JP4973914B2 - Curable resin composition and waterproof material composition - Google Patents
Curable resin composition and waterproof material composition Download PDFInfo
- Publication number
- JP4973914B2 JP4973914B2 JP2006158416A JP2006158416A JP4973914B2 JP 4973914 B2 JP4973914 B2 JP 4973914B2 JP 2006158416 A JP2006158416 A JP 2006158416A JP 2006158416 A JP2006158416 A JP 2006158416A JP 4973914 B2 JP4973914 B2 JP 4973914B2
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- resin composition
- dibasic acid
- acid
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 title claims description 19
- 239000000463 material Substances 0.000 title claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 22
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000344 soap Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 70
- -1 cyclic aliphatic carboxylic acid Chemical class 0.000 description 26
- 238000001723 curing Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000007605 air drying Methods 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 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 8
- 239000000843 powder Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N butane-1,2,3,4-tetrol Chemical compound OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- 238000004078 waterproofing Methods 0.000 description 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 1
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- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-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
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 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
- 150000003053 piperidines Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、硬化時の表面硬化性、塗膜乾燥性に優れ、アスファルトやコンクリート等の下地への追従性に優れる硬化性樹脂組成物、及び防水材組成物を提供するものである。 The present invention provides a curable resin composition and a waterproof material composition that are excellent in surface curability at the time of curing and coating film drying properties, and are excellent in followability to a base such as asphalt or concrete.
不飽和ポリエステル樹脂、ビニルエステル樹脂等の樹脂は、一般的にはスチレンモノマーが使用されており、塗膜材料や防水材料として使用した場合、ラジカル硬化の途中に塗膜表面より揮散するモノマーの臭気が強く、問題となる場合がある。その対策として（メタ）アクリロイル基を有するモノマーや低揮散性の特殊なモノマーが使用されるが、空気中の酸素がラジカル重合を阻害するため、塗膜表面の乾燥性が悪いという欠点がある。さらに、下地に対して追従性を付与するため、二重結合の濃度を下げ、反応性を低下させて樹脂硬化物の引張伸び率を１０％以上、にすると、より一層表面の乾燥性が悪くなるという問題がある。これらの欠点を補うためにワックスを添加したり、あるいは空乾性能を有する樹脂を併用しているのが現状である。 Resin such as unsaturated polyester resin and vinyl ester resin generally uses styrene monomer, and when used as a coating material or waterproof material, the odor of monomer evaporating from the coating surface during radical curing May be a problem. As a countermeasure, a monomer having a (meth) acryloyl group or a special monomer having low volatility is used. However, since oxygen in the air inhibits radical polymerization, there is a drawback that the drying property of the coating film surface is poor. In addition, in order to give followability to the base, if the concentration of double bonds is lowered, the reactivity is lowered and the tensile elongation of the cured resin is 10% or more, the dryness of the surface becomes even worse. There is a problem of becoming. In order to make up for these drawbacks, the present situation is that a wax is added or a resin having air drying performance is used in combination.
しかしながら、ワックスを添加すると、塗膜表面において空気を遮断する作用を有するため、空気乾燥性の向上に寄与する反面、硬化後も塗膜表面に存在し、塗膜の二次接着性及び外観などに影響を与えることが多い。また、空乾性能を有する樹脂を併用する技術が提案されている（例えば特許文献１〜６参照）が、これらの技術は、硬化時にラジカル重合性の空乾性成分の低分子量成分が残存しやすく、特に硬化物物性で伸び率を大きくするために二重結合濃度を低下させると、著しく表面硬化性が低下し、塗膜乾燥性が低下する問題が発生する。また、特に空乾性成分として極めて有効なアリルエーテル基を用いた場合には、金属石鹸との共存化では、その空乾性のために空気との接触部分からゲル化するなど貯蔵安定性に問題がある。 However, the addition of wax has the effect of blocking air on the surface of the coating film, which contributes to the improvement of air drying properties, but still exists on the coating film surface after curing, such as the secondary adhesion and appearance of the coating film. It often affects. Moreover, although the technique which uses together the resin which has air drying performance is proposed (for example, refer patent documents 1-6), the low molecular weight component of the radically polymerizable air-drying component tends to remain at the time of hardening in these techniques. In particular, when the double bond concentration is lowered in order to increase the elongation rate due to the physical properties of the cured product, the surface curability is remarkably lowered, and the problem that the coating film drying property is lowered occurs. In particular, when an allyl ether group, which is extremely effective as an air-drying component, is used, coexistence with a metal soap has a problem in storage stability, such as gelation from the contact area with air due to its air-drying property. is there.
本発明の目的は、硬化時の表面硬化性、塗膜乾燥性が良好で、かつ金属石鹸特にコバルト化合物共存下でも貯蔵安定性に優れ、下地追従性にも優れる硬化性樹脂組成物、および防水材組成物を提供することである。 An object of the present invention is to provide a curable resin composition that has good surface curability at the time of curing, drying of a coating film, excellent storage stability even in the presence of a metal soap, particularly a cobalt compound, and excellent base followability, and waterproofing. It is to provide a material composition.
本発明者らは、これらの課題について鋭意研究の結果、分子中に空乾性成分である環状脂肪族カルボン酸由来の構造単位及びジエチレングリコール由来の構造単位を有するポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート及びウレタン（メタ）アクリレートのいずれかの樹脂を用いると表面硬化性に優れ、かつコバルト化合物共存下での貯蔵安定性に優れ、伸び率が１０％以上の硬化性樹脂組成物が得られることを発見するに及んで、本発明を完成するに至ったものである。 As a result of intensive studies on these problems, the present inventors have found that a polyester (meth) acrylate and an epoxy (meth) having a structural unit derived from a cyclic aliphatic carboxylic acid and a structural unit derived from diethylene glycol, which are air-drying components, in the molecule. Use of a resin of either acrylate or urethane (meth) acrylate provides a curable resin composition having excellent surface curability, excellent storage stability in the presence of a cobalt compound, and an elongation of 10% or more. As a result, the present invention has been completed.
