JP5484804B2 - Resin composition and method of use - Google Patents
Resin composition and method of use Download PDFInfo
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- JP5484804B2 JP5484804B2 JP2009157337A JP2009157337A JP5484804B2 JP 5484804 B2 JP5484804 B2 JP 5484804B2 JP 2009157337 A JP2009157337 A JP 2009157337A JP 2009157337 A JP2009157337 A JP 2009157337A JP 5484804 B2 JP5484804 B2 JP 5484804B2
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- 239000011342 resin composition Substances 0.000 title claims description 78
- 238000000034 method Methods 0.000 title claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000003208 petroleum Substances 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 230000009477 glass transition Effects 0.000 claims description 22
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 20
- 235000019198 oils Nutrition 0.000 claims description 20
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical group C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 claims description 19
- 239000000344 soap Substances 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 5
- 235000021388 linseed oil Nutrition 0.000 claims description 4
- 239000000944 linseed oil Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 33
- 239000000843 powder Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- 238000002156 mixing Methods 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 13
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 238000000691 measurement method Methods 0.000 description 9
- 235000013312 flour Nutrition 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- -1 2-hydroxypropyl Chemical group 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007718 adhesive strength test Methods 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- SBUBPFHJZHQNNT-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene hydrogen peroxide Chemical compound OO.OO.CC(C)C1=CC=CC=C1C(C)C SBUBPFHJZHQNNT-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- COYJIMCVCRLOIW-UHFFFAOYSA-L [Mn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Mn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O COYJIMCVCRLOIW-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical group CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- KWYLNOQTLCTWCF-UHFFFAOYSA-L copper oct-2-enoate Chemical compound [Cu+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O KWYLNOQTLCTWCF-UHFFFAOYSA-L 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XCPQQZKNXRQMIQ-UHFFFAOYSA-L nickel(2+);oct-2-enoate Chemical compound [Ni+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O XCPQQZKNXRQMIQ-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、樹脂組成物を提供することを目的とする。更には本樹脂組成物で構造物を接着する作業に適した樹脂組成物を提供することを目的とする。 An object of this invention is to provide the resin composition. Furthermore, it aims at providing the resin composition suitable for the operation | work which adhere | attaches a structure with this resin composition.
従来、アクリル系樹脂は、耐久性が良く、いろいろな被着体に対する接着性が優れ、環境に優しいこと等から、成形材料、塗料、一般用接着剤、金属用接着剤、コンクリート用接着剤等に幅広く利用されている。 Conventionally, acrylic resins have good durability, excellent adhesion to various adherends, and are environmentally friendly, so molding materials, paints, general adhesives, metal adhesives, concrete adhesives, etc. Widely used.
しかしながら、従来から知られているアクリル系樹脂は、一般にその硬化物が硬く、水膨張性も小さいためコンクリート構造物又は金属構造物の充填接着剤として使用する際に、以下の問題があった。即ち、長期間水に接触する場合には必要な止水性が確保できないという問題があった。 However, since conventionally known acrylic resins are generally hardened and have a small water expansion property, they have the following problems when used as filling adhesives for concrete structures or metal structures. That is, there has been a problem that the necessary water stoppage cannot be ensured when contacting water for a long time.
これらの問題を解決するために、低弾性接着剤組成物を用いてコンクリート構造物を接着することが提案されている（特許文献１〜２参照）。これらの樹脂組成物をコンクリート構造物用接着剤として使用した場合、コンクリートに対する接着性が優れ、冬季の屋外等といった低温においても短時間で硬化することができる。 In order to solve these problems, it has been proposed to bond a concrete structure using a low-elasticity adhesive composition (see Patent Documents 1 and 2). When these resin compositions are used as adhesives for concrete structures, they have excellent adhesion to concrete and can be cured in a short time even at low temperatures such as outdoors in winter.
本願発明のように、水圧の高い状態で長期間水に接触しても、止水性が保てることについて記載はない。本願発明のように、金属製埋設型枠等の充填接着剤として使用した場合、同様に水圧の高い状態で長期間水に接触しても、止水性が保てることについて記載はない。 There is no description that the water-stopping property can be maintained even if it is in contact with water for a long period of time under a high water pressure as in the present invention. As in the present invention, when used as a filling adhesive for a metal embedding formwork or the like, there is no description that the water-stopping property can be maintained even if it is in contact with water for a long period of time under a high water pressure.
本発明者らは、これらの課題を解決すべく鋭意検討した結果、水圧の高い状態で長期間水に接触していても止水性が完全に保たれ、更に、コンクリート構造物等を接着する施工現場での作業に適した樹脂組成物を見いだし本発明に至った。 As a result of diligent studies to solve these problems, the inventors of the present invention are able to maintain a water-stopping property even when they are in contact with water for a long period of time under a high water pressure. The present inventors have found a resin composition suitable for on-site work and have arrived at the present invention.
本発明は、分子中に少なくとも１個以上のフェニル基を有してなり、かつ、硬化物のガラス転移温度が０℃以下である（メタ）アクリル酸エステルモノマー（Ａ）、ヒドロキシアルキル（メタ）アクリレート（Ｂ）、石油樹脂（Ｃ）、充填材（Ｄ）、重合開始剤（Ｅ）及び金属石鹸（Ｆ）を含有する樹脂組成物を、（Ｃ）成分と（Ｅ）成分を少なくとも含有する（Ｏ）剤と、（Ｆ）成分を少なくとも含有する（Ｒ）剤との２剤に分けてなる樹脂組成物であり、（Ｃ）成分の使用量が、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、１〜４０質量部である樹脂組成物であり、（Ｂ）成分の使用量が、（Ａ）成分１００質量部に対して５〜１００質量部であり、（Ｄ）成分の使用量が、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、２０〜３００質量部であり、（Ｅ）成分の使用量が、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、０．５〜８質量部であり、（Ｆ）成分の使用量が、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、含有金属換算で０.０１〜１．０質量部である該樹脂組成物であり、（Ｒ）剤が、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分からなる群のうちの１種又は２種以上を含有する該樹脂組成物であり、石油樹脂（Ｃ）が臭素価２〜３０（ｇ／１００ｇ）の石油樹脂である該樹脂組成物であり、（Ａ）成分が、ノニルフェノールエチレンオキサイド４モル変性アクリレートであり、（Ｂ）成分が、２−ヒドロキシエチル（メタ）アクリレートであり、（Ｃ）成分が、Ｃ９系石油樹脂であり、（Ｄ）成分が、炭酸カルシウムであり、（Ｅ）成分が、クメンハイドロパーオキサイドであり、（Ｆ）成分が、オクテン酸コバルトである該樹脂組成物であり、（Ｒ）剤中の（Ａ）成分の使用量が、（Ｆ）成分中の金属１００質量部に対して、５０〜９４００００質量部である該樹脂組成物であり、（Ｄ）成分の平均粒径が、０．０１〜２００μｍである該樹脂組成物であり、硬化物の水膨張率が１０〜３００％以下であり、かつ、引張弾性率が０．０５〜５Ｎ／ｍｍ２である該樹脂組成物であり、（Ｏ）剤と（Ｒ）剤の質量比が、（Ｏ）剤／（Ｒ）剤＝（０．０２〜３５０）／１である該樹脂組成物であり、半乾性油及び／又は乾性油（Ｇ）を、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して０．２〜２０質量部含有する該樹脂組成物であり、（Ｇ）成分は、亜麻仁油である該樹脂組成物であり、（Ｒ）剤中に溶剤を、（Ｆ）成分１００質量部に対して、１０００００質量部以下含有する該樹脂組成物であり、溶剤は、トルエンである該樹脂組成物であり、該樹脂組成物からなる止水性樹脂組成物であり、該樹脂組成物を、（Ｃ）成分と（Ｅ）成分を少なくとも含有する（Ｏ）剤と、（Ｆ）成分を少なくとも含有する（Ｒ）剤との２剤に分け、使用時に（Ｏ）剤と（Ｒ）剤を混合する樹脂組成物の使用方法であり、半乾性油及び／又は乾性油（Ｇ）が（Ｏ）剤に含有する該樹脂組成物の使用方法であり、溶剤が（Ｒ）剤に含有する樹脂組成物の使用方法であり、樹脂組成物が止水性樹脂組成物である該樹脂組成物の使用方法である。 The present invention has (meth) acrylic acid ester monomer (A), hydroxyalkyl (meth) having at least one phenyl group in the molecule and having a cured product having a glass transition temperature of 0 ° C. or lower. A resin composition containing an acrylate (B), a petroleum resin (C), a filler (D), a polymerization initiator (E), and a metal soap (F) contains at least the (C) component and the (E) component. It is a resin composition divided into two agents, (O) agent and (R) agent containing at least component (F), and the amount of component (C) used is (A) component and component (B). It is a resin composition which is 1-40 mass parts with respect to a total of 100 mass parts, and the usage-amount of (B) component is 5-100 mass parts with respect to 100 mass parts of (A) component, ( D) The amount of component used is 100 parts by mass in total of component (A) and component (B). It is 20-300 mass parts, and the usage-amount of (E) component is 0.5-8 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and (F) component Is a resin composition that is 0.01 to 1.0 part by mass in terms of contained metal with respect to a total of 100 parts by mass of the component (A) and the component (B), and the (R) agent is , (A) component, (B) component, and the resin composition containing 1 type or 2 types or more of the group consisting of component (D), and petroleum resin (C) has a bromine number of 2 to 30 (g / 100 g) petroleum resin, the resin composition (A) is nonylphenol ethylene oxide 4 mol modified acrylate, the component (B) is 2-hydroxyethyl (meth) acrylate, and (C ) Component is a C9 petroleum resin, (D) component is calcium carbonate, ) Component is cumene hydroperoxide, component (F) is a resin composition octene cobalt, (the amount of the component (A) in R) agent, in the component (F) The resin composition is 50 to 940000 parts by mass with respect to 100 parts by mass of the metal, the resin composition having an average particle size of component (D) of 0.01 to 200 μm, and water of the cured product The resin composition has an expansion coefficient of 10 to 300% or less and a tensile modulus of 0.05 to 5 N / mm 2 , and the mass ratio of the (O) agent and the (R) agent is (O ) Agent / (R) agent = (0.02 to 350) / 1, and the semi-drying oil and / or drying oil (G) is the sum of the component (A) and the component (B). The resin composition contains 0.2 to 20 parts by mass with respect to 100 parts by mass, and the component (G) is linseed oil. This resin composition is a resin composition containing (R) a solvent in an amount of 100000 parts by mass or less with respect to 100 parts by mass of the component (F), and the solvent is toluene. A water-stopping resin composition comprising the resin composition, wherein the resin composition contains at least an (O) agent containing at least the (C) component and the (E) component, and at least the (F) component. It is a method of using a resin composition in which the (O) agent and the (R) agent are mixed at the time of use, and the semi-drying oil and / or the drying oil (G) is the (O) agent. In the method of using the resin composition, the solvent is a method of using the resin composition contained in the agent (R), and the resin composition is a water-stopping resin composition. is there.
