containing only the crosslinkable silyl group-containing organic polymer (A). In addition, various additives described above (including metal catalysts and epoxy resins; the same shall apply hereinafter) may be included.
Similarly, the curing agent component containing the adhesion-imparting agent (B) may be a component containing only the adhesion-imparting agent (B) and the heat-foamable microcapsule (C). When it does not contain microcapsules (C), it may be a component containing only the above-mentioned adhesion-imparting agent (B), but it may contain the various additives described above as necessary.
本発明の樹脂組成物の製造方法は、特に限定されず、例えば、上記架橋性シリル基含有有機重合体（Ａ）を含有する基材成分と、上記接着付与剤（Ｂ）および上記未発泡の熱発泡性マイクロカプセル（Ｃ）ならびに上記各種添加剤を含有する硬化剤成分とを混合し、ロール、ニーダー、押出し機、万能撹拌機等を用いて室温下で十分に混合し、均一に分散（混練）させることにより製造することができる。 The method for producing the resin composition of the present invention is not particularly limited. For example, the base component containing the crosslinkable silyl group-containing organic polymer (A), the adhesion-imparting agent (B), and the unfoamed material are used. Mix the heat-foamable microcapsule (C) and the curing agent component containing the above-mentioned various additives, mix thoroughly at room temperature using a roll, kneader, extruder, universal stirrer, etc., and disperse uniformly ( Kneading).
本発明の接着剤組成物の施工方法は、上述した本発明の接着剤組成物の施工方法であって、
上記接着剤組成物を被着体に塗布する塗布工程と、
上記塗布工程により塗布された上記接着剤組成物を加熱する加熱工程とを具備する施工方法である。
以下に、塗布工程、加熱工程について詳述する。
The construction method of the adhesive composition of the present invention is the construction method of the adhesive composition of the present invention described above,
An application step of applying the adhesive composition to an adherend;
And a heating process for heating the adhesive composition applied by the application process.
Below, a coating process and a heating process are explained in full detail.
＜塗布工程＞
上記塗布工程は、本発明の接着剤組成物を断熱材を形成する被着体表面に塗布する工程である。
ここで、被着体は、断熱材が要求される用途、個所により変わるため特に限定されないが、アクリル樹脂、ポリエステル樹脂、フロートガラス、陽極酸化アルミニウム等が挙げられる。
また、本発明の接着剤組成物の被着体への塗布方法としては、具体的には、例えば、スプレー塗布、ディップ塗布、バーコーター塗布、回転塗布等が挙げられる。
<Application process>
The said application | coating process is a process of apply | coating the adhesive composition of this invention to the to-be-adhered body surface which forms a heat insulating material.
Here, the adherend is not particularly limited because it varies depending on the application and location where a heat insulating material is required, and examples thereof include acrylic resin, polyester resin, float glass, and anodized aluminum.
Specific examples of the method for applying the adhesive composition of the present invention to an adherend include spray coating, dip coating, bar coater coating, and spin coating.
＜加熱工程＞
上記加熱工程は、上記塗布工程により塗布された本発明の接着剤組成物を加熱する工程であり、上記未発泡の熱発泡性マイクロカプセル（Ｃ）が発泡するとともに、上記架橋性シリル基含有有機重合体（Ａ）が硬化する工程である。
<Heating process>
The heating step is a step of heating the adhesive composition of the present invention applied in the application step, wherein the unfoamed thermally foamable microcapsule (C) is foamed and the crosslinkable silyl group-containing organic material is used. This is a step of curing the polymer (A).
本発明においては、上記未発泡の熱発泡性マイクロカプセル（Ｃ）が十分に発泡するまでの間、架橋性シリル基含有有機重合体（例えば、変成シリコーン）が硬化してしまうことのないよう、６０〜１５０℃で数十分程度加熱するのが好ましく、９０〜１４０℃で数十分程度で加熱するのがより好ましい。
加熱の方法としては、例えば、電磁波を用いる電磁波加熱（例えば、放射板に熱放射する方法等）、ヒーター（例えば、電気ヒーター等）を用いる方法、温風を送風する方法が挙げられる。中でも、電磁波加熱であるのが好ましい。
In the present invention, until the unfoamed thermally foamable microcapsule (C) is sufficiently foamed, the crosslinkable silyl group-containing organic polymer (for example, modified silicone) is not cured. It is preferable to heat at about 60 to 150 ° C. for several tens of minutes, and more preferably at about 90 to 140 ° C. for about several tens of minutes.
Examples of the heating method include electromagnetic wave heating using an electromagnetic wave (for example, a method for radiating heat to a radiation plate), a method using a heater (for example, an electric heater), and a method for blowing warm air. Among these, electromagnetic heating is preferable.