即ち、本発明は、両末端にそれぞれ１個の（メタ）アクリロイル基を有するポリエステル（メタ）アクリレート樹脂（Ａ）と（メタ）アクリロイル基を有する単量体（Ｂ）、金属石鹸及びワックスとを含有してなる樹脂組成物であって、前記樹脂（Ａ）が、分子中に一般式［１］で表される環状脂肪族不飽和二塩基酸由来の構造単位を含む二塩基酸由来の構造単位、及び一般式［２］で表される多価アルコール由来の構造単位を有し、かつ前記環状脂肪族不飽和二塩基酸由来の構造単位の割合が、二塩基酸由来の構造単位中の５〜４５モル％であり、前記樹脂（Ａ）が、前記一般式［１］で表される環状脂肪族不飽和二塩基酸を含む二塩基酸とジエチレングリコールとから得られるポリエステル樹脂の末端のカルボキシル基に、カルボキシル基と反応性の官能基及び（メタ）アクリロイル基を有する化合物を反応させることによって得られるものであり、前記単量体（Ｂ）がフェノキシエチルメタクリレートであることを特徴とする硬化性樹脂組成物を提供するものである。
That is, the present invention comprises a polyester (meth) acrylate resin (A) having one (meth) acryloyl group at both ends, a monomer (B) having a (meth) acryloyl group, a metal soap and a wax. A dibasic acid-derived structure, wherein the resin (A) contains a structural unit derived from a cyclic aliphatic unsaturated dibasic acid represented by the general formula [1] in the molecule. A unit having a structural unit derived from a polyhydric alcohol represented by the general formula [2], and the proportion of the structural unit derived from the cycloaliphatic unsaturated dibasic acid in the structural unit derived from the dibasic acid 5 to 45 mol% , and the resin (A) is a terminal carboxyl of a polyester resin obtained from a dibasic acid containing a cycloaliphatic unsaturated dibasic acid represented by the general formula [1] and diethylene glycol. Based on carboxyl A curable resin composition obtained by reacting a compound having a reactive functional group and a (meth) acryloyl group, wherein the monomer (B) is phenoxyethyl methacrylate. It is to provide.
また本発明は、前記硬化性樹脂組成物、金属石鹸及びワックスを含んでなる硬化性樹脂組成物を提供するものである。さらに前記硬化性樹脂組成物からなる防水材組成物を提供するものである。 The present invention also provides a curable resin composition comprising the curable resin composition, metal soap and wax. Furthermore, the waterproof material composition which consists of said curable resin composition is provided.
本発明の硬化性樹脂組成物は、伸び率が高く表面硬化性に優れることから、施工性に優れ、アスファルトやコンクリートに塗布することにより防水性能にすぐれる表面被覆層を提供するものである。 The curable resin composition of the present invention provides a surface coating layer that is excellent in workability due to its high elongation rate and excellent surface curability, and is excellent in waterproof performance when applied to asphalt or concrete.
次に本発明を詳細に説明する。
本発明は、分子中に一般式〔１〕で表される構造単位を含む二塩基酸由来の構造単位及び一般式〔２〕で表される構造単位を有する、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート及びウレタン（メタ）アクリレートからなる群から選ばれる少なくとも１種の樹脂（Ａ）と（メタ）アクリロイル基を有する単量体（Ｂ）とを含有してなる硬化性樹脂組成物に関するものである。
一般式〔１〕で表される構造単位は、環状脂肪族不飽和二塩基酸の残基であり、一般式［２］で表される構造単位は、ジエチレングリコール等の残基であり、前記ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート及びウレタン（メタ）アクリレートは、環状脂肪族不飽和二塩基酸およびジエチレングリコール等の多価アルコールを必須の原料とするものである。
前記ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート及びウレタン（メタ）アクリレートのうち、前記構造単位及び(メタ)アクリロイル基を分子中に高濃度に含ませることができ、本発明の効果を効率よく発揮できる点で、ポリエステル(メタ)アクリレートが好ましい。
Next, the present invention will be described in detail.
The present invention relates to a polyester (meth) acrylate, an epoxy (containing a structural unit derived from a dibasic acid containing a structural unit represented by the general formula [1] and a structural unit represented by the general formula [2] in the molecule. A curable resin composition comprising at least one resin (A) selected from the group consisting of (meth) acrylate and urethane (meth) acrylate and a monomer (B) having a (meth) acryloyl group It is.
The structural unit represented by the general formula [1] is a residue of a cycloaliphatic unsaturated dibasic acid, the structural unit represented by the general formula [2] is a residue such as diethylene glycol, and the polyester. (Meth) acrylates, epoxy (meth) acrylates and urethane (meth) acrylates use polyhydric alcohols such as cycloaliphatic unsaturated dibasic acids and diethylene glycol as essential raw materials.
Among the polyester (meth) acrylate, epoxy (meth) acrylate and urethane (meth) acrylate, the structural unit and (meth) acryloyl group can be contained in the molecule at a high concentration, and the effect of the present invention can be efficiently achieved. Polyester (meth) acrylate is preferable in that it can be exhibited.
まず本発明の硬化性樹脂組成物に使用するポリエステル(メタ)アクリレートについて説明する。
かかるポリエステル（メタ）アクリレートは、環状脂肪族不飽和二塩基酸及び飽和二塩基酸を含む二塩基酸とジエチレングリコールとから得られるポリエステル樹脂の末端のカルボキシル基に、カルボキシル基と反応性の官能基及び（メタ）アクリロイル基を有する化合物を反応させることにより得ることができる。
First, the polyester (meth) acrylate used in the curable resin composition of the present invention will be described.
Such a polyester (meth) acrylate has a carboxyl group-reactive functional group and a carboxyl group at the terminal of a polyester resin obtained from a dibasic acid containing a cycloaliphatic unsaturated dibasic acid and a saturated dibasic acid and diethylene glycol, and It can be obtained by reacting a compound having a (meth) acryloyl group.
かかる環状脂肪族不飽和二塩基酸としては、例えばテトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、α−テルピネン・無水マレイン酸付加物、トランス−ピペリレン・無水マレイン酸付加物等が挙げられる。これらのうちでも、空乾性付与の点で、一般式［１］におけるＲ１がメチル基で、Ｒ２、Ｒ３及びＲ４が水素原子である、メチルテトラヒドロ無水フタル酸が好ましい。 Examples of such cycloaliphatic unsaturated dibasic acids include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, α-terpinene / maleic anhydride adduct, trans-piperylene / maleic anhydride adduct Etc. Among these, methyltetrahydrophthalic anhydride in which R1 in the general formula [1] is a methyl group and R2, R3, and R4 are hydrogen atoms is preferable in terms of imparting air-drying property.
前記環状脂肪族不飽和二塩基酸及びその誘導体は、単独、又はその他のα，β−不飽和二塩基酸及び／または飽和二塩基酸を併用することができる。かかるその他のα，β−不飽和二塩基酸としては、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。また、飽和二塩基酸としては、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２−ドデカン２酸，２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４'−ビフェニルジカルボン酸、またこれらのジアルキルエステル等を挙げることができる。これらは、空乾性を阻害しない範囲で、単独でも２種類以上組み合わせて使用することができる。 The cycloaliphatic unsaturated dibasic acid and derivatives thereof may be used alone or in combination with other α, β-unsaturated dibasic acid and / or saturated dibasic acid. Examples of such other α, β-unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. The saturated dibasic acids include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid. Acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3- Examples include naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. These can be used alone or in combination of two or more, as long as the air-drying property is not inhibited.