本発明に用いる樹脂組成物は、止水性を確保できる。更に、コンクリート構造物等を接着する施工現場での作業に適している。 The resin composition used in the present invention can ensure water blocking. Furthermore, it is suitable for work at a construction site where a concrete structure or the like is bonded.
本発明に用いる（Ａ）成分は、分子中に少なくとも１個以上のフェニル基を有してなり、かつ、硬化物のガラス転移温度が０℃以下である（メタ）アクリル酸エステルモノマーであり、例えば、硬化物の引張弾性率を下げ、硬化物を柔軟にし、かつ、高度な伸び特性を付与させる。 The component (A) used in the present invention is a (meth) acrylic acid ester monomer having at least one phenyl group in the molecule and having a cured product having a glass transition temperature of 0 ° C. or lower. For example, the tensile modulus of the cured product is lowered, the cured product is made flexible, and a high elongation property is imparted.
（Ａ）成分の例としては、フェノール（エチレンオキサイド）２モル変性アクリレート、フェノール（エチレンオキサイド４モル変性）アクリレート、ノニルフェノール（エチレンオキサイド４モル変性）アクリレート、ノニルフェノール（プロピレンオキサイド２．５モル変性）アクリレート等が挙げられ、これらは、それぞれアロニックス＃Ｍ−１０１Ａ、＃Ｍ−１０２、＃Ｍ−１１３、＃Ｍ−１１７（東亞合成社製）の商品名で市販されているものがあるが、これらに限定されるものではない。 Examples of the component (A) include phenol (ethylene oxide) 2 mol modified acrylate, phenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (propylene oxide 2.5 mol modified) acrylate. These are commercially available under the trade names of Aronix # M-101A, # M-102, # M-113, and # M-117 (manufactured by Toagosei Co., Ltd.). It is not limited.
これらは、硬化物の物性を調整する目的で、単独で用いても良いし２種類以上混合して使用しても良い。 These may be used alone or in combination of two or more for the purpose of adjusting the physical properties of the cured product.
本発明に用いる（Ｂ）成分は、ヒドロキシアルキル（メタ）アクリレートであり、炭素数１〜１２個のヒドロキシ（メタ）アクリレートが好ましい。（Ｂ）成分の例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等が挙げられる。 (B) component used for this invention is a hydroxyalkyl (meth) acrylate, and a C1-C12 hydroxy (meth) acrylate is preferable. Examples of the component (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
これらは、硬化物の性質の調整を目的として単独で用いても良いし、２種類以上混合して用いても良い。 These may be used alone for the purpose of adjusting the properties of the cured product, or may be used in combination of two or more.
本発明に用いる（Ｂ）成分は、例えば、接着性及び水膨張性を付与させる成分であり、（Ａ）成分１００質量部に対して５〜１００質量部の範囲で用いることが好ましく、１０〜５０質量部が特に好ましい。５質量部未満では接着性及び水膨張性が不十分となり、水圧の高い状態で長期間水に接触していると止水性が完全には保たれなくなる場合がある。１００質量部を超えると水膨張性が大きくなりすぎ、却って接着性及び止水性が低下する場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分の合計の量である。 (B) component used for this invention is a component which provides adhesiveness and water expansibility, for example, and it is preferable to use in the range of 5-100 mass parts with respect to 100 mass parts of (A) component, 50 parts by mass is particularly preferred. If the amount is less than 5 parts by mass, the adhesiveness and water expandability are insufficient, and if the water pressure is high and the water is kept in contact for a long time, the water stoppage may not be maintained completely. If the amount exceeds 100 parts by mass, the water expandability becomes too high, and the adhesiveness and the water stoppage may be lowered. The amount of component (A) and component (B) is the total amount of component (A) and component (B) contained in agent (O) and agent (R).
本発明に用いる（Ｃ）成分である石油樹脂の例としては、Ｃ９系石油樹脂、水添石油樹脂、Ｃ５系石油樹脂、ジシクロペンタジエン系石油樹脂等が挙げられる。低弾性を確保するには臭素価２〜４０（ｇ／１００ｇ）のＣ９系石油樹脂及び／又は水添石油樹脂が特に好ましい。Ｃ９系石油樹脂の例としては、臭素価１５〜３０（ｇ／１００ｇ）のネオポリマー＃Ｌ−９０、＃１２０、＃Ｅ−１００、＃Ｓ等（新日本石油社製）が市販されている。水添石油樹脂の例としては、臭素価２〜６（ｇ／１００ｇ）のアイマーブ＃Ｓ−１１０、＃Ｙ−１００、＃Ｐ−１４０等（出光興産社製）が市販されている。 Examples of the petroleum resin as the component (C) used in the present invention include C9 petroleum resins, hydrogenated petroleum resins, C5 petroleum resins, dicyclopentadiene petroleum resins and the like. In order to ensure low elasticity, a C9 petroleum resin and / or hydrogenated petroleum resin having a bromine number of 2 to 40 (g / 100 g) is particularly preferable. As an example of C9 petroleum resin, neopolymers # L-90, # 120, # E-100, #S and the like (manufactured by Nippon Oil Corporation) having a bromine number of 15 to 30 (g / 100 g) are commercially available. . As examples of hydrogenated petroleum resins, Imabe # S-110, # Y-100, # P-140, etc. (made by Idemitsu Kosan Co., Ltd.) having a bromine number of 2 to 6 (g / 100 g) are commercially available.
Ｃ５系石油樹脂の例としては、臭素価５０〜５５（ｇ／１００ｇ）のクイントン＃１３２５、＃１５００、＃１７００等（日本ゼオン社製）が、ジシクロペンタジエン系石油樹脂の例としては臭素価１２０（ｇ／１００ｇ）のマルカレッツ＃Ｍ−８９０Ａ、＃Ｍ−８４５Ａ等（丸善石油化学社製）が市販されている。本発明はこれらの商品に限定されるものではない。 Examples of C5 petroleum resins include Quinton # 1325, # 1500, # 1700 (manufactured by Nippon Zeon Co., Ltd.) having a bromine number of 50 to 55 (g / 100 g), and examples of dicyclopentadiene petroleum resins include bromine number. 120 (g / 100 g) Marcaretz # M-890A, # M-845A, etc. (manufactured by Maruzen Petrochemical Co., Ltd.) are commercially available. The present invention is not limited to these products.