本発明の接着剤組成物の施工方法により、被着体上に該被着体に接着した断熱材が形成された複合材料が得られる。 By the method for applying the adhesive composition of the present invention, a composite material in which a heat insulating material bonded to the adherend is formed on the adherend is obtained.
このように本発明の接着剤組成物の施工方法によれば、現行の施工方法、即ち、被着体上に接着剤を塗布し、断熱材を圧着させる施工方法において使用する接着剤を用いる必要がなく、施工工程の簡略化および施工時間の短縮化も図ることできる。これは、上述したように、上記架橋性シリル基含有有機重合体（Ａ）および上記接着付与剤（Ｂ）とともに上記熱発泡性マイクロカプセル（Ｃ）を含有する本発明の接着剤組成物を被着体上に塗布し、加熱することにより、接着剤組成物そのものが被着体に接着した断熱材となるためである。 Thus, according to the construction method of the adhesive composition of the present invention, it is necessary to use the adhesive used in the current construction method, that is, the construction method in which the adhesive is applied onto the adherend and the heat insulating material is pressure-bonded. Therefore, it is possible to simplify the construction process and shorten the construction time. As described above, the adhesive composition of the present invention containing the thermally foamable microcapsule (C) together with the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B) is coated. This is because the adhesive composition itself becomes a heat insulating material adhered to the adherend by applying and heating on the adherend.
以下、実施例を用いて、本発明について詳細に説明する。ただし、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.
（実施例１〜３、比較例１〜６）
下記表１に示す各組成成分を、下記表１に示す質量部となるように混合し、接着剤組成物を調製した。
次いで、調製した各接着剤組成物を、被着体であるフロートガラス（５０ｍｍ×５０ｍｍ×５ｍｍ厚）上に塗布した後、１４０℃で１０分間の条件で加熱乾燥させ、被着体上に断熱材が形成された複合材料を作製した。
また、同様の条件で、調製した各接着剤組成物を、陽極酸化アルミニウム板（５０ｍｍ×５０ｍｍ×３ｍｍ厚）、アクリル樹脂板（５０ｍｍ×５０ｍｍ×３ｍｍ厚）およびポリエステル板（５０ｍｍ×５０ｍｍ×３ｍｍ厚）上に塗布し、乾燥させ、被着体上に断熱材が形成された複合材料を作製した。
(Examples 1-3, Comparative Examples 1-6)
Each composition component shown in the following Table 1 was mixed so that it might become a mass part shown in the following Table 1, and the adhesive composition was prepared.
Next, each prepared adhesive composition was coated on float glass (50 mm × 50 mm × 5 mm thickness) as an adherend, and then heated and dried at 140 ° C. for 10 minutes to insulate the adherend. A composite material on which the material was formed was produced.
Also, under the same conditions, each prepared adhesive composition was subjected to an anodized aluminum plate (50 mm × 50 mm × 3 mm thickness), an acrylic resin plate (50 mm × 50 mm × 3 mm thickness), and a polyester plate (50 mm × 50 mm × 3 mm thickness). And a composite material having a heat insulating material formed on the adherend was produced.
得られた各複合材料について、以下の方法により接着性を測定した。その結果を表１に示す。 About each obtained composite material, adhesiveness was measured with the following method. The results are shown in Table 1.
＜接着性＞
各被着体に対する断熱材の接着性の評価は、作製した各複合材料を２３℃、５５％ＲＨの条件下で３日間放置して養生した後、ナイフカットによる手はく離試験を行い、破壊の状態を目視で観察した。
なお、表１中、ＴＣＦは接着剤組成物である断熱材が薄層凝集破壊したこと示し、ＡＦは接着剤組成物である断熱材が接着破壊（界面破壊）したことを示す。
<Adhesiveness>
The evaluation of the adhesion of the heat insulating material to each adherend is carried out by leaving each prepared composite material to stand for 3 days under conditions of 23 ° C. and 55% RH, and then performing a hand peeling test with a knife cut. The state was observed visually.
In Table 1, TCF indicates that the heat insulating material as the adhesive composition has undergone thin-layer cohesive failure, and AF indicates that the heat insulating material as the adhesive composition has undergone adhesive failure (interface failure).
上記と同様の方法で調製した各接着剤組成物を、離型処理した金属性の型（１５０ｍｍ×１００ｍｍ×１５ｍｍ厚）に入れ、１２０℃で１０分間の条件で加熱乾燥した後に型から取り出し、断熱材のみからなる試験片を作製した。
得られた各試験片について、以下の方法により熱伝導率および体積比を測定した。その結果を表１に示す。
Each adhesive composition prepared by the same method as described above is put into a metallic mold (150 mm × 100 mm × 15 mm thickness) that has been subjected to a release treatment, and is heated and dried at 120 ° C. for 10 minutes, and then removed from the mold. A test piece consisting only of a heat insulating material was produced.