また多価アルコールとしては、ジエチレングリコール、トリエチレングリコールおよびポリエチレングリコール等を挙げることができる。またこれらと併用できる多価アルコ−ル類としては、例えばプロピレングリコ−ル、ジプロピレングリコ−ル、ポリプロピレングリコ−ル、２−メチル−１，３−プロパンジオ−ル、１，３−ブタンジオ−ル、ネオペンチルグリコ−ル、水素化ビスフェノ−ルＡ、１，４−ブタンジオ−ル、ビスフェノ−ルＡとプロピレンオキシド又はエチレンオキシドの付加物、１，２，３，４−テトラヒドロキシブタン、グリセリン、トリメチロ−ルプロパン、１，３−プロパンジオ−ル、１，２−シクロヘキサングリコ−ル、１，３−シクロヘキサングリコ−ル、１，４−シクロヘキサングリコ−ル、１，４−シクロヘキサンジメタノ−ル、パラキシレングリコ−ル、ビシクロヘキシル−４，４'−ジオ−ル、２，６−デカリングリコ−ル、２，７−デカリングリコ−ル等を挙げることができる。 Examples of the polyhydric alcohol include diethylene glycol, triethylene glycol, and polyethylene glycol. Examples of polyhydric alcohols that can be used in combination with these include propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol. , Neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, Trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, P-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-deca Examples include phosphoglycol.
得られたポリエステルの末端のカルボキシル基に対して、（メタ）アクリロイル基を有し、かつカルボキシル基との反応性を有する官能基を有する化合物、例えば、グリシジル（メタ）アクリレートと反応させることによって、ポリエステル末端に（メタ）アクリロイル基を導入し、本発明の樹脂（Ａ）を得ることができる。 By reacting a carboxyl group at the terminal of the obtained polyester with a compound having a (meth) acryloyl group and a functional group having reactivity with the carboxyl group, for example, glycidyl (meth) acrylate, By introducing a (meth) acryloyl group into the polyester terminal, the resin (A) of the present invention can be obtained.
次に本発明に使用する樹脂（Ａ）として用いるエポキシ（メタ）アクリレートについて説明する。
かかるエポキシ(メタ)アクリレートは、エポキシ樹脂と環状脂肪族不飽和二塩基酸と（メタ）アクリロイル基を有する一塩基酸とジエチレングリコール等の多価アルコールとの反応生成物であって、末端に（メタ）アクリロイル基などの官能基を有するオリゴマーである。
Next, the epoxy (meth) acrylate used as the resin (A) used in the present invention will be described.
Such an epoxy (meth) acrylate is a reaction product of an epoxy resin, a cycloaliphatic unsaturated dibasic acid, a monobasic acid having a (meth) acryloyl group, and a polyhydric alcohol such as diethylene glycol. ) An oligomer having a functional group such as an acryloyl group.
エポキシ（メタ）アクリレートの原料として使用できるエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、臭素化エポキシ樹脂などの多価フェノール類のグリシジルエーテル類、ビスフェノールＡのアルキレンオキサイド付加物のジグリシジルエーテル、水素化ビスフェノールＡのジグリシジルエーテルなどの多価アルコールのグリシジルエーテル、ヘキサヒドロフタル酸ジグリシジルエステルなどのグリシジルエステル類、テトラグリシジルジアミノジフェニルメタンなどのグリシジルアミン類、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂などが挙げられる。これらのエポキシ樹脂は単独もしくは２種以上を併用してもよい。 Epoxy resins that can be used as raw materials for epoxy (meth) acrylates include bisphenol A type epoxy resins, biphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and brominated epoxy resins such as glycidyl polyhydric phenols. Ethers, diglycidyl ethers of bisphenol A alkylene oxide adducts, glycidyl ethers of polyhydric alcohols such as diglycidyl ether of hydrogenated bisphenol A, glycidyl esters such as diglycidyl hexahydrophthalate, tetraglycidyl diaminodiphenylmethane, etc. And heterocyclic epoxy resins such as glycidylamines and triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more.
環状脂肪族不飽和二塩基酸としては、前記のポリエステル（メタ）アクリレートの原料として記載したものを使用することができる。
また、前記した（メタ）アクリロイル基を有する一塩基酸としては、アクリル酸、メタクリル酸等が挙げられ、これらを単独又は２種以上を併用して用いられる。
As a cycloaliphatic unsaturated dibasic acid, what was described as a raw material of the said polyester (meth) acrylate can be used.
Moreover, acrylic acid, methacrylic acid, etc. are mentioned as a monobasic acid which has an above described (meth) acryloyl group, These are used individually or in combination of 2 or more types.
本発明に使用する樹脂（Ａ）として用いるウレタン（メタ）アクリレートは、ポリイソシアネートと水酸基を含有する（メタ）アクリレートと環状脂肪族不飽和二塩基酸および多価アルコールを原料とするポリエステルポリオールとを反応させて得られる化合物である。この化合物は、末端に（メタ）アクリロイル基などの官能基を有するオリゴマーである。 The urethane (meth) acrylate used as the resin (A) used in the present invention is a polyisocyanate, a (meth) acrylate containing a hydroxyl group, a cyclic polyol unsaturated dibasic acid, and a polyester polyol made from a polyhydric alcohol. It is a compound obtained by reacting. This compound is an oligomer having a functional group such as a (meth) acryloyl group at the terminal.
またポリイソシアネートとしては、例えば１，６−ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート、１，４−シクロヘキサンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、ノルボルネンジイソシアネート等が挙げられる。また各種イソシアネート化合物をイソシアヌレート化せしめて得られるイソシアヌレート化合物も挙げられる。これらは単独もしくは２種以上を併せて用いられる。 Examples of the polyisocyanate include 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4 ′. -Dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate and the like. Moreover, the isocyanurate compound obtained by making various isocyanate compounds isocyanurate is also mentioned. These may be used alone or in combination of two or more.
水酸基を含有する（メタ）アクリレートとしては、例えばヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、グリセリンジ（メタ）アクリレ−ト、ペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。これらは単独もしくは２種以上を併せて用いられる。
ポリエステルポリオールの原料である環状脂肪族不飽和二塩基酸および多価アルコールは、前記で掲げたものを使用することができる。
Examples of the (meth) acrylate containing a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. These may be used alone or in combination of two or more.
As the cycloaliphatic unsaturated dibasic acid and polyhydric alcohol, which are raw materials for the polyester polyol, those listed above can be used.