本発明に用いる（Ｃ）成分である石油樹脂は、例えば、ラジカル重合において、ラジカルが、分子中に存在する不飽和炭化水素結合の第３級水素へ、容易に連鎖移動して、グラフト化が起こり、生成する高分子中に取り込まれる。その他にも空気の作用で、パーオキサイドを形成する。パーオキサイドは、例えば、金属石鹸により、分解されてフリーラジカルとなり、モノマーを重合させる作用、所謂、空気硬化性を発現するものである。 The petroleum resin which is the component (C) used in the present invention, for example, in radical polymerization, the radical is easily chain-transferred to the tertiary hydrogen of the unsaturated hydrocarbon bond existing in the molecule, and grafting is possible. Occurs and is incorporated into the resulting polymer. In addition, peroxide is formed by the action of air. Peroxide is decomposed by, for example, metal soap into free radicals, and exhibits a function of polymerizing monomers, so-called air-curing properties.
例えば、この空気硬化性は、パラフィン等の空気遮断効果とは本質的に異なり、遅速はあるにしても温度に依存しにくい反応である。例えば、空気硬化性を発現させることにより、樹脂組成物の表面硬化性を向上させるだけでなく、コンクリート等の多孔質体に対する接着力が向上するという効果がある。 For example, this air-curing property is essentially different from the air blocking effect of paraffin or the like, and is a reaction that is less dependent on temperature even though it is slow. For example, by exhibiting air curability, not only the surface curability of the resin composition is improved, but also the adhesive force to a porous body such as concrete is improved.
この空気硬化特性を有する化合物の例として、ジシクロペンテニル（メタ）アクリレート系モノマー、ジシクロペンテニルオキシエチル（メタ）アクリレート系モノマー、アクリル変性ポリブタジエン等のアリル基を有するアクリル系モノマー及びオリゴマー等が挙げられるが、何れも、例えば、空気乾燥作用が発現できる量まで添加すると弾性率を激しく上昇させるため、低弾性を有しにくい。 Examples of the compound having air curing characteristics include dicyclopentenyl (meth) acrylate monomers, dicyclopentenyloxyethyl (meth) acrylate monomers, acrylic monomers and oligomers having an allyl group such as acrylic-modified polybutadiene, and the like. However, in any case, for example, if it is added to an amount capable of exhibiting an air drying action, the elastic modulus is increased drastically, so that it is difficult to have low elasticity.
本発明に用いる（Ｃ）成分である石油樹脂は、硬化物の物性を調整する目的で単独にて用いても良いし、２種類以上混合して用いても良い。 The petroleum resin which is the component (C) used in the present invention may be used alone for the purpose of adjusting the physical properties of the cured product, or may be used by mixing two or more kinds.
本発明に用いる（Ｃ）成分である石油樹脂は、例えば、硬化物の柔軟性を損なわず表面の乾燥性を付与させる成分であり、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、１〜４０質量部の範囲で用いることが好ましく、１０〜３０質量部の範囲で用いることが特に好ましい。１質量部未満では表面乾燥効果が不十分である場合があり、４０質量部を超えると、主として引張弾性率が大きくなり、止水性が低下する場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分の合計の量である。 The petroleum resin that is the component (C) used in the present invention is a component that imparts dryness to the surface without impairing the flexibility of the cured product, for example, and a total of 100 parts by mass of the component (A) and the component (B). On the other hand, it is preferable to use in the range of 1-40 mass parts, and it is especially preferable to use in the range of 10-30 mass parts. If the amount is less than 1 part by mass, the surface drying effect may be insufficient. If the amount exceeds 40 parts by mass, the tensile elastic modulus mainly increases and the water stoppage may decrease. The amount of component (A) and component (B) is the total amount of component (A) and component (B) contained in agent (O) and agent (R).
本発明に用いる（Ｄ）成分である充填材の例としては、無機充填材や有機充填材等が挙げられる。 Examples of the filler that is the component (D) used in the present invention include inorganic fillers and organic fillers.
本発明に用いる（Ｄ）成分である無機充填材の例としては、結晶シリカ粉、溶融シリカ粉、球状シリカ粉及びヒュームドシリカ等のシリカ粉、珪砂、カーボンブラック、フォラストナイト、クレー、酸化チタン、酸化マグネシウム、酸化鉄、ベントナイト、マイカ、ニッケルスラグ、水酸化アルミニウム、球状のものを含むアルミナ粉、ステンレス粉、炭化珪素粉、窒化珪素粉、窒化硼素粉、タルク粉、炭酸カルシウム粉、ガラスビーズ、シラスバルーン、アルミニウム粉、並びに、チタン粉等が挙げられる。 Examples of the inorganic filler that is the component (D) used in the present invention include silica powder such as crystalline silica powder, fused silica powder, spherical silica powder and fumed silica, silica sand, carbon black, forastonite, clay, oxidation Titanium, magnesium oxide, iron oxide, bentonite, mica, nickel slag, aluminum hydroxide, spherical alumina powder, stainless steel powder, silicon carbide powder, silicon nitride powder, boron nitride powder, talc powder, calcium carbonate powder, glass Examples thereof include beads, shirasu balloons, aluminum powder, and titanium powder.
本発明に用いる（Ｄ）成分である有機充填材の例としては、ポリエチレン粉末、ウレタン樹脂粉、（メタ）アクリル樹脂粉、シリコーン樹脂粉、フッ素樹脂粉、フェノール樹脂粉、木粉及び再生ゴム粉等が挙げられる。 Examples of the organic filler that is component (D) used in the present invention include polyethylene powder, urethane resin powder, (meth) acrylic resin powder, silicone resin powder, fluororesin powder, phenol resin powder, wood powder, and recycled rubber powder. Etc.
本発明に用いる（Ｄ）成分である充填材は、（Ａ）成分及び（Ｂ）成分に溶解せず、分散又は膨潤するものが好ましく、平均粒径は０．０１〜２００μｍが好ましく、０．１〜５μｍが特に好ましい。 The filler which is the component (D) used in the present invention is preferably one that does not dissolve in the component (A) and the component (B) but disperses or swells, and the average particle diameter is preferably 0.01 to 200 μm. 1-5 micrometers is especially preferable.
本発明に用いる（Ｄ）成分である充填材は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、２０〜３００質量部の範囲で用いることが好ましく、５０〜１５０質量部の範囲で用いることがより好ましい。２０質量部未満では硬化物の引張弾性率が小さくなる場合があり、３００質量部を超えると硬化物の引張弾性率が著しく大きくなる場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分の合計の量である。 The filler which is the component (D) used in the present invention is preferably used in the range of 20 to 300 parts by mass, and 50 to 150 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). It is more preferable to use in the range. If it is less than 20 parts by mass, the tensile modulus of the cured product may be small, and if it exceeds 300 parts by mass, the tensile modulus of the cured product may be remarkably increased. The amount of component (A) and component (B) is the total amount of component (A) and component (B) contained in agent (O) and agent (R).
次に、本発明に用いる（Ｅ）成分である重合開始剤としては、例えば、自然分解性が小さく、（Ｆ）成分である金属石鹸と酸化還元反応、所謂、レドックス反応を惹起して本発明の（Ａ）成分と(Ｂ)成分であるアクリル酸エステルモノマーをラジカル重合させる、ラジカル重合開始剤が好ましい。ラジカル重合開始剤の例としては、有機過酸化物が好ましい。有機過酸化物としては、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ターシャリーブチルハイドロパーオキサイド、ジイソプロピルベンゼンジハイドロパーオキサイド、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド及びターシャリーブチルパーオキシベンゾエート等が挙げられる。これらの中では、クメンハイドロパーオキサイドが好ましい。 Next, as the polymerization initiator (E) used in the present invention, for example, the natural degradability is small, and the metal soap (F) component causes an oxidation-reduction reaction, so-called redox reaction. A radical polymerization initiator that radically polymerizes the acrylate monomer as the component (A) and the component (B) is preferable. As an example of the radical polymerization initiator, an organic peroxide is preferable. Examples of the organic peroxide include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . Of these, cumene hydroperoxide is preferred.
本発明に用いる（Ｅ）成分である重合開始剤は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、０．５〜８質量部の範囲で用いることが好ましく、１〜３質量部が特に好ましい。０．５質量部未満では硬化不良が発生する場合があり、８質量部を超えると保存安定性が著しく低下する場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分の合計の量である。 The polymerization initiator which is the component (E) used in the present invention is preferably used in the range of 0.5 to 8 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). 3 parts by mass is particularly preferred. If it is less than 0.5 part by mass, poor curing may occur, and if it exceeds 8 parts by mass, the storage stability may be significantly reduced. The amount of component (A) and component (B) is the total amount of component (A) and component (B) contained in agent (O) and agent (R).
本発明に用いる（Ｆ）成分である金属石鹸の例としては、ナフテン酸コバルト、オクテン酸コバルト、ナフテン酸マンガン、オクテン酸マンガン、ナフテン酸ニッケル、オクテン酸ニッケル、ナフテン酸バナジウム、オクテン酸銅等が挙げられる。 Examples of the metal soap which is the component (F) used in the present invention include cobalt naphthenate, cobalt octenoate, manganese naphthenate, manganese octenoate, nickel naphthenate, nickel octenoate, vanadium naphthenate, copper octenoate and the like. Can be mentioned.
