JP2005290244A - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
- Publication number
- JP2005290244A JP2005290244A JP2004108753A JP2004108753A JP2005290244A JP 2005290244 A JP2005290244 A JP 2005290244A JP 2004108753 A JP2004108753 A JP 2004108753A JP 2004108753 A JP2004108753 A JP 2004108753A JP 2005290244 A JP2005290244 A JP 2005290244A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- polymer
- acrylic
- group
- crosslinkable silyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 33
- -1 amine compound Chemical class 0.000 claims abstract description 25
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 19
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 14
- 238000010186 staining Methods 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000005395 methacrylic acid group Chemical group 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 229920000620 organic polymer Polymers 0.000 description 17
- 239000003973 paint Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical group [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- FQILZCAXBBSGEC-UHFFFAOYSA-N n-benzyl-n,2-dimethylaniline Chemical compound C=1C=CC=C(C)C=1N(C)CC1=CC=CC=C1 FQILZCAXBBSGEC-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PPFQMADUQXIJLH-UHFFFAOYSA-N nickel;tributylphosphane Chemical compound [Ni].CCCCP(CCCC)CCCC.CCCCP(CCCC)CCCC PPFQMADUQXIJLH-UHFFFAOYSA-N 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 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
- 238000003860 storage Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
耐候性、塗料非汚染性、復元性及び耐久性に優れる硬化性組成物を提供する。
【解決手段】
(A)架橋性シリル基を分子鎖末端に有する(メタ)アクリル系重合体、(B)エポキシ基含有(メタ)アクリル系重合体、(C)2価の錫有機カルボン酸塩、及び(D)有機アミン化合物を含有するようにした。前記(B)エポキシ基含有アクリル系重合体の重量平均分子量が1,000以上7,500以下であることが好ましい。前記重合体(A)が、リビングラジカル重合法で製造された(メタ)アクリル系重合体であることが好適である。
【選択図】 なし
Description
(A)架橋性シリル基含有有機重合体
(B)エポキシ基含有(メタ)アクリル系重合体
(C)2価の錫有機カルボン酸塩
(D)有機アミン化合物
R4CR2YCOOR5・・・(3)
R4CR2YCOR5・・・(4)
R4−C6H5−SO2Y・・・(5)
[式(2)〜(5)中、R2,R3は水素原子又はメチル基、R4,R5は水素原子又は炭素数1〜20のアルキル基、アリール基又はアラルキル基、Yは塩素、臭素又はヨウ素である。)
撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ノルマルブチルアクリレート85重量部、メチルメタクリレート15重量部、γ−メタクリロキシプロピルトリメトキシシラン10重量部、及び金属触媒としてチタノセンジクロライド0.1重量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を70℃に加熱した。
表1に示した如く、成分(A)架橋性シリル基含有有機重合体として変性シリコーンポリマーSA100S(鐘淵化学工業(株)製:商品名SA100S)、成分(B)としてXG−4010(東亜合成(株)製)、重質炭酸カルシウム、表面処理炭酸カルシウム、老化防止剤、成分(C)としてネオスタンU−28(日東化成(株)製)、及び成分(D)としてファーミン20D(花王(株)製)を、それぞれ所定量ずつ仕込み硬化性組成物を調製した。
*1:リビングラジカル重合によって製造された分子末端に架橋性シリル基を有するアクリル系重合体(鐘淵化学工業(株)製:商品名SA100S)
*2:合成例1で得られた架橋性シリル基含有アクリル重合体
*3:架橋性シリル基含有ポリオキシアルキレン重合体(鐘淵化学工業(株)製:商品名S−810)
*4:架橋性シリル基含有アクリル変性ポリオキシアルキレン重合体(鐘淵化学工業(株)製:商品名S−943)
*5:エポキシ基含有アクリル系重合体(東亜合成(株)製:商品名XG−4010、1分子平均エポキシ基数1.4個)
*6:エポキシ系可塑剤(新日本理化(株):商品名サンソサイザーE−145、EPS、分子量410)
*7:フタル酸系可塑剤(DINP)
*8:アクリル系重合体(官能基なし、東亜合成(株)製:商品名UP−1000)
*9:スタナスオクトエート 2価錫化合物(日東化成(株)製:商品名ネオスタンU−28)
*10:ジブチルスズラウレート 4価錫化合物(日東化成(株)製:商品名ネオスタンU−100)
*11:ラウリルアミン(花王(株)製:商品名ファーミン20D)
*12:重質炭酸カルシウム(備北粉化(株)製:商品名ホワイトンSB)
*13:表面処理炭酸カルシウム(丸尾カルシウム(株)製:商品名カルファイン200)
*14:老化防止剤(チバスペシャリティーケミカルズ(株)製:商品名チヌビンB−75)
表1に示した如く、配合物質及び配合割合を変更した以外は実施例1と同様の手順で硬化性組成物を調製した。
JIS A 1439に準じたH形試験体を作成し、23℃50%RH環境下において7日間、50℃環境下において7日間、さらに90℃環境下において14日間養生した。その後23℃50%RH環境下で24時間静置させた。その時の厚み(約12.00mm)を初期とした。次に23℃50%RH環境下において所定の治具を使用し、200%伸張(約24.00mm)させた状態で24時間放置した。24時間後、治具を取り外し1時間静置後、厚みを測定し、下記式を用いて復元性を得た。