本発明の硬化性樹脂組成物の樹脂（Ａ）の数平均分子量は３００〜１０,０００であり、このうち硬化物の物性の点で、５００〜５,０００のものが好ましい。 The number average molecular weight of the resin (A) of the curable resin composition of the present invention is 300 to 10,000, and among these, those having a physical property of the cured product of 500 to 5,000 are preferable.
さらに本発明は、前記樹脂（Ａ）中の環状脂肪族不飽和二塩基酸由来の構造単位の割合が二塩基酸由来の構造単位中の５〜５０モル％未満であることが特徴である。このうち、１０〜４０モル％であることが好ましい。
環状脂肪族不飽和二塩基酸の含有量が、５〜５０モル％未満であれば、塗膜の乾燥性に優れるものとなる。
Furthermore, this invention is characterized by the ratio of the structural unit derived from the cycloaliphatic unsaturated dibasic acid in the said resin (A) being less than 5-50 mol% in the structural unit derived from a dibasic acid. Among these, it is preferable that it is 10-40 mol%.
If content of cycloaliphatic unsaturated dibasic acid is less than 5-50 mol%, it will be excellent in the drying property of a coating film.
本発明に使用される樹脂（Ａ）に、分子量が３００以上の樹脂としてエチレン性不飽和二重結合を有する樹脂を、空乾性を阻害させない範囲で併用することができる。
かかるエチレン性不飽和二重結合を有する樹脂としては、特に限定されるものではないが、例えば、エポキシ樹脂と（メタ）アクリル酸から得られる、前記の本発明に用いるエポキシ（メタ）アクリレート以外のエポキシ（メタ）アクリレート、ポリオール、二官能イソシアネートおよび水酸基とメタクリレートとを有するβ−ヒドロキシエチルメタクリレートから得られる、前記の本発明に用いるウレタン（メタ）アクリレート以外のウレタン(メタ)アクリレート、前記本発明に用いられるポリエステル（メタ）アクリレート以外のポリエステル（メタ）アクリレート、さらにマレイン酸エステルおよびフマル酸エステルから得られる不飽和ポリエステルが挙げられる。これらの樹脂の使用割合は、通常樹脂中の５０重量％以下であるが、２０重量％未満の使用が好ましい。
In the resin (A) used in the present invention, a resin having an ethylenically unsaturated double bond as a resin having a molecular weight of 300 or more can be used in combination as long as air drying is not inhibited.
Such a resin having an ethylenically unsaturated double bond is not particularly limited. For example, a resin other than the epoxy (meth) acrylate used in the present invention, obtained from an epoxy resin and (meth) acrylic acid. Urethane (meth) acrylate other than urethane (meth) acrylate used in the present invention, obtained from epoxy (meth) acrylate, polyol, bifunctional isocyanate and β-hydroxyethyl methacrylate having hydroxyl group and methacrylate, in the present invention Examples include polyesters (meth) acrylates other than the polyester (meth) acrylates used, and unsaturated polyesters obtained from maleic acid esters and fumaric acid esters. The use ratio of these resins is usually 50% by weight or less in the resin, but use of less than 20% by weight is preferable.
本発明に使用される（メタ）アクリロイル基を有する単量体（Ｂ）とは、分子内にラジカル重合反応性の（メタ）アクリロイル基を有する所謂反応性希釈モノマーをいう。具体的には、アクリル酸エステル、メタクリル酸エステル等；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸トリデシル、ジシクロペンテニロキシエチル（メタ）アクリレート、エチレングリコールモノメチルエーテル（メタ）アクリレート、エチレングリコールモノエチルエーテル（メタ）アクリレート、エチレングリコールモノブチルエーテル（メタ）アクリレート、エチレングリコールモノヘキシルエーテル（メタ）アクリレート、エチレングリコールモノ２ーエチルヘキシルエーテル（メタ）アクリレート、ジエチレングリコールモノメチルエーテル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、ジエチレングリコールモノブチルエーテル（メタ）アクリレート、ジエチレングリコールモノヘキシルエーテル（メタ）アクリレート、ジエチレングリコールモノ２ーエチルヘキシルエーテル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコ-ルジ（メタ）アクリレ-ト、ポリテトラメチレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２−ヒドロキシ１，３ジメタクリロキシプロパン、イソシアヌル酸ＥＯ変性ジアクリレート、ペンタエリスリトールジアクリレートモノステアレート等の分子内に不飽和二重結合を有するモノマー或いはそれらのオリゴマー等が挙げられる。
これらの単量体のうち、硬化反応性、組成物の粘度の点で、炭素原子数が１〜５の(メタ)アクリル酸エステルが好ましい。
The monomer (B) having a (meth) acryloyl group used in the present invention refers to a so-called reactive dilution monomer having a radical polymerization reactive (meth) acryloyl group in the molecule. Specifically, acrylic acid ester, methacrylic acid ester and the like; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic T-butyl acid, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate , Ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2 -Ethylhexyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1, Examples thereof include monomers having an unsaturated double bond in the molecule, such as 3-dimethacryloxypropane, isocyanuric acid EO-modified diacrylate, pentaerythritol diacrylate monostearate, and oligomers thereof.
Of these monomers, (meth) acrylic acid esters having 1 to 5 carbon atoms are preferred in view of curing reactivity and the viscosity of the composition.
さらに、臭気の点で問題とならない範囲で、前記単量体（Ｂ）に、スチレン、α-メチルスチレン、クロルスチレン、ジクロルスチレン、ジビニルベンゼン、t-ブチルスチレン、ビニルトルエン、酢酸ビニル、ジアリールフタレ-ト、トリアリールシアヌレ-ト等を併用することもできる。 In addition, styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, and diaryl are added to the monomer (B) within a range that does not cause a problem in terms of odor. Phthalate, triaryl cyanurate, etc. can be used in combination.
また前記した単量体（Ｂ）に、低臭性の目的で、炭素原子数が１〜４のアルキル基を有するヒドロキシアルキル（メタ）アクリレート、フェニル基を有する重合性単量体を併用して用いることができる。
炭素原子数が１〜４のアルキル基を有するヒドロキシアルキル（メタ）アクリレートとしては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート等が挙げられる。
In addition, for the purpose of low odor, the monomer (B) is used in combination with a hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms and a polymerizable monomer having a phenyl group. Can be used.
Examples of the hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. Can be mentioned.