これらの金属石鹸は、金属含有率が１〜２０質量％程度の範囲にあるものが一般に市販されている。金属含有率が８〜１７質量％程度の範囲にあるものが好ましい。使用に際しては有効な金属含有率を換算し、含有金属換算で使用する。 These metal soaps having a metal content in the range of about 1 to 20% by mass are generally commercially available. What has a metal content rate in the range of about 8-17 mass% is preferable. In use, the effective metal content is converted and used in terms of contained metal.
本発明に用いる（Ｆ）成分である金属石鹸は、単独で用いても良く、複数組み合わせて用いても良い。 The metal soap which is the component (F) used in the present invention may be used alone or in combination.
本発明に用いる（Ｆ）成分である金属石鹸は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、含有金属換算で０.０１〜１．０質量部の範囲で用いることが好ましく、０．０３〜０．７質量部の範囲で用いることが特に好ましい。０.０１質量部では硬化不良を発生する場合があり、１．０質量部を超えると高価なものになり、硬化物の着色が顕著となる場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分を含有する。 The metal soap which is the component (F) used in the present invention is used in the range of 0.01 to 1.0 part by mass in terms of contained metal with respect to 100 parts by mass in total of the component (A) and the component (B). It is particularly preferable to use in the range of 0.03 to 0.7 parts by mass. In 0.01 parts by mass, poor curing may occur, and when it exceeds 1.0 parts by mass, it becomes expensive and coloring of the cured product may become remarkable. The amount of the component (A) and the component (B) includes the component (A) and the component (B) contained in the agent (O) and the agent (R).
本発明に用いる（Ｅ）成分と酸化還元反応、所謂、レドックス反応を惹起して本発明の（Ａ）成分と（Ｂ）成分であるアクリル酸エステルモノマーをラジカル重合させる効果のあるものの例として、エチレンチオ尿素、モノベンゾイルチオ尿素等のチオ尿素類が挙げられる。しかしながら、金属を含有しないこれらのものは、（Ｃ）成分である石油樹脂の空気硬化性を促進する効果が小さいので、使用できない。 As an example of the component (E) used in the present invention and an oxidation-reduction reaction, a so-called redox reaction, which has the effect of radically polymerizing the acrylate monomer as the component (A) and component (B) of the present invention, Examples include thioureas such as ethylenethiourea and monobenzoylthiourea. However, those which do not contain a metal cannot be used because the effect of promoting the air curability of the petroleum resin (C) is small.
本発明に用いる（Ｇ）成分である半乾性油及び／又は乾性油は、本発明の（Ｆ）成分である金属石鹸の作用により、空気硬化する不飽和炭化水素結合を分子中に有する油脂類の総称である。ヨウ素価１００〜１３０（ｇ／１００ｇ）の半乾性油の例としては、大豆油、綿実油、なたね油等が挙げられる。ヨウ素価１３０（ｇ／１００ｇ）以上の乾性油の例としては、亜麻仁油、ボイル油、魚油等から変性した乾性油等が挙げられる。ヨウ素価の上限値は、３００（ｇ／１００ｇ）が好ましく、２００（ｇ／１００ｇ）が特に好ましい。 The semi-drying oil and / or drying oil that is the component (G) used in the present invention is an oil or fat that has an unsaturated hydrocarbon bond in the molecule that is air-cured by the action of the metal soap that is the component (F) of the present invention. Is a general term. Examples of the semi-drying oil having an iodine value of 100 to 130 (g / 100 g) include soybean oil, cottonseed oil, rapeseed oil and the like. Examples of the drying oil having an iodine value of 130 (g / 100 g) or more include drying oil modified from linseed oil, boil oil, fish oil and the like. The upper limit of iodine value is preferably 300 (g / 100 g), particularly preferably 200 (g / 100 g).
本発明に用いる（Ｇ）成分である半乾性油及び／又は乾性油は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して０．２〜２０質量部の範囲で用いることが好ましく、１〜１０質量部の範囲で用いることが特に好ましい。０．２質量部未満では低弾性率化の効果が乏しくなる場合があり、２０質量部を超えると弾性率の低下が著しくなる場合がある。（Ａ）成分と（Ｂ）成分の量は、（Ｏ）剤中と（Ｒ）剤中に含有する、（Ａ）成分と（Ｂ）成分の合計の量である。 The semi-drying oil and / or drying oil which is the component (G) used in the present invention is used in the range of 0.2 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). It is particularly preferable to use in the range of 1 to 10 parts by mass. If the amount is less than 0.2 parts by mass, the effect of lowering the elastic modulus may be poor. If the amount exceeds 20 parts by mass, the elastic modulus may be significantly reduced. The amount of component (A) and component (B) is the total amount of component (A) and component (B) contained in agent (O) and agent (R).
この空気硬化性は、例えば、パラフィン等の空気遮断効果とは本質的に異なり、遅速はあるにしても温度に依存しにくい反応である。例えば、空気硬化性を発現させることにより、樹脂組成物の表面硬化性を向上させるだけでなく、コンクリート等の多孔質体に対する接着力が向上するという効果がある。 This air-curing property is essentially different from the air blocking effect of, for example, paraffin, and is a reaction that is less dependent on temperature even though it is slow. For example, by exhibiting air curability, not only the surface curability of the resin composition is improved, but also the adhesive force to a porous body such as concrete is improved.
本発明の樹脂組成物には、貯蔵安定性向上又は硬化速度調整のために、少量の重合禁止剤を使用することができる。重合禁止剤の例としてはメチルハイドロキノン、ハイドロキノン、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５−ジターシャリーブチルハイドロキノン、ｐ−ベンゾキノン、フェノチアジン、ターシャリーブチルカテコール等が挙げられる。 In the resin composition of the present invention, a small amount of a polymerization inhibitor can be used for improving storage stability or adjusting the curing rate. Examples of the polymerization inhibitor include methyl hydroquinone, hydroquinone, catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, phenothiazine, tertiary butyl catechol and the like.
本発明の樹脂組成物には、短時間での硬化性を更に上げる目的で、例えば、トリエタノールアミン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）−ｐ−トルイジン、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）アニリン等の第３級アミン類を促進剤として、単独又は組み合わせて用いることもできる。 In the resin composition of the present invention, for the purpose of further improving the curability in a short time, for example, triethanolamine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2 Tertiary amines such as -hydroxyethyl) aniline can be used alone or in combination as accelerators.
本発明の樹脂組成物には、本発明の目的を損なわない範囲で、一般に使用されている各種エラストマー、溶剤、補強材、可塑剤、キレート化剤、染料、顔料、難燃剤、界面活性剤、シランカップリング剤、紫外線吸収剤、発泡剤等の添加剤を添加しても良い。 The resin composition of the present invention includes various elastomers, solvents, reinforcing materials, plasticizers, chelating agents, dyes, pigments, flame retardants, surfactants, and the like that are generally used within a range that does not impair the purpose of the present invention. You may add additives, such as a silane coupling agent, a ultraviolet absorber, and a foaming agent.
本発明の樹脂組成物を用いる接着方法の例としては、コンクリート構造物や金属構造物に、スプレー、刷毛、ローラー塗布等といった通常の塗布方法により樹脂組成物を塗布し、構造物同士を接着する方法や、構造物間に樹脂組成物を注入充填して構造物同士を接着する方法等が挙げられる。これらの方法により、コンクリート構造物又は金属構造物を得ることができる。 As an example of an adhesion method using the resin composition of the present invention, a resin composition is applied to a concrete structure or a metal structure by a normal application method such as spraying, brushing, or roller application, and the structures are bonded to each other. Examples thereof include a method and a method of injecting and filling a resin composition between structures to bond the structures together. By these methods, a concrete structure or a metal structure can be obtained.
本発明の樹脂組成物は、作業性の点で、（Ｏ）剤と（Ｒ）剤の２剤に分けることが好ましい。本発明の樹脂組成物は、（Ｅ）成分を少なくとも含有する（Ｏ）剤と、（Ｆ）成分を少なくとも含有する（Ｒ）剤との２剤に分けることが好ましい。保存安定性を確保するために、（Ｃ）成分は、（Ｏ）剤側に添加することが好ましい。（Ｏ）剤は、（Ｆ）成分を含有しないことが好ましい。（Ｒ）剤は、（Ｅ）成分を含有しないことが好ましい。（Ｏ）剤は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分を少なくとも含有する（Ｏ）剤と、（Ｆ）成分を少なくとも含有する（Ｒ）剤との２剤に分けることが特に好ましい。（Ｇ）成分は、（Ｏ）剤に含有することが好ましい。 The resin composition of the present invention is preferably divided into two agents (O) agent and (R) agent from the viewpoint of workability. The resin composition of the present invention is preferably divided into two agents: an (O) agent containing at least the (E) component and an (R) agent containing at least the (F) component. In order to ensure storage stability, the component (C) is preferably added to the (O) agent side. The agent (O) preferably does not contain the component (F). The (R) agent preferably does not contain the (E) component. The (O) agent contains at least (A) component, (B) component, (C) component, (D) component and (E) component (O) agent and (F) component (R). It is particularly preferable to divide it into two agents. The component (G) is preferably contained in the agent (O).