About each obtained test piece, the heat conductivity and volume ratio were measured with the following method. The results are shown in Table 1.
＜熱伝導率＞
得られた各試験片の表面の熱伝導率を熱伝導率計（京都電子社製）を用いて測定した。
<Thermal conductivity>
The thermal conductivity of the surface of each obtained test piece was measured using a thermal conductivity meter (manufactured by Kyoto Electronics Co., Ltd.).
＜体積比＞
試験片を作製する際に型に入れた各接着剤組成物の体積（１５０ｍｍ×１００ｍｍ×１５ｍｍ＝２２５ｃｍ3）と、試験片（断熱材）の体積との比（試験片／接着剤組成物）を算出した。その結果を表１に示す。
<Volume ratio>
Ratio of the volume of each adhesive composition (150 mm × 100 mm × 15 mm = 225 cm 3 ) placed in the mold when preparing the test piece to the volume of the test piece (heat insulating material) (test piece / adhesive composition) Was calculated. The results are shown in Table 1.
表１中の各組成成分は、以下に示す通りである。
・架橋性シリル基含有有機重合体Ａ１：変成シリコーン（ＭＳＰ Ｓ２０３、鐘淵化学工業社製）
・架橋性シリル基含有有機重合体Ａ２：変成シリコーン（ＭＳＰ Ｓ３０３、鐘淵化学工業社製）
・接着付与剤Ｂ１：Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン（Ｙ９６６９、日本ユニカー社製）
・未発泡マイクロカプセルＣ１：未発泡の熱発泡性マイクロカプセル（マツモトマイクロスフェアーＦ−２、松本油脂社製、平均粒径：１０〜２０μｍ、壁材：ビニルクロライド系コポリマー、固形分：７０質量％以上）
・スズ触媒：ジブチルスズジラウレート（日本化学産業社製）
・亜鉛触媒：オクチル酸亜鉛（日本化学産業社製）
Each composition component in Table 1 is as shown below.
Crosslinkable silyl group-containing organic polymer A1: Modified silicone (MSP S203, manufactured by Kaneka Chemical Co., Ltd.)
Crosslinkable silyl group-containing organic polymer A2: Modified silicone (MSP S303, Kaneka Chemical Co., Ltd.)
Adhesion imparting agent B1: N-phenyl-γ-aminopropyltrimethoxysilane (Y9669, manufactured by Nihon Unicar)
Unfoamed microcapsule C1: Unfoamed thermally foamable microcapsule (Matsumoto Microsphere F-2, manufactured by Matsumoto Yushi Co., Ltd., average particle size: 10 to 20 μm, wall material: vinyl chloride copolymer, solid content: 70 mass %that's all)
-Tin catalyst: Dibutyltin dilaurate (Nippon Chemical Industry Co., Ltd.)
・ Zinc catalyst: Zinc octylate (Nippon Chemical Industry Co., Ltd.)
表１に示す結果から、実施例１〜３で調製した接着剤組成物から作製した複合材料は、接着付与剤（Ｂ）ないし未発泡の熱発泡性マイクロカプセル（Ｃ）を含有しない比較例１〜６で調製した接着剤組成物から作製した複合材料に比べて接着性が良好であることが分かった。
また、実施例１〜３で調製した接着剤組成物から作製した断熱材のみからなる試験片は、比較例１〜６で調製した接着剤組成物から作製した試験片と同等以上に低い熱伝導率を示すことから断熱性に優れることが分かった。
更に、実施例１〜３で調製した接着剤組成物から作製した断熱材は、１超１００以下であることが分かった。
From the results shown in Table 1, the composite material produced from the adhesive compositions prepared in Examples 1 to 3 does not contain an adhesion-imparting agent (B) or an unfoamed thermally foamable microcapsule (C). It was found that the adhesiveness was better than the composite material prepared from the adhesive composition prepared in -6.
Moreover, the test piece which consists only of the heat insulating material produced from the adhesive composition prepared in Examples 1-3 is a heat conductivity as low as the test piece produced from the adhesive composition prepared in Comparative Examples 1-6. Since the rate was shown, it was found that heat insulation was excellent.
Furthermore, the heat insulating material produced from the adhesive composition prepared in Examples 1 to 3 was found to be more than 1 and 100 or less.