フェニル基を有する単量体としては、例えばフェニル基を有する分子量が１８０以上の（メタ）アクリロイル基を有するアクリル系単量体が好ましく用いられる。かかる単量体の具体例としてフェノキシエチルメタアクリレート、フェノールエチレンオキサイド（ＥＯ）変性アクリレート、ノニルフェニルカルビトールアクリレート、ノニルフェノールＥＯ変性アクリレート、フェノキシプロピルアクリレート、ノニルフェノールＰＯ変性アクリレート、アクリロイルオキシエチルフタレート、フェノールＥＯ変性メタクリレート、ノニルフェニルカルビトールメタクリレート、ノニルフェノールＥＯ変性メタクリレート、フェノキシプロピルメタクリレート、フェノールＰＯ変性メタクリレート、ノニルフェノキシプロピルメタクリレート、ノニルフェノールＰＯ変性メタクリレート、メタクリロイルオキシエチルフタレート等が挙げられる。 As the monomer having a phenyl group, for example, an acrylic monomer having a (meth) acryloyl group having a phenyl group and a molecular weight of 180 or more is preferably used. Specific examples of such monomers include phenoxyethyl methacrylate, phenol ethylene oxide (EO) modified acrylate, nonylphenyl carbitol acrylate, nonylphenol EO modified acrylate, phenoxypropyl acrylate, nonylphenol PO modified acrylate, acryloyloxyethyl phthalate, phenol EO modified. Examples include methacrylate, nonylphenyl carbitol methacrylate, nonylphenol EO-modified methacrylate, phenoxypropyl methacrylate, phenol PO-modified methacrylate, nonylphenoxypropyl methacrylate, nonylphenol PO-modified methacrylate, methacryloyloxyethyl phthalate, and the like.
さらには、本発明の樹脂組成物の硬化物の表面乾燥性を向上させるため、本発明の効果を損なわない範囲で各種の化合物を用いることができる。かかる化合物としては、例えばジシクロペンタジエン、ジシクロデカンまたはトリアジンの如き各種誘導体類、ジシクロペンテニルアクリレート、ジシクロペンテニルオキシエチルアクリレート、トリシクロデカニルアクリレート、トリシクロデカニルメタアクリレートまたはトリス（２−ヒドロキシエチル）イソシアヌルアクリレート等が挙げられる。 Furthermore, in order to improve the surface drying property of the cured product of the resin composition of the present invention, various compounds can be used as long as the effects of the present invention are not impaired. Such compounds include, for example, various derivatives such as dicyclopentadiene, dicyclodecane or triazine, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate or tris (2-hydroxyethyl). ) Isocyanuric acrylate and the like.
また本発明の硬化性樹脂組成物には、必要に応じて、重合禁止剤、硬化促進剤、ラジカル硬化剤等を使用することができる。 Moreover, a polymerization inhibitor, a hardening accelerator, a radical hardening agent, etc. can be used for the curable resin composition of this invention as needed.
かかる重合禁止剤としては、例えばトリハイドロベンゼン、トルハイドロキノン、１４−ナフトキノン、パラベンゾキノン、ハイドロキノン、ベンゾキノン、ハイドロキノンモノメチルエーテル、ｐ−ｔｅｒｔ−ブチルカテコール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−１−オキシル等のピペリジン誘導体等を挙げることができ、これらを単独又は２種以上の組み合わせて使用することができる。重合禁止剤は、本発明の硬化性樹脂組成物に、１０〜１０００ｐｐｍ添加することが好ましい。 Examples of such polymerization inhibitors include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methyl. Examples thereof include piperidine derivatives such as phenol and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, and these can be used alone or in combination of two or more. It is preferable to add 10 to 1000 ppm of the polymerization inhibitor to the curable resin composition of the present invention.
かかる硬化促進剤としては、例えばバナジウムアセチルアセテート、コバルトアセチルアセテート、鉄アセチルアセトネート等の金属キレート類が挙げられる。 Examples of the curing accelerator include metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate.
ラジカル硬化剤としては、熱硬化剤や光硬化剤が挙げられる。熱硬化剤としては、有機過酸化物が挙げられ、具体的にはメチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイド、ベンゾイルパーオキサイド等公知公用のものが挙げられる。熱硬化剤の添加量は、好ましくは樹脂組成物の合計量１００重量部に対して、０．５〜５重量部である。 Examples of the radical curing agent include a thermosetting agent and a photocuring agent. Examples of the thermosetting agent include organic peroxides, and specific examples include known and publicly used ones such as methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and benzoyl peroxide. The addition amount of the thermosetting agent is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total amount of the resin composition.
またかかる光硬化剤としては、例としてベンゾインアルキルエーテルのようなベンゾインエーテル系、ベンゾフェノン、ベンジル、メチルオルソベンゾイルベンゾエートなどのベンゾフェノン系、ベンジルジメチルケタール、２，２−ジエトキシアセトフェノン、２−ヒドロキシ−２−メチルプロピオフェノン、４−イソプロピル−２−ヒドロキシ−２−メチルプロピオフェノン、１，１−ジクロロアセトフェノンなどのアセトフェノン系、２−クロロチオキサントン、２−メチルチオキサントン、２−イソプロピルチオキサントンなどのチオキサントン系等が挙げられる。光硬化剤の添加量は、好ましくは本発明に用いられる樹脂の合計量１００重量部に対して、０．１〜３重量部である。 Examples of such photocuring agents include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2. -Acetophenone series such as methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, thioxanthone series such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Etc. The addition amount of the photocuring agent is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the resin used in the present invention.
本発明の硬化性樹脂組成物は、前記樹脂（Ａ）と（メタ）アクリロイル基を有する単量体（Ｂ）のほか、さらに金属石鹸及びワックスを含むものであるのが好ましい。
かかる金属石鹸として、一般的に硬化促進剤、ドライヤーとして用いられるものであれば特に限定されるものではない。溶解性および硬化性の点から、例えばナフテン酸コバルト、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸バナジウム、ナフテン酸銅、ナフテン酸バリウム等が好ましい。
The curable resin composition of the present invention preferably contains a metal soap and wax in addition to the resin (A) and the monomer (B) having a (meth) acryloyl group.
The metal soap is not particularly limited as long as it is generally used as a curing accelerator and a dryer. From the viewpoint of solubility and curability, for example, cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate and the like are preferable.
前記ワックスとしては、パラフィンワックス、ポリエチレンワックスやステアリン酸、１，２−ヒドロキシステアリン酸等の高級脂肪酸等が挙げられるが、好ましくはパラフィンワックスが用いられる。 Examples of the wax include higher fatty acids such as paraffin wax, polyethylene wax, stearic acid, and 1,2-hydroxystearic acid. Preferably, paraffin wax is used.