復元性(%)=(伸張後の厚み−解除後の厚み)/初期の厚み×100
JIS A 1439(1997)4.17耐久性試験(耐久性区分9030)を行った。耐久性試験結果については、○は合格、×は不合格とした。
シーリング材養生条件:23℃50%RH条件下において7日間
塗料養生条件:23℃50%RH条件下において7日間
評価方法:50℃乾燥機において7日間加熱促進後、黒色珪砂を塗料にふりかけ、砂の付着度により汚染の有無を目視により確認した。全ての塗料に対して汚染が全く見られない場合は○、1つでも汚染が見られる場合は×として評価した。
塗料;ビルデック:溶剤系アクリル、大日本塗料(株)製
ビニローゼ:溶剤系塩化ビニル、大日本塗料(株)製
ビューロン:水系アクリル、大日本塗料(株)製
オーデコートG:水系アクリル、日本ペイント(株)製
DANユニ:水系アクリル、日本ペイント(株)製
ニュートップレスクリーン:水系アクリルシリコーン、SK化研(株)製
プリーズコート:水系アクリル、SK化研(株)製
タイルラックU:ウレタン系、日本ペイント(株)製
ニューソフトリシン:水系アクリル、SK化研(株)製
サンシャインウェザーオメーターにおいて耐候性試験を行い、1000時間後、2000時間後の外観を調べた。耐候性試験結果において、○はクラックがなく、△は僅かにクラックがあり、×はクラックが多数あることを意味する。
Claims (5)
- (A)架橋性シリル基を分子鎖末端に有する(メタ)アクリル系重合体、
(B)エポキシ基含有(メタ)アクリル系重合体、
(C)2価の錫有機カルボン酸塩、及び
(D)有機アミン化合物を含有することを特徴とする硬化性組成物。 - 前記重合体(A)が、リビングラジカル重合法で製造された(メタ)アクリル系重合体であることを特徴とする請求項1記載の硬化性組成物。
- 前記重合体(A)が、原子移動ラジカル重合法で製造された(メタ)アクリル系重合体であることを特徴とする請求項1又は2記載の硬化性組成物。
- 前記重合体(A)が、架橋性シリル基を分子鎖末端に有する(メタ)アクリル系重合体と架橋性シリル基含有ポリオキシアルキレン系重合体との混合物であることを特徴とする請求項1〜3のいずれか1項記載の硬化性組成物。
- 前記エポキシ基含有(メタ)アクリル系重合体(B)の重量平均分子量が1,000以上7,500以下であることを特徴とする請求項1〜4のいずれか1項記載の硬化性組成物。
4
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004108753A JP5097330B2 (ja) | 2004-04-01 | 2004-04-01 | 建築用弾性シーリング材組成物 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004108753A JP5097330B2 (ja) | 2004-04-01 | 2004-04-01 | 建築用弾性シーリング材組成物 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005290244A true JP2005290244A (ja) | 2005-10-20 |
JP5097330B2 JP5097330B2 (ja) | 2012-12-12 |
Family
ID=35323541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004108753A Expired - Lifetime JP5097330B2 (ja) | 2004-04-01 | 2004-04-01 | 建築用弾性シーリング材組成物 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5097330B2 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007036981A1 (ja) * | 2005-09-27 | 2007-04-05 | Cemedine Co., Ltd. | 硬化性組成物 |
WO2007069600A1 (ja) * | 2005-12-13 | 2007-06-21 | Kaneka Corporation | 制振材用硬化性組成物および制振材 |
JP2008019300A (ja) * | 2006-07-11 | 2008-01-31 | Cemedine Co Ltd | 被塗装性に優れた硬化性組成物 |
WO2008041768A1 (fr) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Composition durcissable |
JP2010116444A (ja) * | 2008-11-11 | 2010-05-27 | Kaneka Corp | 硬化性組成物 |
WO2010150361A1 (ja) * | 2009-06-24 | 2010-12-29 | 株式会社カネカ | 硬化性樹脂組成物 |
WO2021157583A1 (ja) * | 2020-02-04 | 2021-08-12 | 株式会社カネカ | 組成物、硬化性組成物、硬化物および貯蔵方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0347871A (ja) * | 1989-04-07 | 1991-02-28 | Kanegafuchi Chem Ind Co Ltd | 熱硬化性組成物およびそれを塗装した塗装物 |
JPH0559289A (ja) * | 1991-08-29 | 1993-03-09 | Dainippon Ink & Chem Inc | 硬化性樹脂組成物 |
JPH11116686A (ja) * | 1997-10-09 | 1999-04-27 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JP2001271055A (ja) * | 2000-03-27 | 2001-10-02 | Kanegafuchi Chem Ind Co Ltd | シーリング材組成物 |
JP2004083606A (ja) * | 2001-08-14 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性樹脂組成物 |
-
2004
- 2004-04-01 JP JP2004108753A patent/JP5097330B2/ja not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0347871A (ja) * | 1989-04-07 | 1991-02-28 | Kanegafuchi Chem Ind Co Ltd | 熱硬化性組成物およびそれを塗装した塗装物 |
JPH0559289A (ja) * | 1991-08-29 | 1993-03-09 | Dainippon Ink & Chem Inc | 硬化性樹脂組成物 |
JPH11116686A (ja) * | 1997-10-09 | 1999-04-27 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JP2001271055A (ja) * | 2000-03-27 | 2001-10-02 | Kanegafuchi Chem Ind Co Ltd | シーリング材組成物 |