Claims (4)
接着付与剤（Ｂ）を含有する硬化剤成分とからなり、
前記基材成分および／または前記硬化剤成分に、未発泡の熱発泡性マイクロカプセル（Ｃ）を含有し、
前記熱発泡性マイクロカプセル（Ｃ）の含有量が、前記架橋性シリル基含有有機重合体（Ａ）および前記接着付与剤（Ｂ）の合計１００質量部に対し、０．１〜１０質量部であり、
前記接着付与剤（Ｂ）が、シランカップリング剤であり、
前記シランカップリング剤の含有量が、前記架橋性シリル基含有有機重合体（Ａ）１００質量部に対して、０．１〜５０質量部である、接着剤組成物。 A base material component containing a crosslinkable silyl group-containing organic polymer (A);
It comprises a curing agent component containing an adhesion promoter (B),
The base component and / or the curing agent component contains unfoamed thermally foamable microcapsules (C),
The content of the thermally foamable microcapsule (C) is 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the crosslinkable silyl group-containing organic polymer (A) and the adhesion-imparting agent (B). Oh it is,
The adhesion-imparting agent (B) is a silane coupling agent,
The adhesive composition whose content of the said silane coupling agent is 0.1-50 mass parts with respect to 100 mass parts of said crosslinkable silyl group containing organic polymers (A) .
前記接着剤組成物を被着体に塗布する塗布工程と、
前記塗布工程により塗布された前記接着剤組成物を加熱する加熱工程とを具備する施工方法。 It is the construction method of the adhesive composition according to claim 1 or 2 ,
An application step of applying the adhesive composition to an adherend;
And a heating step of heating the adhesive composition applied in the application step.
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| JP2006322227A JP5394607B2 (en) | 2006-11-29 | 2006-11-29 | Adhesive composition |
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| JP2006322227A JP5394607B2 (en) | 2006-11-29 | 2006-11-29 | Adhesive composition |
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| JP2008133404A JP2008133404A (en) | 2008-06-12 |
| JP5394607B2 true JP5394607B2 (en) | 2014-01-22 |
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| JP2011032987A (en) * | 2009-08-05 | 2011-02-17 | Nitto Denko Corp | Reinforcing sheet for wind turbine generator blade, reinforcing structure of wind turbine generator blade, wind turbine generator, and method of reinforcing wind turbine generator blade |
| WO2017223173A1 (en) | 2016-06-21 | 2017-12-28 | Bridgestone Americas Tire Operations, Llc | Methods for treating inner liner surface, inner liners resulting therefrom and tires containing such inner liners |
| BR112018077027B1 (en) | 2016-06-30 | 2023-03-14 | Bridgestone Americas Tire Operations, Llc | METHOD FOR TREATMENT OF A CURED INNER LINER FOR A TIRE; METHOD FOR PRODUCING A TIRE AND CURED TIRE |
| JP6848062B2 (en) | 2016-12-15 | 2021-03-24 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | A method of forming a polymer-containing coating on a cured inner liner, a method of manufacturing a tire containing such an inner liner, and a tire containing such an inner liner. |
| CN110214076A (en) | 2016-12-15 | 2019-09-06 | 普利司通美国轮胎运营有限责任公司 | Tire and correlation technique containing sealant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6144965A (en) * | 1984-08-10 | 1986-03-04 | Matsushita Refrig Co | Expandable adhesive |
| JPH07251477A (en) * | 1994-03-16 | 1995-10-03 | Nippon Zeon Co Ltd | Foamed metal structure and its manufacture |
| EP0870790A1 (en) * | 1995-08-04 | 1998-10-14 | Asahi Denka Kogyo Kabushiki Kaisha | Curable epoxy resin composition |
| US20040210019A1 (en) * | 2001-06-21 | 2004-10-21 | Nobuhiro Hasegawa | Quick curing compositions |
| JP4101632B2 (en) * | 2002-11-01 | 2008-06-18 | 株式会社カネカ | CURABLE COMPOSITION AND METHOD OF IMPROVING RESTORE AND CREEP |
| US20060079645A1 (en) * | 2003-02-24 | 2006-04-13 | Nobuhiro Hasegawa | Curable compositions |
| EP1666536B1 (en) * | 2003-09-02 | 2014-03-12 | Kaneka Corporation | Curable composition |
| WO2005071015A1 (en) * | 2004-01-26 | 2005-08-04 | Kaneka Corporation | Curing composition |
| CN100595230C (en) * | 2004-02-03 | 2010-03-24 | 株式会社钟化 | Curable composition |
| CA2561385A1 (en) * | 2004-03-30 | 2005-10-13 | Kaneka Corporation | Hardenable composition |
| JP5185530B2 (en) * | 2004-05-13 | 2013-04-17 | 株式会社カネカ | Sealing material |
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