また本発明の硬化性樹脂組成物は、さらにアミンを含むことができる。アミンとしては、アニリン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ビス（２-ヒドロキシエチル）−ｐ−トルイジン、4-（Ｎ，Ｎ−ジメチルアミノ）ベンズアルデヒド、４−［Ｎ，Ｎ−ビス（２-ヒドロキシエチル）アミノ］ベンズアルデヒド、４−（Ｎ−メチル−Ｎ−ヒドロキシエチルアミノ）ベンズアルデヒド、Ｎ，Ｎ−ビス（２−ヒドロキシプロピル）−ｐ−トルイジン、Ｎ−エチル−ｍ−トルイジン、トリエタノールアミン、ｍ−トルイジン、ジエチレントリアミン、Ｎ，Ｎ−ジメチルアセトアセトアミド、ジメチルピリジン、フェニリモルホリン、ピペリジン、Ｎ，Ｎ−ビス（ヒドロキシエチル）アニリン、ジエタノールアニリン等のＮ，Ｎ−置換アニリン、Ｎ，Ｎ−置換−ｐ−トルイジン、4-（Ｎ，Ｎ−置換アミノ）ベンズアルデヒド等が挙げられる。 Moreover, the curable resin composition of this invention can contain an amine further. Examples of the amine include aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, N, N-dimethylacetoacetamide, dimethylpyridine, phenylmorpholine, piperidine, N, N- N, N-substituted amines such as bis (hydroxyethyl) aniline and diethanolaniline Nilin, N, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde and the like can be mentioned.
さらに本発明の硬化性樹脂組成物は、土木建築用として使用することができる。この場合、例えば充填剤、チキソ剤、チキソ助剤、紫外線吸収剤、顔料、減粘剤等の粘度調節剤、低収縮化剤、老化防止剤、可塑剤、難燃剤、安定剤、消泡剤、レベリング剤、シランカップリング剤等の各種添加剤を使用することができる。 Furthermore, the curable resin composition of the present invention can be used for civil engineering and construction. In this case, for example, viscosity modifiers such as fillers, thixotropic agents, thixotropic agents, ultraviolet absorbers, pigments, thinning agents, low shrinkage agents, anti-aging agents, plasticizers, flame retardants, stabilizers, antifoaming agents. Various additives such as a leveling agent and a silane coupling agent can be used.
かかる充填剤としては、例えば水硬性ケイ酸塩材料、炭酸カルシウム粉、クレー、アルミナ粉、硅石粉、タルク、硫酸バリウム、シリカパウダー、ガラス粉、ガラスビーズ、マイカ、水酸化アルミニウム、セルロース系、硅砂、川砂、寒水石、大理石屑、砕石等が挙げられる。これらのうち、硬化時の半透明性を考慮すると、好ましくは水酸化アルミニウム、ガラス粉および炭酸カルシウムである。 Examples of such fillers include hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, aragonite powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose-based, and cinnabar. , River sand, cold water stone, marble waste, crushed stone and the like. Of these, aluminum hydroxide, glass powder, and calcium carbonate are preferred in consideration of translucency during curing.
かかるチキソ剤としては、例えばヒュームドシリカ等のシリカ粉末、アスベスト、スメクタイト、硫酸カルシウムウィスカー等が挙げられる。必要に応じて前記の２種以上を併用しても良い。チキソ剤の市販品としては、レオロシールＱＳシリーズ（ヒュームドシリカ、（株）トクヤマ製）、アエロジルシリーズ（ヒュームドシリカ、日本アエロジル（株）社製）ＢＥＮＡＴＨＩＸシリーズ（ヒュームドシリカ、ウィルバーエリス社製、ＣＡＢＯＳＩＬシリーズ（ヒュームドシリカ、ＣＡＢＯＴ社製、ＨＤＫシリーズ（ヒュームドシリカ、ＷＡＣＫＥＲ社製）等が使用できる。 Examples of such thixotropic agents include silica powder such as fumed silica, asbestos, smectite, calcium sulfate whisker and the like. If necessary, two or more of the above may be used in combination. Commercially available thixotropic agents include Leolosil QS series (fumed silica, manufactured by Tokuyama Co., Ltd.), Aerosil series (fumed silica, manufactured by Nippon Aerosil Co., Ltd.) BENATHIX series (fumed silica, manufactured by Wilber Ellis, The CABOSIL series (fumed silica, manufactured by CABOT, HDK series (fumed silica, manufactured by WACKER)) and the like can be used.
かかる顔料としては、たとえばチタンホワイト、カーボンブラック等無機顔料類やフタロシアニンブルー、キナクリドンレッド等有機顔料類があり、色相に応じて、種々の着色剤を用いることができる。
また、建築用被覆材としても、スプレー工法、ローラー工法により、アスファルトやコンクリート下地に対して直接塗布することができる。またこの作業は、冬季においても、空乾性に優れることから短時間で施工でき、作業性に優れるものである。
Examples of such pigments include inorganic pigments such as titanium white and carbon black, and organic pigments such as phthalocyanine blue and quinacridone red, and various colorants can be used depending on the hue.
Moreover, it can apply | coat directly with respect to asphalt or a concrete foundation | substrate by the spray method and a roller method as a coating material for construction. In addition, this work can be performed in a short time since it is excellent in air-drying even in winter, and is excellent in workability.
また、高い伸び率を有する樹脂でありながら、空気酸化反応による表面乾燥性が優れている点から、土木建築材として、砂利、砕石等の骨材、セラミック骨材、その他硅砂、天然石、木材等と混合して、硬化性および柔軟性に優れるモルタル、レジンコンクリートに用いることもできる。
これら土木建築用被覆材および土木建築材にベンゾイルパーオキサイド等の硬化剤を添加して硬化させた土木建築物は耐久性に優れるものである。
In addition, although it is a resin with a high elongation rate, it has excellent surface dryness by air oxidation reaction, so as civil engineering and construction materials, aggregates such as gravel and crushed stone, ceramic aggregates, other dredged sand, natural stone, wood, etc. And can be used for mortar and resin concrete having excellent curability and flexibility.
Civil engineering buildings obtained by adding a curing agent such as benzoyl peroxide to these civil engineering building covering materials and civil engineering construction materials and curing them are excellent in durability.
本発明の硬化性樹脂組成物の硬化物は、アスファルトやコンクリート等の下地に対する追従性および耐久性の点で、引張強度が５ＭＰａ以上であり、引張伸び率が１０％以上であることが好ましい。 The cured product of the curable resin composition of the present invention preferably has a tensile strength of 5 MPa or more and a tensile elongation of 10% or more from the viewpoint of followability and durability with respect to the base such as asphalt or concrete.
本発明の防水材組成物は、前記硬化性樹脂組成物からなるものである。かかる防水材組成物は、アスファルトやコンクリートへの追従性に優れ、防水用ガラスマット＃３８０、＃４５０等に含浸させＦＲＰ防水層とすることができる。 The waterproofing material composition of the present invention comprises the curable resin composition. Such a waterproof material composition has excellent followability to asphalt and concrete and can be impregnated into a waterproof glass mat # 380, # 450 or the like to form an FRP waterproof layer.