JP2004083606A (ja) * | 2001-08-14 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性樹脂組成物 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8519049B2 (en) | 2005-09-27 | 2013-08-27 | Cemedine Co., Ltd. | Curable composition |
WO2007036981A1 (ja) * | 2005-09-27 | 2007-04-05 | Cemedine Co., Ltd. | 硬化性組成物 |
WO2007069600A1 (ja) * | 2005-12-13 | 2007-06-21 | Kaneka Corporation | 制振材用硬化性組成物および制振材 |
JP5438902B2 (ja) * | 2005-12-13 | 2014-03-12 | 株式会社カネカ | 制振材用硬化性組成物および制振材 |
JP2008019300A (ja) * | 2006-07-11 | 2008-01-31 | Cemedine Co Ltd | 被塗装性に優れた硬化性組成物 |
WO2008041768A1 (fr) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Composition durcissable |
US7977399B2 (en) | 2006-10-05 | 2011-07-12 | Kaneka Corporation | Curable composition |
JP2010116444A (ja) * | 2008-11-11 | 2010-05-27 | Kaneka Corp | 硬化性組成物 |
WO2010150361A1 (ja) * | 2009-06-24 | 2010-12-29 | 株式会社カネカ | 硬化性樹脂組成物 |
US8658738B2 (en) | 2009-06-24 | 2014-02-25 | Kaneka Corporation | Curable resin composition |
WO2021157583A1 (ja) * | 2020-02-04 | 2021-08-12 | 株式会社カネカ | 組成物、硬化性組成物、硬化物および貯蔵方法 |
CN115038753A (zh) * | 2020-02-04 | 2022-09-09 | 株式会社钟化 | 组合物、固化性组合物、固化物及储存方法 |
CN115038753B (zh) * | 2020-02-04 | 2024-03-19 | 株式会社钟化 | 组合物、固化性组合物、固化物及储存方法 |
Also Published As
Publication number | Publication date |
---|---|
JP5097330B2 (ja) | 2012-12-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2342788C (en) | Resin composition, polymer and process for producing polymer | |
US8217130B2 (en) | Curable composition and method for producing the same | |
WO2006104097A1 (ja) | アクリル系ブロック共重合体、反応性ホットメルト接着剤組成物 | |
JP2002155145A (ja) | 硬化性組成物 | |
JP5582333B2 (ja) | 硬化性組成物 | |
JP6557030B2 (ja) | 非接着性湿気硬化型樹脂組成物 | |
JP5097330B2 (ja) | 建築用弾性シーリング材組成物 | |
JP6198180B2 (ja) | 2液型硬化性組成物 | |
JP2005082750A (ja) | 接着性に優れた硬化性組成物 | |
JP4754455B2 (ja) | 硬化性組成物 | |
JP4504007B2 (ja) | 建築用弾性シーリング材組成物 | |
JP3953995B2 (ja) | 1液型硬化性組成物 | |
WO1997006212A1 (fr) | Composition polymere durcissante | |
JP2009108246A (ja) | 石目地用シーリング材組成物 | |
JPS5978222A (ja) | 室温硬化性弾性組成物 | |
JP2012107103A (ja) | 硬化性組成物 | |
JP3962184B2 (ja) | 樹脂組成物、重合体及び重合体の製造方法 | |
JP4808430B2 (ja) | 室温硬化性組成物の製造方法 | |
JP2015078568A (ja) | クラック補修方法 | |
JP4889251B2 (ja) | 速硬化型接着剤組成物 | |
JP6866098B2 (ja) | 硬化性組成物 | |
JP5311529B2 (ja) | 硬化性組成物 | |
JP2015025689A (ja) | 放射線遮蔽材の接合方法 | |
JP4739457B2 (ja) | 硬化性組成物 | |
JP4339531B2 (ja) | ポリイソブチレン系シーリング材用プライマー組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070112 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090903 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090907 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090908 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091029 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100225 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100524 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20100701 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100726 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20101015 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120924 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5097330 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150928 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |