JP2005281636A - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- JP2005281636A JP2005281636A JP2004101904A JP2004101904A JP2005281636A JP 2005281636 A JP2005281636 A JP 2005281636A JP 2004101904 A JP2004101904 A JP 2004101904A JP 2004101904 A JP2004101904 A JP 2004101904A JP 2005281636 A JP2005281636 A JP 2005281636A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- curable composition
- fine particles
- silane
- mass parts
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 147
- 239000010419 fine particle Substances 0.000 claims abstract description 51
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000005060 rubber Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 57
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 239000012974 tin catalyst Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229920003049 isoprene rubber Polymers 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 5
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004658 ketimines Chemical class 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- -1 aminosilyl group Chemical group 0.000 description 30
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229920003244 diene elastomer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000010734 process oil Substances 0.000 description 4
- 229920005989 resin Chemical class 0.000 description 4
- 239000011347 resin Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- SOXALKOOANKAEB-UHFFFAOYSA-N 2-(2-phenyl-1,3-oxazolidin-3-yl)ethanol Chemical compound OCCN1CCOC1C1=CC=CC=C1 SOXALKOOANKAEB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 229920005549 butyl rubber Polymers 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
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 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 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- CDGSOUOOAKXNKU-RPYYYHSRSA-N (z,12r)-2-acetyl-12-hydroxyoctadec-9-enoic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCC(C(C)=O)C(O)=O CDGSOUOOAKXNKU-RPYYYHSRSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QCPKTLDULZJCLB-UHFFFAOYSA-N 2-(1,3-oxazolidin-2-yl)ethanol Chemical compound OCCC1NCCO1 QCPKTLDULZJCLB-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-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
- 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
- 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
- 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
- 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
- QJIVRICYWXNTKE-UHFFFAOYSA-N 4-(8-methylnonoxy)-4-oxobutanoic acid Chemical compound CC(C)CCCCCCCOC(=O)CCC(O)=O QJIVRICYWXNTKE-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 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
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003054 adipate polyester Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 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
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 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
- 230000002463 transducing effect Effects 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 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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Abstract
Description
本発明は、加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体を用いた硬化性組成物に関する。 The present invention relates to a curable composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group.
加水分解性ケイ素含有基を有する重合体は、室温での優れた硬化性、配合設計の容易さ等から、シーリング材、接着剤等の用途の硬化性組成物に用いられている。特に、ポリオキシアルキレン系の主鎖を有する重合体（以下「ポリオキシアルキレン系重合体」ともいう。）は、硬化性、耐候性および安全性に優れ、配合処方により各種の被着体に対する接着性を優れたものにすることができ、比較的低粘度で扱いやすいため、シーリング材、シール剤、ポッティング剤、弾性接着剤、コーティング材、ライニング材、接着剤等の用途に好適に用いられる。このうち、シーリング材としては、室温湿気硬化型一成分形および室温湿気硬化型二成分形のいずれにも用いられる。
しかしながら、上述した加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体を用いた組成物は、良好な接着性を発現させるためには、以下のような問題を有している。即ち、一成分形シーリング材として用いる場合には、多量の接着付与成分を配合しなければならない。また、二成分形シーリング材として用いる場合には、プライマーを用いなければならず、プライマーを用いても十分に優れた接着性を得ることができるとは言えない。
Polymers having hydrolyzable silicon-containing groups are used in curable compositions for applications such as sealants and adhesives because of their excellent curability at room temperature and ease of compounding design. In particular, a polymer having a polyoxyalkylene main chain (hereinafter also referred to as “polyoxyalkylene polymer”) is excellent in curability, weather resistance and safety, and adheres to various adherends depending on the formulation. Therefore, it is suitable for applications such as sealing materials, sealing agents, potting agents, elastic adhesives, coating materials, lining materials, and adhesives. Among these, as a sealing material, it is used for both room temperature moisture hardening type one component form and room temperature moisture hardening type two component form.
However, the composition using the polyoxyalkylene-based polymer having a hydrolyzable silicon-containing group described above has the following problems in order to develop good adhesiveness. That is, when used as a one-component sealant, a large amount of an adhesion-imparting component must be blended. In addition, when used as a two-component sealant, a primer must be used, and it cannot be said that sufficiently excellent adhesiveness can be obtained even if a primer is used.
また、加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体を用いた組成物は、ポリウレタン系、ポリサルファイド系、シリコーン系等のシーリング材組成物と比べて、伸び等の硬化後の物性に著しく劣るという問題も有しており、特に、建築用シーリング材としては問題となっている。 In addition, a composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group is remarkably improved in properties after curing, such as elongation, as compared to a sealing material composition such as polyurethane, polysulfide, or silicone. It also has the problem of being inferior, and is particularly problematic as a sealing material for construction.
したがって、本発明は、接着性および硬化後の伸びに優れる、加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体を用いた硬化性組成物を提供することを課題とする。 Therefore, an object of the present invention is to provide a curable composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group, which is excellent in adhesion and elongation after curing.
本発明者は、上記目的を達成すべく鋭意検討した結果、加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体に、液状ゴムが３次元架橋してなるポリマー微粒子を分散させると、接着性および硬化後の伸びが向上することを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventor has found that when polymer fine particles formed by three-dimensionally cross-linking liquid rubber are dispersed in a polyoxyalkylene polymer having a hydrolyzable silicon-containing group, adhesiveness is obtained. And it discovered that the elongation after curing was improved, and completed the present invention.
即ち、本発明は、以下の（１）〜（１３）を提供する。 That is, the present invention provides the following (1) to (13).
（１）重合体と、前記重合体中に分散したポリマー微粒子とを含有し、
前記重合体が、主鎖がアルキレンオキシド単量体単位を含み、加水分解性ケイ素含有基を１分子あたり少なくとも１個有する重合体であり、
前記ポリマー微粒子が、液状ゴムが３次元架橋してなるポリマー微粒子である、硬化性組成物。
(1) containing a polymer and fine polymer particles dispersed in the polymer,
The polymer is a polymer whose main chain includes an alkylene oxide monomer unit and has at least one hydrolyzable silicon-containing group per molecule;
A curable composition, wherein the polymer particles are polymer particles obtained by three-dimensionally cross-linking liquid rubber.
（２）前記ポリマー微粒子が、３次元架橋可能な官能基を有する前記液状ゴムの前記官能基の反応により３次元架橋してなるポリマー微粒子である上記（１）に記載の硬化性組成物。 (2) The curable composition according to the above (1), wherein the polymer fine particles are polymer fine particles obtained by three-dimensional crosslinking by reaction of the functional group of the liquid rubber having a functional group capable of three-dimensional crosslinking.
（３）前記ポリマー微粒子が、前記液状ゴムが架橋剤および／または硬化剤により３次元架橋してなるポリマー微粒子である上記（１）または（２）に記載の硬化性組成物。 (3) The curable composition according to the above (1) or (2), wherein the polymer fine particles are polymer fine particles obtained by three-dimensionally crosslinking the liquid rubber with a crosslinking agent and / or a curing agent.
（４）前記液状ゴムが、イソプレンゴムである上記（１）〜（３）のいずれかに記載の硬化性組成物。 (4) The curable composition according to any one of (1) to (3), wherein the liquid rubber is isoprene rubber.
（５）前記ポリマー微粒子が、加水分解性ケイ素含有基を有する上記（１）〜（４）のいずれかに記載の硬化性組成物。 (5) The curable composition according to any one of (1) to (4), wherein the polymer fine particles have a hydrolyzable silicon-containing group.
（６）前記ポリマー微粒子が有する前記加水分解性ケイ素含有基の全部または一部が、シランカップリング剤との反応により、前記ポリマー微粒子に導入されたものである、上記（５）に記載の硬化性組成物。 (6) The curing according to (5) above, wherein all or part of the hydrolyzable silicon-containing group of the polymer fine particles is introduced into the polymer fine particles by reaction with a silane coupling agent. Sex composition.
（７）前記シランカップリング剤が、アミノシラン、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、これらとエポキシ樹脂またはポリイソシアネートとの反応により得られる化合物である上記（６）に記載の硬化性組成物。 (7) The silane coupling agent is an aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with an epoxy resin or polyisocyanate. The curable composition as described in said (6).
（８）前記シランカップリング剤の量が、前記重合体１００質量部に対し、０．１〜１０質量部である上記（６）または（７）に記載の硬化性組成物。 (8) The curable composition as described in said (6) or (7) whose quantity of the said silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers.
（９）更に、前記重合体１００質量部に対し、０．１〜１０質量部の相溶化剤を含有する上記（１）〜（８）のいずれかに記載の硬化性組成物。 (9) The curable composition according to any one of (1) to (8) above, further containing 0.1 to 10 parts by mass of a compatibilizer with respect to 100 parts by mass of the polymer.
（１０）更に、前記重合体１００質量部に対し、５０〜４００質量部の炭酸カルシウムを含有する上記（１）〜（９）のいずれかに記載の硬化性組成物。 (10) The curable composition according to any one of (1) to (9), further containing 50 to 400 parts by mass of calcium carbonate with respect to 100 parts by mass of the polymer.
（１１）更に、前記重合体１００質量部に対し、０．１〜１０質量部の分子量１０００以下の加水分解性化合物を含有する上記（１）〜（１０）のいずれかに記載の硬化性組成物。 (11) The curable composition according to any one of (1) to (10), further containing 0.1 to 10 parts by mass of a hydrolyzable compound having a molecular weight of 1000 or less with respect to 100 parts by mass of the polymer. Stuff.
（１２）更に、スズ触媒および／またはチタン触媒を含有する上記（１）〜（１１）のいずれかに記載の硬化性組成物。 (12) The curable composition according to any one of (1) to (11), further containing a tin catalyst and / or a titanium catalyst.
（１３）前記重合体１００質量部に対して、１〜１００質量部の前記ポリマー微粒子を含有する上記（１）〜（１２）のいずれかに記載の硬化性組成物。 (13) The curable composition according to any one of (1) to (12) above, containing 1 to 100 parts by mass of the polymer fine particles with respect to 100 parts by mass of the polymer.
本発明の硬化性組成物は、従来の加水分解性ケイ素含有基を有するポリオキシアルキレン系重合体を用いた硬化性組成物に比べ、接着性および硬化後の伸びに優れる。 The curable composition of the present invention is superior in adhesiveness and elongation after curing as compared with a curable composition using a conventional polyoxyalkylene polymer having a hydrolyzable silicon-containing group.
以下に、本発明を詳細に説明する。
本発明の硬化性組成物は、重合体と、前記重合体中に分散したポリマー微粒子とを含有し、前記重合体が、主鎖がアルキレンオキシド単量体単位を含み、加水分解性ケイ素含有基を１分子あたり少なくとも１個有する重合体であり、前記ポリマー微粒子が、液状ゴムが３次元架橋してなるポリマー微粒子である、硬化性組成物である。
The present invention is described in detail below.
The curable composition of the present invention contains a polymer and polymer fine particles dispersed in the polymer, and the polymer includes an alkylene oxide monomer unit in the main chain, and a hydrolyzable silicon-containing group. Is a polymer having at least one per molecule, and the polymer fine particles are polymer fine particles obtained by three-dimensionally cross-linking liquid rubber.
初めに、重合体について説明する。
本発明に用いられる重合体は、主鎖がアルキレンオキシド単量体単位を含み、加水分解性ケイ素含有基を１分子あたり少なくとも１個有する重合体である。本発明においては、加水分解性ケイ素含有基は、重合体の分子内の末端に存在していても、側鎖に存在していてもよく、また、両方に存在していてもよい。
First, the polymer will be described.
The polymer used in the present invention is a polymer having a main chain containing an alkylene oxide monomer unit and at least one hydrolyzable silicon-containing group per molecule. In the present invention, the hydrolyzable silicon-containing group may be present at the terminal in the molecule of the polymer, may be present in the side chain, or may be present in both.
重合体に含まれるアルキレンオキシド単量体単位としては、例えば、−ＣＨ2ＣＨ2Ｏ−、−ＣＨ2ＣＨ（ＣＨ3）Ｏ−、−ＣＨ2ＣＨ（Ｃ2Ｈ5）Ｏ−、−ＣＨ（ＣＨ3）ＣＨ2Ｏ−、−ＣＨ（Ｃ2Ｈ5）ＣＨ2Ｏ−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−または−ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ−で表される繰り返し単位が挙げられる。
重合体の主鎖は、これらの繰り返し単位の１種のみからなっていてもよく、２種以上からなっていてもよい。
重合体の主鎖は、単独で用いてもよく、２種以上を併用してもよい。
The alkylene oxide monomer units contained in the polymer, for example, -CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH The repeating unit represented by (CH 3 ) CH 2 O—, —CH (C 2 H 5 ) CH 2 O—, —CH 2 CH 2 CH 2 O— or —CH 2 CH 2 CH 2 CH 2 O— Can be mentioned.
The main chain of the polymer may consist of only one of these repeating units, or may consist of two or more.
The main chain of the polymer may be used alone or in combination of two or more.
加水分解性ケイ素含有基は、ケイ素原子に結合した水酸基および／または加水分解性基を有し、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してシロキサン結合を形成することにより架橋しうるケイ素含有基である。例えば、アルコキシシリル基、アルケニルオキシシリル基、アシロキシシリル基、アミノシリル基、アミノオキシシリル基、オキシムシリル基、アミドシリル基が挙げられる。具体的には、下記式で例示される、アルコキシシリル基、アルケニルオキシシリル基、アシロキシシリル基、アミノシリル基、アミノオキシシリル基、オキシムシリル基、アミドシリル基等が好適に用いられる。 The hydrolyzable silicon-containing group has a hydroxyl group and / or hydrolyzable group bonded to a silicon atom, and causes a condensation reaction by using a catalyst or the like in the presence of moisture or a cross-linking agent, if necessary. A silicon-containing group that can be cross-linked by forming a bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.
中でも、取扱いが容易である点で、アルコキシシリル基が好ましい。
アルコキシシリル基のケイ素原子に結合するアルコキシ基は、特に限定されないが、原料の入手が容易なことからメトキシ基、エトキシ基またはプロポキシ基が好適に挙げられる。
アルコキシシリル基のケイ素原子に結合するアルコキシ基以外の基は、特に限定されず、例えば、水素原子またはメチル基、エチル基、プロピル基、イソプロピル基等の炭素原子数が２０以下である、アルキル基、アルケニル基もしくはアリールアルキル基が好適に挙げられる。
Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.
重合体としては、２官能以上、即ち、分子内にアルコキシシリル基を２個以上有するアルコキシシラン類が好ましく、３〜２０官能のアルコキシシラン類が原料の入手が容易なことからより好ましい。 As the polymer, alkoxysilanes having two or more functional groups, that is, having two or more alkoxysilyl groups in the molecule are preferable, and 3-20 functional alkoxysilanes are more preferable because of easy availability of raw materials.
重合体の分子量は特に限定されないが、高分子のものは高粘度であり、ハンドリングしにくい場合があるため、数平均分子量５０，０００以下であるのが好ましい。 The molecular weight of the polymer is not particularly limited, but a polymer having a high viscosity is difficult to handle, and therefore, the number average molecular weight is preferably 50,000 or less.
重合体は、単独で用いてもよく、２種以上を併用してもよい。 A polymer may be used independently and may use 2 or more types together.
重合体は、公知の方法によって製造することができる。 The polymer can be produced by a known method.
このような加水分解性ケイ素含有基を含有するポリオキシアルキレン系重合体としては、公知のものを用いることができる。
例えば、特公昭４５−３６３１９号、同４６−１２１５４号、同４９−３２６７３号、特開昭５０−１５６５９９号、同５１−７３５６１号、同５４−６０９６号、同５５−８２１２３号、同５５−１２３６２０号、同５５−１２５１２１号、同５５−１３１０２２号、同５５−１３５１３５号、同５５−１３７１２９号および特開平３−７２５２７号の各公報等に記載されているものを用いることができる。また、市販品としては、例えば、鐘淵化学工業社製のＭＳＰ Ｓ２０３、Ｓ３０３、８１１およびＳ９４３、旭硝子社製のＥＸＣＥＳＴＡＲ ＥＳ−Ｓ２４１０、ＥＳ−Ｓ２４２０、ＥＳ−Ｓ３４３０およびＥＳ−Ｓ３６３０を用いることができる。
Known polyoxyalkylene polymers containing such hydrolyzable silicon-containing groups can be used.
For example, Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55- Nos. 123620, 55-125121, 55-131022, 55-135135, 55-137129, and JP-A-3-72527 can be used. As commercially available products, for example, MSP S203, S303, 811 and S943 manufactured by Kaneka Chemical Co., Ltd., EXCESTAR ES-S2410, ES-S2420, ES-S3430 and ES-S3630 manufactured by Asahi Glass Co., Ltd. can be used. .
つぎに、ポリマー微粒子について説明する。
本発明に用いられるポリマー微粒子は、液状ゴムが３次元架橋してなるポリマー微粒子であり、上述した重合体中に分散している。
Next, polymer fine particles will be described.
The polymer fine particles used in the present invention are polymer fine particles obtained by three-dimensionally cross-linking liquid rubber, and are dispersed in the above-described polymer.
液状ゴムは、特に限定されず、例えば、ジエン系ゴムおよび非ジエン系ゴムが挙げられる。
ジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）が挙げられる。
非ジエン系ゴムとしては、例えば、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム、エチレン−プロピレンゴム（ＥＰＭ）、クロロスルホン化ポリエチレンゴム、塩素化ポリエチレン、ウレタンゴム、アクリルゴム、シリコーンゴム、ポリサルファイドが挙げられる。
中でも、ジエン系ゴムが好ましく、イソプレンゴムがより好ましい。
これらは単独で用いてもよく、２種以上を併用してもよい。
The liquid rubber is not particularly limited, and examples thereof include diene rubber and non-diene rubber.
Examples of the diene rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber (CR), ethylene-propylene- Examples include diene rubber (EPDM).
Examples of the non-diene rubber include butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene rubber (EPM), chlorosulfonated polyethylene rubber, chlorinated polyethylene, urethane rubber, acrylic rubber, silicone rubber, and polysulfide.
Among these, diene rubber is preferable, and isoprene rubber is more preferable.
These may be used alone or in combination of two or more.
液状ゴムは、酸無水物を有する官能基を分子内に有するのが好ましい。これにより、接着性がより優れたものとなる。
酸無水物を有する官能基は、特に限定されず、例えば、無水マレイン酸を有する官能基が挙げられる。
酸無水物を有する官能基を分子内に有する液状ゴムは、例えば、酸無水物を有する官能基を分子内に有しない液状ゴムの主鎖に、酸無水物を有する官能基を有する化合物を反応させる方法により得ることができる。
The liquid rubber preferably has a functional group having an acid anhydride in the molecule. Thereby, adhesiveness will become more excellent.
The functional group having an acid anhydride is not particularly limited, and examples thereof include a functional group having maleic anhydride.
A liquid rubber having a functional group having an acid anhydride in the molecule reacts, for example, a compound having a functional group having an acid anhydride with the main chain of the liquid rubber having no functional group having an acid anhydride in the molecule. It can obtain by the method of making it.
液状ゴムの分子量は、特に限定されない。 The molecular weight of the liquid rubber is not particularly limited.
ポリマー微粒子は、上述した液状ゴムが３次元架橋してなる。３次元架橋の態様は、特に限定されない。
例えば、一つの態様として、液状ゴムが３次元架橋可能な官能基を有している場合に、この官能基の反応により３次元架橋している態様が挙げられる。具体的には、ジエン系ゴムの二重結合部分に、無水マレイン酸等の酸無水物を有する官能基が導入されている場合、この酸無水物の反応により、３次元架橋することができる。
この際、官能基の硬化剤、触媒等を用いてもよい。硬化剤および触媒としては、従来公知のものを用いることができる。例えば、無水マレイン酸を有する官能基の場合、硬化剤として、オキサゾリジン化合物およびそれを加水分解するための水を用いることができる。この例では、水がオキサゾリジン化合物を加水分解させて、第二級アミンが生成し、この第二級アミンが無水マレイン酸を開環させて、三次元架橋が行われる。なお、水は、後述する炭酸カルシウム等の充填剤を未乾燥の状態で加えて供給することもできる。
The polymer fine particles are formed by three-dimensionally cross-linking the liquid rubber described above. The mode of three-dimensional crosslinking is not particularly limited.
For example, as one aspect, when the liquid rubber has a functional group capable of three-dimensional crosslinking, an aspect in which the liquid rubber is three-dimensionally cross-linked by the reaction of the functional group. Specifically, when a functional group having an acid anhydride such as maleic anhydride is introduced into the double bond portion of the diene rubber, three-dimensional crosslinking can be performed by the reaction of the acid anhydride.
At this time, a functional group curing agent, a catalyst, or the like may be used. A conventionally well-known thing can be used as a hardening | curing agent and a catalyst. For example, in the case of a functional group having maleic anhydride, an oxazolidine compound and water for hydrolyzing it can be used as a curing agent. In this example, water hydrolyzes the oxazolidine compound to form a secondary amine, which opens the maleic anhydride and performs three-dimensional crosslinking. In addition, water can also be supplied by adding a filler such as calcium carbonate described later in an undried state.
また、別の態様として、液状ゴムが架橋剤および／または硬化剤により３次元架橋している態様が挙げられる。架橋剤としては、従来公知のものを用いることができる。例えば、有機過酸化物、硫黄系化合物が挙げられる。 Another embodiment includes an embodiment in which the liquid rubber is three-dimensionally crosslinked with a crosslinking agent and / or a curing agent. A conventionally well-known thing can be used as a crosslinking agent. For example, an organic peroxide and a sulfur type compound are mentioned.
ポリマー微粒子は、上述した重合体中に分散している。分散させる方法は、特に限定されないが、重合体中に、この重合体と相溶性の低い液状ゴムを添加しかくはんして、相分離により分散させて、その後、液状ゴムを、３次元架橋可能な官能基の反応または架橋剤等により、３次元架橋させる方法が好ましい。
また、液状ゴムと重合体との相溶性が低くない場合には、高速でかくはんすることにより分散させて、その後、上記と同様に、３次元架橋させる方法も好ましい。高速でかくはんするためには、例えば、バイブロミキサー、ジャイロミキサー、高速ディスパー等を有するかくはん機を用いることができる。
The polymer fine particles are dispersed in the polymer described above. The dispersion method is not particularly limited, but a liquid rubber having low compatibility with the polymer is added to the polymer, stirred, dispersed by phase separation, and then the liquid rubber can be cross-linked three-dimensionally. A method of three-dimensional crosslinking by a functional group reaction or a crosslinking agent is preferred.
Further, when the compatibility between the liquid rubber and the polymer is not low, it is also preferable to disperse the mixture by stirring at a high speed and then perform three-dimensional crosslinking in the same manner as described above. In order to stir at high speed, for example, a stirrer having a vibro mixer, a gyro mixer, a high speed disper, etc. can be used.
これらの方法では、重合体が硬化しない条件下、即ち、湿気しゃ断条件下、または、触媒、硬化剤等の未添加の条件下で、重合体中に液状ゴムを分散させて、かくはん中に重合体を硬化させずに、液状ゴムの架橋反応により、３次元架橋を行わせる。架橋反応の進行に従って、かくはんによりポリマー微粒子が重合体中で均一に分散した状態となる。この際、重合体は、反応に関与しない。 In these methods, the liquid rubber is dispersed in the polymer under conditions where the polymer is not cured, that is, under moisture-blocking conditions, or without addition of a catalyst, a curing agent, etc. Three-dimensional crosslinking is performed by a crosslinking reaction of liquid rubber without curing the coalescence. As the cross-linking reaction proceeds, the fine polymer particles are uniformly dispersed in the polymer by stirring. At this time, the polymer does not participate in the reaction.
本発明においては、液状ゴムの架橋反応速度、かくはん時のかくはん速度および温度、重合体と液状ゴムとの相分離エネルギー等を考慮すると、ポリマー微粒子の大きさを調整することができ、ポリマー微粒子を重合体中に均一に分散させることができる。
これらの物性（パラメータ）の好ましい範囲は、用いる重合体、液状ゴム等によって異なり、一概には決定しえないが、例えば、かくはん速度（回転速度）は５０〜２０，０００ｒｐｍであるのが、ポリマー微粒子を均一に分散させられる点で好ましい。
In the present invention, in consideration of the crosslinking reaction speed of liquid rubber, the stirring speed and temperature at the time of stirring, the phase separation energy between the polymer and the liquid rubber, etc., the size of the polymer fine particles can be adjusted. It can be uniformly dispersed in the polymer.
The preferred range of these physical properties (parameters) varies depending on the polymer used, liquid rubber, etc. and cannot be determined unconditionally. For example, the stirring speed (rotational speed) is 50 to 20,000 rpm. This is preferable in that the fine particles can be uniformly dispersed.
なお、重合体中に液状ゴムを分散させて、３次元架橋させる際に、後述する各種の添加剤、例えば、炭酸カルシウム等の充填剤、プロセスオイル等を添加することができる。プロセスオイルは、重合体との相溶性が低く、かつ、液状ゴムとの相溶性が高いため、液状ゴムの３次元架橋を安定的に行わせつつ、ポリマー微粒子の中に取り込まれる。 When the liquid rubber is dispersed in the polymer and three-dimensionally crosslinked, various additives described later, for example, fillers such as calcium carbonate, process oil, and the like can be added. Since the process oil has low compatibility with the polymer and high compatibility with the liquid rubber, the process oil is taken into the polymer fine particles while stably performing the three-dimensional crosslinking of the liquid rubber.
本発明においては、ポリマー微粒子が、加水分解性ケイ素含有基を有するのが好ましい態様の一つである。ポリマー微粒子が加水分解性ケイ素含有基を有すると、重合体の加水分解性ケイ素含有基が加水分解して硬化する際に、ポリマー微粒子の加水分解性ケイ素含有基も同時に加水分解して反応するため、重合体とポリマー微粒子との間の結合が形成され、硬化後の物性がより優れたものになる。
ポリマー微粒子が加水分解性ケイ素含有基を有するようにする方法は、特に限定されないが、その全部または一部が、シランカップリング剤との反応により導入されるのが好ましい。例えば、液状ゴムが官能基を有する場合には、この官能基と反応しうる官能基と加水分解性ケイ素含有基とを有するシランカップリング剤を直接に反応させる方法が挙げられる。また、これらのシランカップリング剤を、エポキシ樹脂、ポリイソシアネート等を介して間接的に液状ゴムに導入する方法も挙げられる。
In the present invention, it is one of preferred embodiments that the polymer fine particles have a hydrolyzable silicon-containing group. If the polymer fine particles have hydrolyzable silicon-containing groups, the hydrolyzable silicon-containing groups of the polymer fine particles simultaneously hydrolyze and react when the hydrolyzable silicon-containing groups of the polymer are hydrolyzed and cured. A bond between the polymer and the polymer fine particles is formed, and the physical properties after curing become better.
The method for causing the polymer fine particles to have a hydrolyzable silicon-containing group is not particularly limited, but it is preferable that all or part of the polymer fine particles be introduced by reaction with a silane coupling agent. For example, when the liquid rubber has a functional group, a method of directly reacting a silane coupling agent having a functional group capable of reacting with the functional group and a hydrolyzable silicon-containing group can be mentioned. Moreover, the method of introduce | transducing these silane coupling agents into liquid rubber indirectly through an epoxy resin, polyisocyanate, etc. is also mentioned.
シランカップリング剤は、特に限定されないが、アミノシラン、ビニルシラン、エポキシシラン、（メタ）アクリルシラン、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、これらとエポキシ樹脂またはポリイソシアネートとの反応により得られる化合物であるのが好ましい。 The silane coupling agent is not particularly limited, but can be obtained by reacting aminosilane, vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, ketimine silane, or a mixture or reaction thereof, or an epoxy resin or polyisocyanate. It is preferable that it is a compound obtained.
アミノシランとしては、例えば、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が挙げられる。
ビニルシランとしては、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）ビニルシランが挙げられる。
エポキシシランとしては、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が挙げられる。
メタクリルシランとしては、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が挙げられる。
イソシアネートシランとしては、例えば、イソシアネートプロピルトリエトキシシランが挙げられる。
ケチミンシランとしては、例えば、ケチミン化プロピルトリメトキシシランが挙げられる。
これらは単独で用いてもよく、２種以上を併用してもよい。
Examples of aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, and bistriethoxysilylpropylamine. Bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, Examples thereof include N-2- (aminoethyl) -3-aminopropyltriethoxysilane and N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane.
Examples of the vinyl silane include vinyl trimethoxy silane, vinyl triethoxy silane, and tris- (2-methoxy ethoxy) vinyl silane.
Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyl. Examples include dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
Examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Examples of the isocyanate silane include isocyanate propyl triethoxysilane.
Examples of the ketimine silane include ketiminated propyltrimethoxysilane.
These may be used alone or in combination of two or more.
シランカップリング剤の量は、前記重合体１００質量部に対し、０．１〜１０質量部であるのが好ましい。 It is preferable that the quantity of a silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers.
これらの方法においては、ポリマー微粒子の生成後（即ち、液状ゴムの３次元架橋後）にシランカップリング剤と反応させることもでき、ポリマー微粒子の生成中（即ち、液状ゴムの３次元架橋の反応進行中）にシランカップリング剤と反応させることもできる。 In these methods, it is possible to react with a silane coupling agent after the production of polymer fine particles (that is, after the three-dimensional crosslinking of the liquid rubber), and during the production of polymer fine particles (that is, the reaction of the three-dimensional crosslinking of the liquid rubber) It can also be reacted with a silane coupling agent during the process.
ポリマー微粒子は、重合体中に均一に分散する点、接着性および硬化後の伸びが優れたものになる点等から、平均粒子径が０．０１〜１００μｍであるのが好ましく、０．１〜５０μｍであるのがより好ましい。 The polymer fine particles preferably have an average particle diameter of 0.01 to 100 μm from the viewpoint of being uniformly dispersed in the polymer and having excellent adhesion and elongation after curing. More preferably, it is 50 μm.
本発明の硬化性組成物におけるポリマー微粒子の含有量は、上述した重合体１００質量部に対し、１〜１００質量部、好ましくは５〜７０質量部、より好ましくは１０〜４０質量部である。上記範囲であると、従来の硬化性組成物と同等以上の作業性（例えば、粘度、揺変性等の物性）、外観特性（例えば、色調、光沢等）等を有する硬化性組成物となる。 Content of the polymer fine particle in the curable composition of this invention is 1-100 mass parts with respect to 100 mass parts of polymers mentioned above, Preferably it is 5-70 mass parts, More preferably, it is 10-40 mass parts. Within the above range, a curable composition having workability (for example, physical properties such as viscosity and thixotropic properties) and appearance characteristics (for example, color tone, gloss, etc.) equivalent to or higher than those of conventional curable compositions is obtained.
本発明の硬化性組成物は、相溶化剤を含有するのが好ましい態様の一つである。相溶化剤は、種々の目的で含有される。目的としては、例えば、ポリマー微粒子の生成、ポリマー微粒子の分散、硬化後の物性の調整が挙げられる。
相溶化剤は、一般的には、例えば、ポリマーＡとポリマーＢとが非相溶な混合系となる場合に、ポリマーＡのモノマーとポリマーＢのモノマーとの共重合体が、界面活性剤のような役割を果たし、ポリマーＡとポリマーＢとの界面において、界面張力を低下させたり、界面層の制御や分散層の反発作用等の機能を発揮する。即ち、相溶化剤は、微細分散化、界面での両者の接着性向上等の重要な機能を担う。
In one preferred embodiment, the curable composition of the present invention contains a compatibilizing agent. The compatibilizing agent is contained for various purposes. Examples of the purpose include generation of polymer fine particles, dispersion of polymer fine particles, and adjustment of physical properties after curing.
In general, for example, when the polymer A and the polymer B are in an incompatible mixed system, the copolymer of the polymer A monomer and the polymer B monomer is a surfactant. It plays such a role, and at the interface between the polymer A and the polymer B, functions such as lowering the interfacial tension, controlling the interface layer, and repelling action of the dispersion layer are exhibited. That is, the compatibilizing agent bears important functions such as fine dispersion and improved adhesion between the two at the interface.
相溶化剤としては、例えば、ブレンド成分と同じもの；ブレンド成分と相溶性のある他成分が一部同じもの；ポリマーＡおよびポリマーＢとは別のモノマーを含む共重合体であって、それぞれの溶解性パラメータの値が同じか、または近いかであるもの；ポリマーＡまたはポリマーＢと反応して、他のポリマーと相溶性を示す別のモノマーの共重合体；ポリマーＡとポリマーＢとのブレンド過程で反応により、グラフトおよび／またはブロック共重合体が一部形成されて相溶化剤として作用するものが挙げられる。 Examples of the compatibilizer include, for example, the same as the blend component; some of the other components compatible with the blend component are the same; a copolymer containing a monomer different from the polymer A and the polymer B, The solubility parameter value is the same or close; copolymer of another monomer that reacts with polymer A or polymer B and is compatible with other polymers; blend of polymer A and polymer B In the process, a part of the graft and / or block copolymer is formed by the reaction and acts as a compatibilizing agent.
本発明における相溶化剤は、異なる化学的特性の二つ以上の物質を、同一の分子中に有するものであり、その機能により、界面活性剤、混和剤、乳化剤、可溶化剤、分散剤等と呼ばれる。
本発明に用いられる相溶化剤としては、例えば、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等の非イオン性界面活性剤が好適に挙げられる。
相溶化剤は、ポリマー微粒子の生成後（即ち、液状ゴムの３次元架橋後）に添加してもよく、ポリマー微粒子の生成中（即ち、液状ゴムの３次元架橋の反応進行中）に添加してもよく、ポリマー微粒子の生成前に添加してもよく、種々の条件に応じて、適宜方法を選択するのが好ましい。
The compatibilizing agent in the present invention has two or more substances having different chemical characteristics in the same molecule, and depending on its function, a surfactant, an admixture, an emulsifier, a solubilizer, a dispersant, etc. Called.
Suitable examples of the compatibilizer used in the present invention include nonionic surfactants such as polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.
The compatibilizing agent may be added after the production of the polymer fine particles (that is, after the three-dimensional crosslinking of the liquid rubber) or during the formation of the polymer fine particles (that is, during the progress of the three-dimensional crosslinking of the liquid rubber). It may be added before the production of polymer fine particles, and it is preferable to select a method as appropriate according to various conditions.
相溶化剤は、１種単独でまたは２種以上を組み合わせて用いることができる。２種以上を併用する場合の割合は、本発明の硬化性組成物が用いられる用途、本発明の硬化性組成物に要求される物性等に応じて、適宜決定することができる。 Compatibilizers can be used alone or in combination of two or more. The ratio in the case of using 2 or more types in combination can be appropriately determined according to the use in which the curable composition of the present invention is used, the physical properties required for the curable composition of the present invention, and the like.
相溶化剤の含有量は、上述した重合体１００質量部に対し、０．１〜１０質量部、好ましくは０．２〜５質量部である。 The content of the compatibilizing agent is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polymer described above.
本発明の硬化性組成物は、炭酸カルシウムを含有するのが好ましい態様の一つである。
本発明に用いられる炭酸カルシウムは、特に限定されず、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム（軽質炭酸カルシウム）、コロイダル炭酸カルシウムが挙げられる。
また、脂肪酸、樹脂酸、脂肪酸エステル、高級アルコール付加イソシアネート化合物等により表面処理された表面処理炭酸カルシウムも用いることができる。具体的には、脂肪酸で表面処理された炭酸カルシウムとして、カルファイン２００（丸尾カルシウム社製）、ホワイトン３０５（重質炭酸カルシウム、白石カルシウム社製）、白艶華ＣＣＲ（白石工業社製）、変性脂肪酸で表面処理された炭酸カルシウムとして、ライトンＡ−４（重質炭酸カルシウム、備北粉化工業社製）、脂肪酸エステルで表面処理された炭酸カルシウムとして、シーレッツ２００（丸尾カルシウム社製）、スノーライトＳＳ（重質炭酸カルシウム、丸尾カルシウム社製）等が好適に用いられる。中でも、脂肪酸、変性脂肪酸、脂肪酸エステル、高級アルコール付加イソシアネート化合物等で表面処理されたものが、特に好ましい。表面処理炭酸カルシウムは、粘度を高くするため形状保持性および作業性に寄与し、また、表面が疎水性であるため貯蔵安定性に寄与する。
これらは単独で用いてもよく、２種以上を併用してもよい。
In one preferred embodiment, the curable composition of the present invention contains calcium carbonate.
The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with a fatty acid, Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Whiteon 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), Hakusyo Hana CCR (manufactured by Shiroishi Kogyo Co., Ltd.), modified As calcium carbonate surface-treated with fatty acid, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Flour Industries Co., Ltd.), as calcium carbonate surface-treated with fatty acid ester, Sealets 200 (manufactured by Maruo Calcium Co., Ltd.), Snowlight SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) or the like is preferably used. Of these, those that have been surface-treated with fatty acids, modified fatty acids, fatty acid esters, higher alcohol-added isocyanate compounds, and the like are particularly preferred. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.
炭酸カルシウムの含有量は、前記重合体１００質量部に対し、５０〜４００質量部であるのが好ましい。 The content of calcium carbonate is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the polymer.
本発明の硬化性組成物は、分子量１０００以下の加水分解性化合物を含有するのが好ましい態様の一つである。加水分解性化合物は、重合体、炭酸カルシウム等が持つ水分を吸収し、貯蔵安定性を向上させるために効果的に用いられる。
このような加水分解性化合物としては、例えば、ビニルシラン、オキシムシラン、アミノシラン、エポキシシラン、メルカプトシラン等の比較的低分子量のシランカップリング剤；オルトギ酸メチル、オルトギ酸エチル、２−フェニル−３−オキサゾリジンエタノール、ポリオキシアルキレン−メチルステアロキシポリシロキサンコポリマー等の加水分解性化合物が挙げられる。
これらは単独で用いてもよく、２種以上を併用してもよい。
In one preferred embodiment, the curable composition of the present invention contains a hydrolyzable compound having a molecular weight of 1000 or less. The hydrolyzable compound is effectively used to absorb moisture contained in the polymer, calcium carbonate, etc. and improve storage stability.
Examples of such hydrolyzable compounds include relatively low molecular weight silane coupling agents such as vinyl silane, oxime silane, amino silane, epoxy silane, and mercapto silane; methyl orthoformate, ethyl orthoformate, 2-phenyl-3- Examples include hydrolyzable compounds such as oxazolidineethanol and polyoxyalkylene-methylstearoxypolysiloxane copolymers.
These may be used alone or in combination of two or more.
分子量１０００以下の加水分解性化合物の含有量は、前記重合体１００質量部に対し、０．１〜１０質量部であるのが好ましい。 The content of the hydrolyzable compound having a molecular weight of 1000 or less is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer.
本発明の硬化性組成物は、ポリマー微粒子に加水分解性ケイ素含有基を導入させるためのものとは別に、上述したシランカップリング剤を含有することができる。
シランカップリング剤の含有量は、ポリマー微粒子に加水分解性ケイ素含有基を導入させるためのものと別に含有させるものとの合計で、上記範囲とするのが好ましい。
The curable composition of the present invention can contain the above-mentioned silane coupling agent separately from the one for introducing a hydrolyzable silicon-containing group into polymer fine particles.
The content of the silane coupling agent is preferably the above-mentioned range, which is the sum of the amount of the silane coupling agent and the amount of the silane coupling agent to be incorporated separately from that for introducing the hydrolyzable silicon-containing group.
本発明の硬化性組成物は、スズ触媒および／またはチタン触媒を含有するのが好ましい。
スズ触媒および／またはチタン触媒は、従来公知のものを用いることができる。
スズ触媒としては、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。
チタン触媒としては、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。
これらは単独で用いてもよく、２種以上を併用してもよい。
The curable composition of the present invention preferably contains a tin catalyst and / or a titanium catalyst.
A conventionally well-known thing can be used for a tin catalyst and / or a titanium catalyst.
Examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; reaction products of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate.
Examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
These may be used alone or in combination of two or more.
スズ触媒および／またはチタン触媒の含有量は、前記重合体１００質量部に対し、０．０１〜５．０質量部であるのが好ましい。 The content of the tin catalyst and / or titanium catalyst is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the polymer.
本発明の硬化性組成物は、本発明の目的を損なわない範囲で、その他の硬化剤を含有することができる。
例えば、アミン系硬化剤、酸または酸無水物系硬化剤、塩基性活性水素化合物、イミダゾール類、ポリメルカプタン系硬化剤、フェノール樹脂、ユリア樹脂、メラミン樹脂、イソシアネート系硬化剤、潜在性硬化剤、紫外線硬化剤が挙げられる。
The curable composition of this invention can contain another hardening | curing agent in the range which does not impair the objective of this invention.
For example, amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles, polymercaptan curing agents, phenol resins, urea resins, melamine resins, isocyanate curing agents, latent curing agents, An ultraviolet curing agent is mentioned.
本発明の硬化性組成物は、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、炭酸カルシウム以外の充填剤、可塑剤、軟化剤、チクソトロピー性付与剤、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、溶剤が挙げられる。 The curable composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate, plasticizers, softeners, thixotropy imparting agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, and dispersions. Agents and solvents.
炭酸カルシウム以外の充填剤としては、各種形状のものを使用することができる。例えば、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；炭酸マグネシウム、炭酸亜鉛；ろう石クレー、カオリンクレー、焼成クレー；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。 As fillers other than calcium carbonate, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Fired clays; 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.
可塑剤または軟化剤としては、例えば、フタル酸ジイソノニル（ＤＩＮＰ）、フタル酸ジオクチル、フタル酸ジブチル；アジピン酸ジオクチル、コハク酸イソデシル；ジエチレングリコールジペンゾエート、ペンタエリスリトールエステル；オレイン酸ブチル、アセチルリシノール酸メチル；リン酸トリクレジル、リン酸トリオクチル；アジピン酸プロピレングリコールポリエステル、アジピン酸ブチレングリコールポリエステル；パラフィン系オイル、ナフテン系オイル、アロマ系オイル等の石油系軟化剤が挙げられる。 Examples of the plasticizer or softener include diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol ester; butyl oleate, acetylricinoleic acid Examples include methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol polyester adipate; petroleum softeners such as paraffinic oil, naphthenic oil, and aroma oil.
チクソトロピー性付与剤としては、例えば、乾式シリカ、ホワイトカーボン、水素添加ひまし油、炭酸カルシウム、テフロン（登録商標）が挙げられる。
顔料としては、例えば、二酸化チタン、酸化亜鉛、群青、ベンガラ、リトポン、鉛、カドミウム、鉄、コバルト、アルミニウム、塩酸塩、硫酸塩等の無機顔料；アゾ顔料、銅フタロシアニン顔料等の有機顔料が挙げられる。
Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, and Teflon (registered trademark).
Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; organic pigments such as azo pigments and copper phthalocyanine pigments. It is done.
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。
接着性付与剤としては、例えば、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、エポキシ樹脂が挙げられる。
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 adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.
上記のような各成分から本発明の硬化性組成物を製造する方法は、特に限定されないが、上述したように、重合体中でポリマー微粒子を形成させた後、その他の成分を、減圧下または窒素等の不活性ガス雰囲気下で、混合ミキサー等のかくはん装置を用いて十分に混練し、均一に分散させる方法が挙げられる。 The method for producing the curable composition of the present invention from each component as described above is not particularly limited. As described above, after forming polymer fine particles in the polymer, other components are reduced under reduced pressure or Examples thereof include a method in which the mixture is sufficiently kneaded and uniformly dispersed using a stirring apparatus such as a mixing mixer in an inert gas atmosphere such as nitrogen.
本発明の硬化性組成物は、一成分形としてもよく、二成分形としてもよい。二成分形の場合、硬化剤以外を主剤とし、使用前に、主剤と硬化剤とを常法に従って混合して用いる。
本発明の硬化性組成物は、湿気にさらすと、加水分解性ケイ素含有基の加水分解により、硬化反応が進行する。また、適宜水分を供給して、硬化反応を進行させることもできる。
The curable composition of the present invention may be a one-component form or a two-component form. In the case of the two-component form, the main agent is other than the curing agent, and the main agent and the curing agent are mixed and used according to a conventional method before use.
When the curable composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silicon-containing group. In addition, the curing reaction can be advanced by appropriately supplying water.
本発明の硬化性組成物をシーリング材等として用いる場合、被着体にプライマーを塗布してから用いてもよい。プライマーとしては、従来公知のものを用いることができる。 When using the curable composition of this invention as a sealing material etc., you may use it, after apply | coating a primer to a to-be-adhered body. A conventionally well-known thing can be used as a primer.
本発明の硬化性組成物は、土木建築用、コンクリート用、木材用、金属用、ガラス用、プラスチック用等のシーリング材、シール剤、ポッティング剤、弾性接着剤、コーティング材、ライニング材、接着剤等の用途に好適に用いられる。 The curable composition of the present invention is a sealing material, a sealing agent, a potting agent, an elastic adhesive, a coating material, a lining material, and an adhesive for civil engineering, concrete, wood, metal, glass, and plastic. It is suitably used for such applications.
以下、本発明を実施例により具体的に説明する。ただし、本発明は、これらに限定されない。
（実施例１）
ポリオキシアルキレン系重合体（ＭＳポリマー８１０、鐘淵化学工業社製）７０質量部に、後述する方法で得られたオキサゾリジン化合物（ＰＨＯ−ＸＤＩ）０．８質量部を添加し、約２分間かくはんして均一に混合させた。
その後、無水マレイン酸変性液状ポリイソプレンゴム（ＬＩＲ４０３、クラレ社製、数平均分子量３０，０００）２０質量部およびプロセスオイル（ＰＳ３２、出光石油化学社製）１０質量部を添加し、２分間かくはんして混合させた。
Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.
(Example 1)
To 70 parts by mass of a polyoxyalkylene polymer (MS polymer 810, manufactured by Kaneka Chemical Co., Ltd.), 0.8 part by mass of an oxazolidine compound (PHO-XDI) obtained by the method described later is added and stirred for about 2 minutes. And uniformly mixed.
Thereafter, 20 parts by mass of maleic anhydride-modified liquid polyisoprene rubber (LIR403, manufactured by Kuraray Co., Ltd., number average molecular weight 30,000) and 10 parts by mass of process oil (PS32, manufactured by Idemitsu Petrochemical Co., Ltd.) were added and stirred for 2 minutes. And mixed.
その後、未乾燥の炭酸カルシウム１（表面処理重質炭酸カルシウム、スノーライトＳＳ、丸尾カルシウム社製）５０質量部を添加し、３０分間かくはんして、液状ポリイソプレンゴムを３次元架橋させてポリマー微粒子１を形成させ、ポリオキシアルキレン系重合体中に、ポリマー微粒子１と炭酸カルシウム１とが分散した分散混合物を得た。
３次元架橋したポリマー微粒子１をレーザー顕微鏡で観察したところ、粒径は２０〜５０μｍ程度であった。
Thereafter, 50 parts by mass of undried calcium carbonate 1 (surface-treated heavy calcium carbonate, Snowlite SS, manufactured by Maruo Calcium Co., Ltd.) was added, and the mixture was stirred for 30 minutes to three-dimensionally crosslink the liquid polyisoprene rubber to form polymer particles. 1 was formed to obtain a dispersion mixture in which polymer fine particles 1 and calcium carbonate 1 were dispersed in a polyoxyalkylene polymer.
When the three-dimensionally crosslinked polymer fine particles 1 were observed with a laser microscope, the particle size was about 20 to 50 μm.
ついで、得られた分散混合物に、炭酸カルシウム２（表面処理炭酸カルシウム、カルファイン２００、丸尾カルシウム社製）、紫外線吸収剤（チヌビン３２７、チバ・スペシャルティ・ケミカルズ社製）、老化防止剤（９４４ＬＤ、チバ・スペシャルティ・ケミカルズ社製）、酸化チタン（タイペークＲ−８２０、石原産業社製）、フタル酸ジイソノニル（ＤＩＮＰ、ジェイ・プラス社製）、エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、エピコート８２８、ジャパンエポキシレジン社製）、スズ触媒（ネオスタンＵ−２８、日東化成社製）およびアミン触媒（ファーミン２０Ｄ、花王社製）を、第１表に示す量比（質量部）で添加してかくはんして混合させ、硬化性組成物を得た。 Next, calcium carbonate 2 (surface treated calcium carbonate, Calfine 200, manufactured by Maruo Calcium Co., Ltd.), ultraviolet absorber (Tinuvin 327, manufactured by Ciba Specialty Chemicals Co., Ltd.), anti-aging agent (944LD, Ciba Specialty Chemicals), titanium oxide (Taipeke R-820, manufactured by Ishihara Sangyo Co., Ltd.), diisononyl phthalate (DINP, manufactured by J Plus), epoxy resin (bisphenol A type epoxy resin, Epicoat 828, Japan Epoxy) Resin Co.), tin catalyst (Neostan U-28, Nitto Kasei Co., Ltd.) and amine catalyst (Pharmin 20D, Kao Co., Ltd.) are added at the quantitative ratio (parts by mass) shown in Table 1 and stirred. To obtain a curable composition.
＜オキサゾリジン化合物（ＰＨＯ−ＸＤＩ）の合成＞
オキサゾリジン化合物は、一般に、例えば、アルカノールアミンとケトンまたはアルデヒドとを脱水縮合させて得ることができる。本実施例においては、以下のようにしてオキサゾリジン化合物（ＰＨＯ−ＸＤＩ）の合成を行った。
ジエタノールアミン３０．０ｇとベンズアルデヒド３１．８ｇとトルエン３３．０ｇとを１Ｌ容のフラスコに入れ、１１０℃で６時間、脱水反応させた。その後、９０℃で、減圧することにより、トルエンと未反応物とを除去して、ヒドロキシアルキルオキサゾリジンである、２−フェニル−３−（２−ヒドロキシエチル）オキサゾリジン５４．０ｇを得た。得られた２−フェニル−３−（２−ヒドロキシエチル）オキサゾリジン３１．８ｇと、キシリレンジイソシアネート１５．６ｇとを混合し、６０℃で３時間反応させ、オキサゾリジン化合物（ＰＨＯ−ＸＤＩ）を得た。
<Synthesis of Oxazolidine Compound (PHO-XDI)>
The oxazolidine compound can be generally obtained by, for example, dehydrating condensation of an alkanolamine and a ketone or aldehyde. In this example, an oxazolidine compound (PHO-XDI) was synthesized as follows.
30.0 g of diethanolamine, 31.8 g of benzaldehyde, and 33.0 g of toluene were placed in a 1 L flask and subjected to dehydration reaction at 110 ° C. for 6 hours. Then, by reducing the pressure at 90 ° C., toluene and unreacted substances were removed to obtain 54.0 g of 2-phenyl-3- (2-hydroxyethyl) oxazolidine, which is a hydroxyalkyloxazolidine. 31.8 g of the obtained 2-phenyl-3- (2-hydroxyethyl) oxazolidine and 15.6 g of xylylene diisocyanate were mixed and reacted at 60 ° C. for 3 hours to obtain an oxazolidine compound (PHO-XDI). .