本発明は、（Ｏ）剤や（Ｒ）剤の保存容器として、（Ｏ）剤や（Ｒ）剤が保存された状態のところに、（Ｒ）剤や（Ｏ）剤を添加して混合できる容器を用いることが好ましい。即ち、保存容器と混合容器を兼ねる容器を用いれば、接着作業の現場で容器を用意する必要がなくなるので、実用上有益である。 In the present invention, as a storage container for the (O) agent and (R) agent, the (R) agent and (O) agent are added and mixed in the state where the (O) agent and (R) agent are stored. It is preferable to use a container that can be used. That is, if a container that serves as both a storage container and a mixing container is used, there is no need to prepare the container at the site of the bonding operation, which is practically beneficial.
（Ｒ）剤は、作業性や混合性の点で、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分からなる群のうちの１種又は２種以上を含有することが好ましい。（Ｒ）剤中の（Ａ）成分の使用量は、（Ｆ）成分中の金属１００質量部に対して、５０〜９４００００質量部が好ましく、５００〜４０００００質量部が特に好ましい。（Ｒ）剤中の（Ｂ）成分の使用量は、（Ｆ）成分中の金属１００質量部に対して、９５〜３００００００質量部が好ましく、５００〜２０００００質量部が特に好ましい。（Ｒ）剤中の（Ｄ）成分の使用量は、（Ｆ）成分中の金属１００質量部に対して、２０００〜３００００００質量部が好ましく、４０００〜６０００００質量部が特に好ましい。 The (R) agent preferably contains one or more of the group consisting of the component (A), the component (B) and the component (D) in terms of workability and mixing properties. The amount of the component (A) in the agent (R) is preferably 50 to 940000 parts by mass and particularly preferably 500 to 400,000 parts by mass with respect to 100 parts by mass of the metal in the component (F). The amount of the component (B) in the agent (R) is preferably 95 to 3000000 parts by mass, particularly preferably 500 to 200000 parts by mass with respect to 100 parts by mass of the metal in the component (F). (R) The usage-amount of (D) component in an agent has preferable 2000-3000000 mass parts with respect to 100 mass parts of metals in (F) component, and 4000-600000 mass parts is especially preferable.
（Ｏ）剤と（Ｒ）剤の質量比は、（Ｏ）剤／（Ｒ）剤＝（０．０２〜３５０）／１の範囲が好ましく、（０．０５〜１００）／１の範囲が特に好ましく、（３〜３０）／１の範囲が最も好ましい。この比が０．０２より小さい場合、又は、３５０より大きい場合には、（Ｏ）剤と（Ｒ）剤を均一に混合することが困難になり、樹脂組成物の硬化反応が不良となって、所定の物性の樹脂組成物の硬化体が得られずに、接着性能や止水性が確保できなくなる場合もある。 The mass ratio of the (O) agent to the (R) agent is preferably in the range of (O) agent / (R) agent = (0.02-350) / 1, and in the range of (0.05-100) / 1. Particularly preferred is a range of (3-30) / 1. When this ratio is smaller than 0.02 or larger than 350, it becomes difficult to uniformly mix the (O) agent and the (R) agent, and the curing reaction of the resin composition becomes poor. In some cases, a cured product of a resin composition having predetermined physical properties cannot be obtained, and adhesion performance and water stopping properties cannot be ensured.
又、（Ｏ）剤と（Ｒ）剤の質量比を調整するために、例えばトルエンやアセトンなどの溶剤で希釈すると、所定の物性の樹脂組成物の硬化体が得られず、接着性能や止水性が確保できない場合がある。（Ｒ）剤中の溶剤の使用量は、（Ｆ）成分１００質量部に対して、１０００００質量部以下が好ましく、５００００質量部以下がより好ましく、２００００質量部が特に好ましく、０質量部が最も好ましい。 Further, in order to adjust the mass ratio of the (O) agent and the (R) agent, for example, when diluted with a solvent such as toluene or acetone, a cured product of a resin composition having predetermined physical properties cannot be obtained, and adhesion performance and Aqueous properties may not be ensured. The amount of the solvent in the (R) agent is preferably 100000 parts by mass or less, more preferably 50000 parts by mass or less, particularly preferably 20000 parts by mass, and most preferably 0 parts by mass with respect to 100 parts by mass of the component (F). preferable.
以下に、実施例により本発明を詳細に説明する。実施例の樹脂組成物を実施例組成物、比較例の樹脂組成物を比較例組成物ということもある。 Hereinafter, the present invention will be described in detail by way of examples. The resin composition of the example may be referred to as an example composition, and the resin composition of a comparative example may be referred to as a comparative example composition.
（実施例１）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１．６ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート５ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）０．５２５ｇを添加、攪拌し、実施例組成物１（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃，東亞合成社製）９８．４ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．０８７５ｇを添加混合して得た実施例組成物１（Ｒ）剤を添加混合し、実施例硬化体１を形成した。実施例組成物１は２５℃条件下、１８０分で硬化した。 (Example 1) Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 1.6 g as component (A), 2-hydroxyethyl methacrylate as component (B) 5 g, 25 g of Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) as component (C), dissolved by heating at 60 ° C., mixed and room temperature Until cooled. Furthermore, 0.525 g of park mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide-containing liquid) was added and stirred as component (E) to obtain Example Composition 1 (O). To this, 98.4 g of Aronix M113 (nonylphenol ethylene oxide 4 mol-modified acrylate, glass transition temperature of cured product −20 ° C., manufactured by Toagosei Co., Ltd.) as component (A), calcium carbonate powder (trade name “ # NS400 ", average particle size 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) 130 g, and octolife Co12 (made by Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) 0.0875 g as component (F) Example composition 1 (R) agent obtained by addition and mixing was added and mixed to form Example cured body 1. Example composition 1 was cured in 180 minutes at 25 ° C.
（実施例２）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃，東亞合成社製）９９ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０gを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）２．２ｇを添加、攪拌し、実施例組成物２（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１００ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）１６．６ｇを添加混合して得た実施例組成物２（Ｒ）剤を添加混合し、実施例硬化体２を形成した。実施例組成物２は２５℃条件下、３０分で硬化した。 (Example 2) Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 99 g as component (A), Nisseki Neopolymer # 120 (C) as component (A) Aromatic petroleum resin, brominated 25 (g / 100 g), Nippon Petrochemical Co., Ltd. 25 g, calcium carbonate powder (trade name “# NS400”, average particle size 1.71 μm, Nitto powdered as component (D)) 130 g) was dissolved by heating at 60 ° C., and after mixing, cooled to room temperature. Further, 2.2 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide containing liquid) was added and stirred as component (E) to obtain Example Composition 2 (O). To this, 1 g of Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product −20 ° C., manufactured by Toagosei Co., Ltd.) 1 g as component (A), 100 g of 2-hydroxyethyl methacrylate as component (B), (F ) Example composition 2 (R) agent obtained by adding and mixing 16.6 g of Octlife Co12 (manufactured by Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) as a component is added and mixed to cure the examples. Body 2 was formed. Example composition 2 was cured in 25 minutes at 25 ° C.
（実施例３）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１００ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）２．２ｇを添加、攪拌し、実施例組成物３（Ｏ）剤を得た。これに、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１００ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．１６６７ｇを添加混合して得た実施例組成物３（Ｒ）剤を添加混合し、実施例硬化体３を形成した。実施例組成物３は２５℃条件下、９０分で硬化した。 (Example 3) Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 100 g as component (A), Nisseki Neopolymer # 120 as component (C) Aromatic petroleum resin, brominated 25 (g / 100 g), Nippon Petrochemical Co., Ltd. 25 g, calcium carbonate powder (trade name “# NS400”, average particle size 1.71 μm, Nitto powdered as component (D)) 130g) was dissolved by heating at 60 ° C, and after mixing, cooled to room temperature. Furthermore, Park Mill H (manufactured by Nippon Oil & Fats Co., Ltd., 80% cumene hydroperoxide containing liquid) (2.2 g) was added and stirred as component (E) to obtain Example Composition 3 (O). To this, 100 g of 2-hydroxyethyl methacrylate as component (B) and 0.1667 g of Octlife Co12 (manufactured by Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) as component (F) were added and mixed. Example composition 3 (R) was added and mixed to form an example cured product 3. Example composition 3 was cured in 90 minutes at 25 ° C.
（実施例４）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１００ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート４ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）１．１６ｇを添加、攪拌し、実施例組成物４（Ｏ）剤を得た。これに、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）８．７５ｇを添加混合して得た実施例組成物４（Ｒ）剤を添加混合し、実施例硬化体４を形成した。実施例組成物４は２５℃条件下、３０分で硬化した。 (Example 4) Aronix M113 (nonylphenol ethylene oxide 4 mol-modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 100 g as component (A), 4 g of 2-hydroxyethyl methacrylate as component (B), (C) Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) 25 g as component, calcium carbonate powder (trade name “# NS400 ”, 130 g of an average particle diameter of 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) was dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Furthermore, 1.16 g of park mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide) as component (E) was added and stirred to obtain Example Composition 4 (O). This was obtained by adding and mixing 1 g of 2-hydroxyethyl methacrylate as the component (B) and 8.75 g of Octlife Co12 (product of Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) as the component (F). Example composition 4 (R) was added and mixed to form an example cured body 4. Example composition 4 was cured in 25 minutes at 25 ° C.
（実施例５）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１２．５ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）１ｇを添加、攪拌し、実施例組成物５（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃，東亞合成社製）８７．５ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１００ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）６００ｇを用い、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．１６６７ｇを添加混合して得た実施例組成物５（Ｒ）剤を添加混合し、実施例硬化体５を形成した。実施例組成物５は２５℃条件下、１８０分で硬化した。 (Example 5) Aronix M113 (nonylphenol ethylene oxide 4 mole modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 12.5 g as component (A), Nisseki Neopolymer # as component (C) 2 g of 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) was used, dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Furthermore, 1 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide containing liquid) was added and stirred as component (E) to obtain Example Composition 5 (O). To this, 87.5 g of Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product −20 ° C., manufactured by Toagosei Co., Ltd.) as component (A), 100 g of 2-hydroxyethyl methacrylate as component (B), As component (D), 600 g of calcium carbonate powder (trade name “# NS400”, average particle size 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) is used, and Octlife Co12 (made by Shinto Fine Co., metal soap cobalt) is used as component (F). Example composition 5 (R) agent obtained by adding and mixing 0.1667 g of 12% cobalt octenoate) was added and mixed to form Example Cured Body 5. Example composition 5 was cured in 180 minutes at 25 ° C.
（実施例６）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１００ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート４ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）１．１ｇを添加、攪拌し、実施例組成物６（Ｏ）剤を得た。これに、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）２１ｇを用い、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）８．７５ｇを添加混合して得た実施例組成物６（Ｒ）剤を添加混合し、実施例硬化体６を形成した。実施例組成物６は２５℃条件下、３０分で硬化した。 (Example 6) Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 100 g as component (A), 4 g of 2-hydroxyethyl methacrylate as component (B), As component (C), 25 g of Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) is used, dissolved by heating at 60 ° C., and cooled to room temperature after mixing. did. Furthermore, 1.1 g of park mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide containing liquid) as component (E) was added and stirred to obtain Example Composition 6 (O). To this, 1 g of 2-hydroxyethyl methacrylate as the component (B) and 21 g of calcium carbonate powder (trade name “# NS400”, average particle size 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) as the component (D) are used. ) Example composition 6 (R) agent obtained by adding and mixing 8.75 g of Octlife Co12 (manufactured by Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) as a component was added and mixed, and the example was cured. Body 6 was formed. Example composition 6 was cured in 25 minutes at 25 ° C.
（実施例７）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）１００ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート９９ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）８０ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）６００ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。加熱溶解、混合時に（Ｇ）成分として亜麻仁油（ヨウ素価１７８（ｇ／１００ｇ）、関東化学社製）４０ｇを添加した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）１５．９ｇを添加、攪拌し、実施例組成物７（Ｏ）剤を得た。これに、（Ｂ）成分として２−ヒドロキシエチルメタクリレート１ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）１．６７ｇを添加混合して得た実施例組成物７（Ｒ）剤を添加混合し、実施例硬化体７を形成した。実施例組成物７は２５℃条件下、３０分で硬化した。 (Example 7) Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 100 g as component (A), 99 g of 2-hydroxyethyl methacrylate as component (B), (C) Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) 80 g as component, calcium carbonate powder (trade name “# NS400” as component (D) ”, 600 g of an average particle diameter of 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) was dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Linseed oil (iodine number 178 (g / 100 g), manufactured by Kanto Chemical Co., Inc.) 40 g was added as a component (G) during heating and dissolution. Furthermore, 15.9 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide-containing solution) was added and stirred as component (E) to obtain Example Composition 7 (O). To this, 1 g of 2-hydroxyethyl methacrylate as component (B) and 1.67 g of Octlife Co12 (manufactured by Shinto Fine Co., Ltd., metal soap cobalt content 12% cobalt octenoate) as component (F) were added and mixed. Example composition 7 (R) was added and mixed to form Example Cured Product 7. Example composition 7 was cured in 25 minutes at 25 ° C.
（実施例８）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃，東亞合成社製）８０ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート２０ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。加熱溶解、混合時に（Ｇ）成分として亜麻仁油（ヨウ素価１７８（ｇ／１００ｇ）、関東化学社製）１０ｇを添加した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）２．２ｇを添加、攪拌し、実施例組成物８（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）２０ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．５ｇを添加混合して得た実施例組成物８（Ｒ）剤を添加混合し、実施例硬化体８を形成した。実施例組成物８は２５℃条件下、７０分で硬化した。 (Example 8) Aronix M113 (nonylphenol ethylene oxide 4 mol-modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 80 g as component (A), 20 g of 2-hydroxyethyl methacrylate as component (B), (C) Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) 25 g as component, calcium carbonate powder (trade name “# NS400 ”, 130 g of an average particle diameter of 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) was dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Lining oil (iodine number 178 (g / 100 g), manufactured by Kanto Chemical Co., Inc.) 10 g was added as a component (G) at the time of heat dissolution and mixing. Furthermore, 2.2 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide containing liquid) as component (E) was added and stirred to obtain Example Composition 8 (O). To this, 20 g of Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, cured product glass transition temperature -20 ° C, manufactured by Toagosei Co., Ltd.) as component (A), Octlife Co12 (produced by Shinto Fine Co., Ltd.) Example composition 8 (R) agent obtained by adding and mixing 0.5 g of metal soap (cobalt content 12% cobalt octenoate) was added and mixed to form Example hardened body 8. Example composition 8 was cured in 25 minutes at 25 ° C.
（実施例９）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）８０ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート２０ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）２．２ｇを添加、攪拌し、実施例組成物９（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）２０ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．５ｇを添加混合して得た実施例組成物９（Ｒ）剤を添加混合し、実施例硬化体９を形成した。実施例組成物９は２５℃条件下、６０分で硬化した。 (Example 9) Aronix M113 (nonylphenol ethylene oxide 4 mole modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 80 g as component (A), 20 g of 2-hydroxyethyl methacrylate as component (B), (C) Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) 25 g as component, calcium carbonate powder (trade name “# NS400 ”, 130 g of an average particle diameter of 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) was dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Furthermore, 2.2 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide containing liquid) was added and stirred as component (E) to obtain Example Composition 9 (O). To this, 20 g of Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, cured product glass transition temperature -20 ° C, manufactured by Toagosei Co., Ltd.) as component (A), Octlife Co12 (produced by Shinto Fine Co., Ltd.) Example composition 9 (R) agent obtained by adding and mixing 0.5 g of metal soap cobalt content 12% cobalt octenoate) was added and mixed to form Example cured body 9. Example composition 9 was cured in 25 minutes at 25 ° C.
（実施例１０）（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）８０ｇ、（Ｂ）成分として２−ヒドロキシエチルメタクリレート２０ｇ、（Ｃ）成分として日石ネオポリマー＃１２０（芳香族系石油樹脂、臭素化２５（ｇ／１００ｇ）、新日本石油化学社製）２５ｇ、（Ｄ）成分として炭酸カルシウム粉（商品名「＃ＮＳ４００」、平均粒径１．７１μｍ、日東粉化社製）１３０ｇを用い、６０℃で加熱溶解し、混合後に室温まで冷却した。更に、（Ｅ）成分としてパークミルＨ（日本油脂社製、クメンハイドロパーオキサイド８０％含有液）２．２ｇを添加、攪拌し、実施例組成物１０（Ｏ）剤を得た。これに、（Ａ）成分としてアロニックスＭ１１３（ノニルフェノールエチレンオキサイド４モル変性アクリレート、硬化物のガラス転移温度−２０℃、東亞合成社製）２０ｇ、（Ｆ）成分としてオクトライフＣo１２（シントーファイン社製、金属石鹸コバルト含有量１２％オクテン酸コバルト）０．５ｇ、トルエン１０ｇからなる実施例組成物１０（Ｒ）剤を添加混合し、実施例硬化体１０を形成した。実施例組成物１０は２５℃条件下、１２０分で硬化した。 (Example 10) Aronix M113 (nonylphenol ethylene oxide 4 mole modified acrylate, glass transition temperature of cured product -20 ° C, manufactured by Toagosei Co., Ltd.) 80 g as component (A), 20 g of 2-hydroxyethyl methacrylate as component (B), (C) Nisseki Neopolymer # 120 (aromatic petroleum resin, brominated 25 (g / 100 g), manufactured by Shin Nippon Petrochemical Co., Ltd.) 25 g as component, calcium carbonate powder (trade name “# NS400 ”, 130 g of an average particle diameter of 1.71 μm, manufactured by Nitto Flour Chemical Co., Ltd.) was dissolved by heating at 60 ° C., and cooled to room temperature after mixing. Furthermore, 2.2 g of Park Mill H (manufactured by NOF Corporation, 80% cumene hydroperoxide) was added and stirred as component (E) to obtain Example Composition 10 (O). To this, 20 g of Aronix M113 (nonylphenol ethylene oxide 4 mol modified acrylate, cured product glass transition temperature -20 ° C, manufactured by Toagosei Co., Ltd.) as component (A), Octlife Co12 (produced by Shinto Fine Co., Ltd.) Example composition 10 (R) agent consisting of 0.5 g of metal soap cobalt content (cobalt octenoate 12%) and 10 g of toluene was added and mixed to form Example cured body 10. Example composition 10 was cured in 120 minutes at 25 ° C.
以下に、比較例を示す。 A comparative example is shown below.
（比較例１）（Ａ）成分としてアロニックスＭ１１１（ノニルフェノールエチレンオキサイド１モル変性アクリレート、硬化物のガラス転移温度１７℃、東亞合成社製）１００ｇを用いた以外は実施例１と同様の方法で比較例組成物１を得た。比較例組成物１は２５℃条件下、６０分で硬化し、比較例硬化体１を形成した。 (Comparative Example 1) Comparison was made in the same manner as in Example 1 except that 100 g of Aronix M111 (nonylphenol ethylene oxide 1 mol modified acrylate, glass transition temperature of cured product 17 ° C, manufactured by Toagosei Co., Ltd.) 100 g was used as component (A). Example composition 1 was obtained. The comparative example composition 1 was cured in 25 minutes at 25 ° C. to form a comparative example cured body 1.
（比較例２）（Ｆ）成分の代わりにモノベンゾイルチオ尿素２．２部を用いたこと以外は実施例１と同様の方法で比較例組成物２を得た。比較例組成物２は２５℃条件下、６０分で硬化し、比較例硬化体２を形成した。 Comparative Example 2 Comparative Example Composition 2 was obtained in the same manner as in Example 1 except that 2.2 parts of monobenzoylthiourea was used instead of component (F). The comparative composition 2 was cured in 25 minutes at 25 ° C. to form a comparative cured body 2.
測定方法は以下の通りである。 The measuring method is as follows.
（測定方法１）：ガラス転移温度
ガラス転移温度の測定はＪＩＳ Ｋ ７１２１「プラスチックの転移温度測定法」によって測定した。
(Measurement method 1): Glass transition temperature The glass transition temperature was measured according to JIS K 7121 “Plastic transition temperature measurement method”.
（測定方法２）：ヨウ素価
ヨウ素化の測定はＪＩＳ Ｋ ００７０「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化価物の試験方法」によって測定した。
(Measurement method 2): Iodine value Iodination was measured according to JIS K 0070 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and non-saponification value of chemical products”.
（測定方法３）：臭素化
臭素化の測定はＪＩＳ Ｋ ２６０５「石油製品−臭素価試験方法−電気滴定法」によって測定した。
(Measurement method 3): Bromination bromination was measured according to JIS K 2605 “Petroleum products—Bromine number test method—Electro titration method”.
（測定方法４）：硬化時間
硬化時間の測定は以下に従った。樹脂組成物１００ｇを容器に入れ混合し、発泡スチロール系断熱材で覆った。樹脂組成物にＫ型熱伝対（０．３×１ＰＫ−Ｓ、二宮電線工業（株）製）を挿入し、温度変化を測定し、樹脂組成物を容器に加えてから発熱ピークを示すまでの時間を硬化時間とした。
(Measurement method 4): Curing time The curing time was measured as follows. 100 g of the resin composition was placed in a container and mixed, and covered with a polystyrene foam heat insulating material. Insert a K-type thermocouple (0.3 × 1PK-S, manufactured by Ninomiya Electric Wire & Cable Co., Ltd.) into the resin composition, measure the temperature change, add the resin composition to the container, and then show an exothermic peak Was set as the curing time.
（測定方法５）：硬化物の水膨張率
硬化物の水膨張率は寸法２０×５×５０ｍｍの実施例硬化体又は比較例硬化体試験片を作製し、次式によって硬化物の水膨張率を求めた。
硬化物の水膨張率（％）＝［（水浸漬後の試験片の体積−水浸漬前の試験片の体積）／（水浸漬前の試験片の体積）］×１００
ここで、水浸漬前の試験片の体積（ｃｍ３）は温度２３℃、湿度６０％ＲＨで１週間硬化養生した後の試験片の体積であり、水浸漬後の試験片の体積（ｃｍ３）は上記試験片を５０±５℃の水中に１週間浸漬した後の試験片の体積である。
(Measuring method 5): Water expansion coefficient of the cured product The water expansion coefficient of the cured product is an example cured body or comparative cured body test piece having a size of 20 × 5 × 50 mm, and the water expansion coefficient of the cured product according to the following formula: Asked.
Water expansion coefficient (%) of cured product = [(Volume of test piece after water immersion−Volume of test piece before water immersion) / (Volume of test piece before water immersion)] × 100
Here, the volume (cm 3 ) of the test piece before water immersion is the volume of the test piece after curing for 1 week at a temperature of 23 ° C. and a humidity of 60% RH, and the volume of the test piece after water immersion (cm 3). ) Is the volume of the test piece after the test piece is immersed in water at 50 ± 5 ° C. for 1 week.
（測定方法６）：硬化物の引張弾性率
硬化物の引張弾性率はＪＩＳ Ｋ ７１１３「プラスチックの引張試験方法」によって測定した。試験片の種類は１（１／２）号形とし、温度２３℃、湿度６０％ＲＨで１週間硬化養生した後の実施例硬化体又は比較例硬化体試験片を用い、試験速度Ｈ（２００ｍｍ／ｍｉｎ±１０％）で測定した。
(Measurement Method 6): Tensile Elastic Modulus of Cured Product The tensile elastic modulus of the cured product was measured according to JIS K 7113 “Plastic Tensile Test Method”. The type of the test piece is 1 (1/2) type, and the test speed H (200 mm) was used using the test specimens of the cured examples and comparative examples after curing for 1 week at a temperature of 23 ° C. and a humidity of 60% RH. / Min ± 10%).
（測定方法７）：止水性試験
試験体の作製：ＪＩＳ Ａ ５３７１「プレキャスト無筋コンクリート製品」のＩ類、舗装用平板、略号Ｎ（寸法３００×３００×６０ｍｍ）を寸法１５０×３００×６０ｍｍに切断し、切断面の両端に厚み５ｍｍのスペーサーを配置した後、５ｍｍの空隙を実施例組成物又は比較例組成物で充填接着し、試験体とした。樹脂組成物の硬化養生は温度２３℃、湿度６０％ＲＨで１週間とした。
止水性試験：社団法人日本道路協会「道路床版防水便覧（平成１９年３月）」の防水性試験Ｉの方法に準じて実施し、試験時間３０分間における減水量０．２ｍｌ以下を初期の止水性試験の合格判定とした。但し、長期止水性試験の試験時間は１週間、４週間、１２週間とした。漏水の有無を目視で観察し、漏水が認められない場合を合格判定とした。防水性試験Ｉの方法は、以下（１）〜（５）の順序に従った方法である（図１参照）。
（１）舗装用平板１を実施例組成物又は比較例組成物の硬化体２で接着し、試験体を作製する。試験体を取り付け治具３により止水性試験装置に取り付ける。
（２）水注入口４から水を入れ、目盛り５の数値を読む（０分時）。
（３）エアーコンプレッサー７で０．１ＭＰａの圧力を掛ける。圧力は圧力計８により確認する。３分後と３３分後の水位６の数値を読み、減水量を０．１ｍｌ単位まで測定する。
（４）３０分間減水量を下式により求める。
３０分間減水量（ｍｌ）＝３３分後の減水量（ｍｌ）−３分後の減水量（ｍｌ）
（５）試験を継続して、１週間後、４週間後、１２週間後の舗装用平板接着部の下部からの漏水の有無を目視で確認する。
(Measurement method 7): Preparation of water-stopping test specimen: Class I of JIS A 5371 “Precast unreinforced concrete product”, pavement flat plate, abbreviation N (dimension 300 × 300 × 60 mm) to 150 × 300 × 60 mm After cutting and arranging spacers having a thickness of 5 mm at both ends of the cut surface, a 5 mm gap was filled and bonded with the example composition or the comparative example composition to obtain a test specimen. The resin composition was cured for 1 week at a temperature of 23 ° C. and a humidity of 60% RH.
Water-stop test: Conducted according to the method of waterproof test I of the Japan Road Association's "Road Floor Waterproof Manual (March 2007)". It was determined to pass the water-stop test. However, the test time of the long-term water-stopping test was 1 week, 4 weeks, and 12 weeks. The presence or absence of water leakage was visually observed, and the case where water leakage was not observed was determined to be acceptable. The method of the waterproof test I is a method according to the following order (1) to (5) (see FIG. 1).
(1) A pavement flat plate 1 is bonded with a cured body 2 of an example composition or a comparative example composition to prepare a test body. The test body is attached to the water-stopping test apparatus with the attachment jig 3.
(2) Pour water from the water inlet 4 and read the value on the scale 5 (at 0 minutes).
(3) A pressure of 0.1 MPa is applied by the air compressor 7. The pressure is confirmed with a pressure gauge 8. Read the value of the water level 6 after 3 minutes and 33 minutes, and measure the amount of water reduction to 0.1 ml.
(4) The amount of water reduction for 30 minutes is obtained by the following equation.
Water loss for 30 minutes (ml) = Water loss after 33 minutes (ml)-Water loss after 3 minutes (ml)
(5) The test is continued, and the presence or absence of water leakage from the lower part of the flat plate bonding portion for paving after 1 week, 4 weeks, and 12 weeks is visually confirmed.
（測定方法８）：接着強さ試験
試験体の作製： ＪＩＳ Ｒ ５２０１の９．４に規定する方法によって調整したモルタルを用い、寸法７０×７０×２０ｍｍのモルタル試験片を作製した。このモルタルとＪＩＳ Ａ ５５４８にて規定する寸法４０×４０×１０ｍｍの鉄片を実施例組成物又は比較例組成物で接着し試験体とした。
組成物の膜厚はスペーサーで１ｍｍとなるように調整し、養生条件は標準条件（温度２０℃、湿度６５％ＲＨ、１６８時間）とした。処理条件は温水浸漬処理（標準条件で養生後、５０℃温水中、２４時間）とした。
接着強さ試験：ＪＩＳ Ａ ５５４８に規定する接着強さ試験により、接着強さ及び破断状態を測定した。本発明では、凝集破壊が好ましい。凝集破壊は、樹脂組成物と被着体（試験片）との界面の接着力があるからである。界面破壊は、樹脂組成物と被着体（試験片）との界面の接着力が不足しており、好ましくない。
(Measurement method 8): Production of adhesion strength test specimen: Using a mortar prepared by the method defined in 9.4 of JIS R 5201, a mortar test piece having a size of 70 × 70 × 20 mm was produced. This mortar was bonded to an iron piece having a size of 40 × 40 × 10 mm defined by JIS A 5548 with an example composition or a comparative example composition to obtain a test specimen.
The film thickness of the composition was adjusted to 1 mm with a spacer, and the curing conditions were standard conditions (temperature 20 ° C., humidity 65% RH, 168 hours). The treatment conditions were hot water immersion treatment (after curing under standard conditions, 50 ° C. warm water for 24 hours).
Adhesive strength test: Adhesive strength and breaking state were measured by an adhesive strength test specified in JIS A 5548. In the present invention, cohesive failure is preferred. This is because the cohesive failure has an adhesive force at the interface between the resin composition and the adherend (test piece). Interfacial fracture is not preferable because the adhesive force at the interface between the resin composition and the adherend (test piece) is insufficient.
（測定方法９）：平均粒径：レーザー回折法により平均粒径を測定。機種は、ＬＡ−９２０（堀場製作所）を使用した。 (Measurement method 9): Average particle diameter: The average particle diameter is measured by a laser diffraction method. The model used was LA-920 (Horiba Seisakusho).
（実施例測定結果）実施例の測定結果を表１に示す。 (Example measurement results) Table 1 shows the measurement results of the examples.
（比較例測定結果）比較例の測定結果を表２に示す。 Comparative Example Measurement Results Table 2 shows the measurement results of the comparative example.
表１〜２から、本発明に用いる樹脂組成物は、以下の傾向を示す。
（１）水膨張率が大きく、コンクリート構造物や金属構造物等といった構造物の接着部が長期間水に接触していても止水性を確保することができる。
（２）弾性率が低いので硬化物が柔軟であり、地震等で構造物が振動しても、接着部から構造物が破壊することがない。
（３）樹脂組成物と被着体（試験片）との界面の接着力が大きく、破壊状態は凝集破壊である。
（４）石油樹脂を使用したため、止水性が大きい。
（５）（Ｏ）剤と（Ｒ）剤の質量比が、（Ｏ）剤／（Ｒ）剤＝（０．０２〜３５０）／１の範囲外であったり、（Ｏ）剤と（Ｒ）剤の質量比を調整するために、例えばトルエンなどの溶剤で希釈したりすると、所定の物性の樹脂組成物の硬化体が得られず、接着性能や止水性が小さい場合がある。
From Tables 1-2, the resin composition used for this invention shows the following tendencies.
(1) The water expansion coefficient is large, and waterproofness can be ensured even if the adhesion part of a structure such as a concrete structure or a metal structure is in contact with water for a long time.
(2) Since the elastic modulus is low, the cured product is flexible, and even if the structure vibrates due to an earthquake or the like, the structure does not break from the bonded portion.
(3) The adhesive force at the interface between the resin composition and the adherend (test piece) is large, and the fracture state is cohesive failure.
(4) Since the petroleum resin is used, the water stoppage is large.
(5) The mass ratio of the (O) agent and the (R) agent is outside the range of (O) agent / (R) agent = (0.02-350) / 1, or the (O) agent and (R) In order to adjust the mass ratio of the agent, for example, when diluted with a solvent such as toluene, a cured product of a resin composition having predetermined physical properties may not be obtained, and the adhesive performance and water stoppage may be small.
（発明の実施の形態１）
全国プレホール工業会の組立マンホールの０号マンホール底版と高さ６００ｍｍの直壁を実施例組成物８で、又、比較として比較例組成物２で接着した。接着した組立マンホールの内部に水を張り、漏水の有無を観察した結果、実施例組成物８で接着したマンホールは３ヶ月経過後でも漏水はないが、比較例組成物２で接着したマンホールは１週間後に漏水が認められた。
(Embodiment 1 of the invention)
A No. 0 manhole bottom plate of an assembly manhole of the National Prehall Industry Association and a straight wall having a height of 600 mm were bonded with Example Composition 8 and Comparative Example Composition 2 as a comparison. As a result of applying water to the inside of the bonded assembly manhole and observing the presence or absence of water leakage, the manhole adhered with Example Composition 8 did not leak even after 3 months, but the manhole adhered with Comparative Composition 2 was 1 Leakage was observed after a week.
（発明の実施の形態２）
漏水の認められるＰ−Ｔ型鋼管矢板継手の継手部に実施例組成物８を圧力０．５ＭＰａで注入し、充填硬化させた。充填硬化後は１ヶ月後でも漏水は認められない結果であった。比較として比較例１組成物を同様の漏水状態の継手部に注入し充填硬化させた結果、充填硬化直後は漏水が止まったが、１週間後に再び漏水が認められた。
(Embodiment 2 of the invention)
Example composition 8 was injected at a pressure of 0.5 MPa into a joint portion of a PT steel pipe sheet pile joint where water leakage was observed, and was cured by filling. After filling and curing, no water leakage was observed even after one month. As a comparison, the composition of Comparative Example 1 was poured into a joint portion in the same water leakage state and filled and cured. As a result, water leakage stopped immediately after filling and curing, but water leakage was observed again after one week.
例えば、硬化物の水膨張率が１０〜３００％以下であり、かつ、引張弾性率が０．０５〜５Ｎ／ｍｍ２である樹脂組成物は、コンクリート構造物又は金属構造物といった構造物の接着材として使用した場合、水圧の高い状態で長期間水に接触しても、必要な止水性を確保できる。本発明の樹脂組成物で接着した構造物は、止水性に優れる。本発明の樹脂組成物は、止水性樹脂組成物として、産業上の利用可能性が大きい。 For example, the resin composition having a water expansion coefficient of a cured product of 10 to 300% or less and a tensile elastic modulus of 0.05 to 5 N / mm 2 is used for adhesion of a structure such as a concrete structure or a metal structure. When used as a material, even if it is in contact with water for a long period of time under a high water pressure, the required water-stopping property can be secured. The structure bonded with the resin composition of the present invention is excellent in water blocking. The resin composition of the present invention has great industrial applicability as a water-stopping resin composition.
１ 舗装用平板
２ 実施例組成物又は比較例組成物の硬化体
３ 取り付け治具
４ 水注入口
５ 目盛り
６ 水位
７ エアーコンプレッサー
８ 圧力計
DESCRIPTION OF SYMBOLS 1 Pavement flat plate 2 Cured body of Example composition or Comparative example composition 3 Mounting jig 4 Water inlet 5 Scale 6 Water level 7 Air compressor 8 Pressure gauge
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