以下、本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また、文中「部」及び「％」とあるのは、特段の断りがない限り重量基準のものである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Further, “parts” and “%” in the text are based on weight unless otherwise specified.
実施例１、２及び３
無水フタル酸（以下ＰＡという）、ジエチレングリコール（以下ＤＥＧという）およびシス−３−メチル−４−シクロヘキセン−シス−１，２−ジカルボキシリックアンハイドライド（以下ＰＭＡＡという）を温度計、攪拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに仕込み、エステル化触媒としてジブチルチンオキサイドを０．０５重量％添加し、２０５℃で反応させた。 ２０５℃での反応時間は実施例１で２時間、実施例２で３時間、実施例３で１５時間とした、その後、１４０℃まで冷却し、次いでグリシジルメタクリレート（以下ＧＭＡという）を所定量投入し、３時間反応させた後、６０℃まで冷却してから反応性モノマーとしてフェノキシエチルメタクリレート（以下ＰｈＯＥＭＡという）を投入し、樹脂組成物を得た。
ＰｈＯＥＭＡの投入量は実施例１で５０％、実施例２で４０％、実施例３で６０％とし、この樹脂組成物のうち実施例３で得られた組成物を組成物ａとした。
Examples 1, 2 and 3
Phthalic anhydride (hereinafter referred to as PA), diethylene glycol (hereinafter referred to as DEG) and cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxyl anhydride (hereinafter referred to as PMAA) are thermometer, stirrer, inert Into a four-necked flask equipped with a gas inlet and a reflux condenser, 0.05% by weight of dibutyltin oxide was added as an esterification catalyst and reacted at 205 ° C. The reaction time at 205 ° C. was 2 hours in Example 1, 3 hours in Example 2, and 15 hours in Example 3. Thereafter, the reaction was cooled to 140 ° C., and then a predetermined amount of glycidyl methacrylate (hereinafter referred to as GMA) was added. Then, after reacting for 3 hours, after cooling to 60 ° C., phenoxyethyl methacrylate (hereinafter referred to as PhOEMA) was added as a reactive monomer to obtain a resin composition.
The input amount of PhOEMA was 50% in Example 1, 40% in Example 2, and 60% in Example 3. Among these resin compositions, the composition obtained in Example 3 was used as Composition a.
比較例１
実施例１と同様の装置、触媒量にて、ＰＡとＤＥＧとを３時間反応させた後、その後、１４０℃でＧＭＡを所定量投入し、３時間反応させた後、６０℃まで冷却し、反応性モノマーとしてＰｈＯＥＭＡを所定量投入し樹脂組成物を得た。
比較例２
実施例１と同様の装置、触媒量にて、ＰＡとＤＥＧおよびＰＭＡＡとを１５時間反応させた後、その後、１４０℃でＧＭＡを所定量投入し、３時間反応させた後、６０℃まで冷却し、反応性モノマーとしてＰｈＯＥＭＡを所定量投入し樹脂組成物を得た。
Comparative Example 1
After reacting PA and DEG for 3 hours in the same apparatus and catalyst amount as in Example 1, after that, a predetermined amount of GMA was added at 140 ° C. and reacted for 3 hours, and then cooled to 60 ° C., A predetermined amount of PhOEMA was added as a reactive monomer to obtain a resin composition.
Comparative Example 2
After reacting PA, DEG, and PMAA for 15 hours in the same apparatus and catalyst amount as in Example 1, then add a predetermined amount of GMA at 140 ° C., react for 3 hours, and cool to 60 ° C. A predetermined amount of PhOEMA was added as a reactive monomer to obtain a resin composition.
合成例１［エポキシメタクリレート樹脂（組成物ｂ）の調製］
温度計、攪拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコにビスフェノールＡとエピクロルヒドリンとの反応により得られたエポキシ当量が１８５なるエピクロン８５０（大日本インキ化学工業（株）製）１８５０ｇ、メタクリル酸８６０ｇ、ハイドロキノン１．３６ｇおよびトリエチルアミン１０．８ｇを仕込み、１２０℃まで昇温させ、同温度で１０時間反応させ、酸価３．５のエポキシアクリレートとした。これにＰｈＯＥＭＡを投入し、エポキシメタクリレート樹脂組成物を得た。ＰｈＯＥＭＡの投入量は６０％とし、この組成物を組成物ｂとした。
Synthesis Example 1 [Preparation of epoxy methacrylate resin (composition b)]
Epicron 850 having an epoxy equivalent of 185 obtained by the reaction of bisphenol A and epichlorohydrin in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser (Dainippon Ink Chemical Co., Ltd.) 1850 g, 860 g of methacrylic acid, 1.36 g of hydroquinone and 10.8 g of triethylamine were charged, the temperature was raised to 120 ° C., and the mixture was reacted at the same temperature for 10 hours to obtain an epoxy acrylate having an acid value of 3.5. PhOEMA was added thereto to obtain an epoxy methacrylate resin composition. The input amount of PhOEMA was 60%, and this composition was designated as composition b.
合成例２［ウレタンメタクリレート樹脂組成物（組成物ｃ）の調製］
温度計、攪拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに数平均分子量１０００のプロピレングリコール（ＰＰＧ）５００ｇとトリレンジイソシアネート（ＴＤＩ）１７４ｇを仕込み窒素気流下８０℃で４時間反応させた。ＮＣＯ当量が６００とほぼ理論当量値になったので、５０℃まで冷却した。空気気流下でハイドロキノン０．０７ｇを加え、９０℃で５時間反応を続け、ＮＣＯ％が０．１％以下のウレタンアクリレートを得た。これにＰｈＯＥＭＡを投入し、ウレタンアクリレート樹脂組成物を得た。ＰｈＯＥＭＡの投入量は６０％とし、この組成物を組成物ｃとする。
Synthesis Example 2 [Preparation of urethane methacrylate resin composition (composition c)]
A four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser was charged with 500 g of propylene glycol (PPG) having a number average molecular weight of 1000 and 174 g of tolylene diisocyanate (TDI) at 80 ° C. for 4 hours under a nitrogen stream. Reacted. Since the NCO equivalent was almost theoretical equivalent to 600, it was cooled to 50 ° C. Under an air stream, 0.07 g of hydroquinone was added, and the reaction was continued at 90 ° C. for 5 hours to obtain a urethane acrylate having an NCO% of 0.1% or less. PhOEMA was added thereto to obtain a urethane acrylate resin composition. The input amount of PhOEMA is 60%, and this composition is designated as composition c.