（実施例２）
実施例１と同様の方法により、分散混合物を得た。この分散混合物に、シランカップリング剤（アミノシラン化合物、ＫＢＭ６０２、信越化学工業社製）０．５質量部を添加し、２分間かくはんして、ポリマー微粒子１に加水分解性ケイ素含有基が導入されたポリマー微粒子２を得た。
３次元架橋したポリマー微粒子２をレーザー顕微鏡で観察したところ、粒径は２０〜５０μｍ程度であった。
その後、実施例１と同様の方法により、種々の添加剤を第１表に示す量比（質量部）で添加してかくはんして混合させ、硬化性組成物を得た。
(Example 2)
A dispersion mixture was obtained in the same manner as in Example 1. To this dispersion mixture, 0.5 part by mass of a silane coupling agent (aminosilane compound, KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 2 minutes to introduce hydrolyzable silicon-containing groups into the polymer fine particles 1. Polymer fine particles 2 were obtained.
When the three-dimensionally crosslinked polymer fine particles 2 were observed with a laser microscope, the particle size was about 20 to 50 μm.
Thereafter, by the same method as in Example 1, various additives were added at the quantitative ratios (parts by mass) shown in Table 1 and stirred and mixed to obtain a curable composition.
（実施例３）
添加剤として更に相溶化剤（脂肪酸エステル、レオドールＴＷ−Ｓ３２０Ｗ、花王社製）を第１表に示す量比（質量部）で用いた以外は、実施例２と同様の方法により、硬化性組成物を得た。
３次元架橋したポリマー微粒子３をレーザー顕微鏡で観察したところ、粒径は５μｍ程度であった。
(Example 3)
In the same manner as in Example 2, except that a compatibilizer (fatty acid ester, Rheodor TW-S320W, manufactured by Kao Co., Ltd.) was used as an additive in the quantitative ratio (parts by mass) shown in Table 1, a curable composition was obtained. I got a thing.
When the three-dimensionally crosslinked polymer fine particles 3 were observed with a laser microscope, the particle size was about 5 μm.
（比較例１）
分散混合物の代わりに、ポリオキシアルキレン系重合体（ＭＳポリマー８１０、鐘淵化学工業社製）１００質量部および未乾燥の炭酸カルシウム１（表面処理重質炭酸カルシウム、スノーライトＳＳ、丸尾カルシウム社製）５０質量部を用いた以外は、実施例１と同様の方法により、硬化性組成物を得た。
(Comparative Example 1)
Instead of the dispersion mixture, 100 parts by mass of a polyoxyalkylene polymer (MS polymer 810, Kaneka Chemical Co., Ltd.) and undried calcium carbonate 1 (surface-treated heavy calcium carbonate, Snowlite SS, Maruo Calcium Co., Ltd.) ) A curable composition was obtained in the same manner as in Example 1 except that 50 parts by mass was used.
得られた硬化性組成物について、以下のようにして接着性および硬化後の伸びを評価した。
陽極酸化アルミニウム板２枚と硬化性組成物とを用いて、ＪＩＳ Ａ５７５８：１９９７の規定に準じて、Ｈ型試験片を作製した。
具体的には、プライマーを用いた場合は、陽極酸化アルミニウム板の表面に、２０℃、５５％ＲＨの条件下で、プライマー（ハマタイトプライマーＮｏ．４０、横浜ゴム（株）製）を塗布し、約１時間放置した後に、Ｈ型試験片を作製した。
また、プライマーを用いなかった場合は、陽極酸化アルミニウム板の表面をメチルエチルケトンで脱脂処理し、その直後に、Ｈ型試験片を作製した。
About the obtained curable composition, adhesiveness and the elongation after hardening were evaluated as follows.
Using two anodized aluminum plates and a curable composition, an H-type test piece was prepared in accordance with JIS A5758: 1997.
Specifically, when using a primer, a primer (Hamatite Primer No. 40, manufactured by Yokohama Rubber Co., Ltd.) was applied to the surface of the anodized aluminum plate under the conditions of 20 ° C. and 55% RH. After leaving for about 1 hour, an H-type test piece was prepared.
When the primer was not used, the surface of the anodized aluminum plate was degreased with methyl ethyl ketone, and immediately after that, an H-type test piece was produced.
ついで、得られたＨ型試験片を、２３℃、５５％ＲＨの条件下で５日間放置し、更に、５０℃で２日間放置して養生した。
養生後のＨ型試験片について、引張速度５０ｍｍ／ｍｉｎで引張試験を行い、破壊の状態を目視で観察し、また、破断時の伸びを測定した。
結果を第１表に示す。第１表中、破壊の状態をＣＦ（凝集破壊）、ＴＣＦ（薄層凝集破壊）およびＡＦ（界面はく離）で示した。
Subsequently, the obtained H-type test piece was left to stand for 5 days under the conditions of 23 ° C. and 55% RH, and further allowed to stand for 2 days at 50 ° C. for curing.
The cured H-type test piece was subjected to a tensile test at a tensile speed of 50 mm / min, the state of fracture was observed visually, and the elongation at break was measured.
The results are shown in Table 1. In Table 1, the state of failure is indicated by CF (cohesive failure), TCF (thin layer cohesive failure) and AF (interface debonding).
第１表から明らかなように、本発明の硬化性組成物（実施例１〜３）は、プライマー不使用時およびプライマー使用時のいずれにおいても、従来の硬化性組成物（比較例１）に比べ、接着性および硬化後の伸びに優れる。 As is clear from Table 1, the curable compositions of the present invention (Examples 1 to 3) are the same as the conventional curable composition (Comparative Example 1) both when the primer is not used and when the primer is used. In comparison, it is excellent in adhesion and elongation after curing.
Claims (13)
前記重合体が、主鎖がアルキレンオキシド単量体単位を含み、加水分解性ケイ素含有基を１分子あたり少なくとも１個有する重合体であり、
前記ポリマー微粒子が、液状ゴムが３次元架橋してなるポリマー微粒子である、硬化性組成物。 Containing a polymer and fine polymer particles dispersed in the polymer,
The polymer is a polymer whose main chain includes an alkylene oxide monomer unit and has at least one hydrolyzable silicon-containing group per molecule;
A curable composition, wherein the polymer particles are polymer particles obtained by three-dimensionally cross-linking liquid rubber.
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| JP2006342234A (en) * | 2005-06-08 | 2006-12-21 | Yokohama Rubber Co Ltd:The | Curable composition, method for producing the same and double-glazed glass using the same |
| JP2007131660A (en) * | 2005-11-08 | 2007-05-31 | Yokohama Rubber Co Ltd:The | Method for producing curable composition and curable composition produced thereby |
| JP2009029972A (en) * | 2007-07-28 | 2009-02-12 | Tajima Roofing Co Ltd | One component curable resin composition and asphalt roofing waterproof structure |
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| JP2006342234A (en) * | 2005-06-08 | 2006-12-21 | Yokohama Rubber Co Ltd:The | Curable composition, method for producing the same and double-glazed glass using the same |
| JP2007131660A (en) * | 2005-11-08 | 2007-05-31 | Yokohama Rubber Co Ltd:The | Method for producing curable composition and curable composition produced thereby |
| JP2009029972A (en) * | 2007-07-28 | 2009-02-12 | Tajima Roofing Co Ltd | One component curable resin composition and asphalt roofing waterproof structure |
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