ＤＥＧ：ジエチレングリコール
ＰＡ：無水フタル酸
ＰＭＡＡ：シス−３−メチル−４−シクロヘキセン−シス−１，２−ジカルボキシリックアンハイドライド（メチルテトラヒドロ無水フタル酸）
ＧＭＡ：グリシジルメタクリレート
ＰｈＯＥＭＡ：フェノキシエチルメタクリレート
DEG: diethylene glycol PA: phthalic anhydride PMAA: cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic anhydride (methyltetrahydrophthalic anhydride)
GMA: Glycidyl methacrylate PhOEMA: Phenoxyethyl methacrylate
＜測定方法及び評価基準＞
乾燥時間：実施例及び比較例で得られた樹脂組成物を下記配合にて、２５℃条件下で塗布厚み０．２５ｍｍでガラス板上に塗装した後、指で触わったとき乾燥したと認められる時間（分）
塗装時の配合条件：硬化促進剤 ８％オクチル酸コバルト １．０％
空乾性助剤 パラフィンワックス（１１５〜１３０°Ｆ）０．１％
硬化剤 ５５％メチルエチルケトンパーオキサイド １．０％
貯蔵安定性：実施例及び比較例で得られた樹脂組成物を下記配合にて、５０℃条件下で
長期保管した場合に、樹脂中にゲル物が発生するまでの日数
試験時の配合条件：
硬化遅延剤 ２，６−ジターシャリーブチル−４−メチルフェノール ０．０５％ 硬化促進剤 ８％オクチル酸コバルト １．０％
空乾性助剤 パラフィンワックス（１１５〜１３０°Ｆ） ０．１％
引張強度及び伸び率：実施例で得られた樹脂組成物を試料として、ＪＩＳ Ｋ７１１３に準じて測定した。
<Measurement method and evaluation criteria>
Drying time: The resin compositions obtained in the examples and comparative examples were coated on a glass plate with the following composition at a coating thickness of 0.25 mm under the conditions of 25 ° C. Time (minutes)
Blending conditions at the time of painting: Curing accelerator 8% Cobalt octylate 1.0%
Air-drying aid Paraffin wax (115-130 ° F) 0.1%
Curing agent 55% Methyl ethyl ketone peroxide 1.0%
Storage stability: When the resin compositions obtained in Examples and Comparative Examples are stored for a long time under the following blending conditions at 50 ° C., blending conditions at the time test until a gel product is generated in the resin:
Curing retarder 2,6-ditertiary butyl-4-methylphenol 0.05% Curing accelerator 8% Cobalt octylate 1.0%
Air-drying aid Paraffin wax (115-130 ° F) 0.1%
Tensile strength and elongation: The resin composition obtained in the examples was used as a sample and measured according to JIS K7113.
実施例４ ＦＲＰ防水ライニング
旭コンクリート（株）製ＪＩＳ規格歩道用コンクリート平板（３００×３００×６０ｍｍ）の表面を＃６０でサンディングし、その上にプライマーＰＤ（一液湿気硬化型ウレタン、大日本インキ化学工業株式会社製）を０．２ｋｇｆ／ｍ２塗布し乾燥させ、その上に実施例１，２及び３で得た樹脂組成物に硬化促進剤、８％オクチル酸コバルト１．０％、空乾性助剤、パラフィンワックス（１１５〜１３０°Ｆ）０．１％、硬化剤、５５％メチルエチルケトンパーオキサイド１．０％を配合したものをローラにて塗布した後、防水用ガラスマット＃４５０に含浸、脱泡させ、ＦＲＰ防水層とした。含浸、脱泡終了後、約６０分以内に硬化、乾燥することにより、良好なＦＲＰ防水層が得られた。
Example 4 FRP waterproof lining The surface of a JIS standard sidewalk concrete plate (300 × 300 × 60 mm) manufactured by Asahi Concrete Co., Ltd. was sanded with # 60, and then primer PD (one-component moisture-curing urethane, Dainippon Ink, Ltd.) Chemical Industries Co., Ltd.) was applied 0.2kgf / m 2 and dried, on which the resin compositions obtained in Examples 1, 2 and 3 were added to a curing accelerator, 1.0% cobalt octylate 1.0%, empty Drying aid, paraffin wax (115-130 ° F) 0.1%, curing agent, 55% methyl ethyl ketone peroxide 1.0% blended with a roller and then impregnated into a waterproof glass mat # 450 And defoamed to obtain an FRP waterproof layer. After completion of impregnation and defoaming, a good FRP waterproof layer was obtained by curing and drying within about 60 minutes.
Claims (3)
前記樹脂（Ａ）が、分子中に一般式［１］で表される環状脂肪族不飽和二塩基酸由来の構造単位を含む二塩基酸由来の構造単位、及び一般式［２］で表される多価アルコール由来の構造単位を有し、
かつ前記環状脂肪族不飽和二塩基酸由来の構造単位の割合が、二塩基酸由来の構造単位中の５〜４５モル％であり、
前記樹脂（Ａ）が、前記一般式［１］で表される環状脂肪族不飽和二塩基酸を含む二塩基酸とジエチレングリコールとから得られるポリエステル樹脂の末端のカルボキシル基に、カルボキシル基と反応性の官能基及び（メタ）アクリロイル基を有する化合物を反応させることによって得られるものであり、
前記単量体（Ｂ）がフェノキシエチルメタクリレートであることを特徴とする硬化性樹脂組成物。
ルキル基を表す。）
The resin (A) is represented by a structural unit derived from a dibasic acid including a structural unit derived from a cycloaliphatic unsaturated dibasic acid represented by the general formula [1] in the molecule, and the general formula [2]. Having a structural unit derived from polyhydric alcohol,
And the ratio of the structural unit derived from the said cycloaliphatic unsaturated dibasic acid is 5-45 mol% in the structural unit derived from a dibasic acid,
The resin (A) is reactive with a carboxyl group at the terminal carboxyl group of a polyester resin obtained from a dibasic acid containing a cycloaliphatic unsaturated dibasic acid represented by the general formula [1] and diethylene glycol. It is obtained by reacting a compound having a functional group and a (meth) acryloyl group,
A curable resin composition, wherein the monomer (B) is phenoxyethyl methacrylate.
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| WO2011101968A1 (en) * | 2010-02-18 | 2011-08-25 | Dic株式会社 | Polyester (meth)acrylate resin composition, coated structure, and method for constructing same |
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| KR101185166B1 (en) | 2012-06-25 | 2012-09-25 | 우리개발주식회사 | Self-propelled steel aggregate parking lot room temperature curing type eco-friendly waterproof and anti-slip flooring composition |
| JP2016029125A (en) * | 2014-07-25 | 2016-03-03 | 昭和電工株式会社 | Two-pack curable resin composition, covering material, covering method and covering structure |
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