JP2008189735A - Primer composition and method for producing the same - Google Patents
Primer composition and method for producing the same Download PDFInfo
- Publication number
- JP2008189735A JP2008189735A JP2007023701A JP2007023701A JP2008189735A JP 2008189735 A JP2008189735 A JP 2008189735A JP 2007023701 A JP2007023701 A JP 2007023701A JP 2007023701 A JP2007023701 A JP 2007023701A JP 2008189735 A JP2008189735 A JP 2008189735A
- Authority
- JP
- Japan
- Prior art keywords
- polyisocyanate
- primer composition
- average molecular
- number average
- diisocyanate
- 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 78
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 105
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 105
- -1 acrylic polyol Chemical class 0.000 claims abstract description 69
- 229920005862 polyol Polymers 0.000 claims abstract description 43
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000010454 slate Substances 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 206010008428 Chemical poisoning Diseases 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 5
- 230000002265 prevention Effects 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 150000007529 inorganic bases Chemical class 0.000 abstract description 10
- 238000007711 solidification Methods 0.000 abstract description 10
- 230000008023 solidification Effects 0.000 abstract description 10
- 239000002987 primer (paints) Substances 0.000 description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 125000003118 aryl group Chemical group 0.000 description 22
- 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 21
- 238000009835 boiling Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 2
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000007815 allergy Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical class N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- UWJRJUDLJQOQSP-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1C UWJRJUDLJQOQSP-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 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
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 238000005728 strengthening 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、プライマー組成物およびその製造方法に関する。 The present invention relates to a primer composition and a method for producing the same.
従来、スレート瓦などの建築物の無機質基材のプライマーとしては、エポキシ／アミンの２液硬化システム（特許文献１：特開２００２−２５６２２１号公報参照）が汎用されている。
このエポキシ／アミン系のプライマーは、無機質基材への浸透固化性に優れているものの、人体へのアレルギー性や、環境負荷が大きい等の問題を抱えている。
Conventionally, as a primer for an inorganic base material of a building such as a slate roof tile, an epoxy / amine two-component curing system (see Japanese Patent Application Laid-Open No. 2002-256221) is widely used.
Although this epoxy / amine-based primer is excellent in penetrability and solidification into an inorganic base material, it has problems such as allergenicity to the human body and a large environmental load.
この点に鑑み、近年、アクリル系やウレタン系のプライマーが提案されている（特許文献２：特開２００２−３０８９６１号公報、特許文献３：特開２００５−３５０８９２号公報、特許文献４：特開２００６−２０６７０８号公報、特許文献５：特開２００６−８３３７２号公報参照）。
しかし、これらのプライマーは、エポキシ／アミン系のプライマーと比べて人体や環境に対する負荷は小さいものの、スレート瓦等の無機質基材に対する浸透固化性、特に、劣化の激しい基材に対する浸透固化性が低いため、必ずしもプライマーとして実用上十分な性能を有しているとは言えない。
In view of this point, in recent years, acrylic and urethane primers have been proposed (Patent Document 2: Japanese Patent Laid-Open No. 2002-308961, Patent Document 3: Japanese Patent Laid-Open No. 2005-350892, and Patent Document 4: Japanese Patent Laid-Open No. 2004-26883. 2006-206708, Patent Document 5: Japanese Patent Laid-Open No. 2006-83372).
However, these primers have a smaller load on the human body and the environment than the epoxy / amine-based primers, but they have low osmotic solidification properties on inorganic substrates such as slate roof tiles, in particular, poorly osmotic solidification properties on substrates with severe deterioration. Therefore, it cannot always be said that the primer has sufficient performance as a primer.
本発明は、上記事情に鑑みてなされたものであり、建築物などの無機質基材に対する浸透固化性に優れるとともに、人体や環境に優しいプライマー組成物およびその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a primer composition that is excellent in penetrability and solidification with respect to an inorganic base material such as a building and is friendly to the human body and the environment, and a method for producing the same. .
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、所定のアクリル変性（ポリ）イソシアネートと、分子量の異なる２種類のポリイソシアネートとを所定割合で配合してなる組成物が、スレート瓦等の無機質基材に対する浸透固化性能に優れ、建造物の塗膜のプライマーとして好適であることを見出し、本発明を完成した。 As a result of intensive studies in order to achieve the above object, the present inventors have obtained a composition comprising a predetermined acrylic-modified (poly) isocyanate and two polyisocyanates having different molecular weights in a predetermined ratio. The present invention was completed by discovering that it is excellent in permeation and solidification performance for inorganic base materials such as slate roof tiles and is suitable as a primer for a coating film of a building.
すなわち、本発明は、
１． 数平均分子量４，０００〜１２０，０００、水酸基価５〜１５０ｍｇＫＯＨ／ｇのアクリルポリオール（Ａ１）と、ポリイソシアネート（Ａ２）とを反応させて得られ、分子中にイソシアネート基を１個以上有するアクリル変性（ポリ）イソシアネート（Ａ）、分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）、および分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）を含有し、前記アクリル変性（ポリ）イソシアネート（Ａ）の含有量が、前記アクリル変性（ポリ）イソシアネート（Ａ）、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）の合計質量に対して２０〜６５質量％であり、かつ、前記ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）の含有比が、質量比で（Ｂ）／（Ｃ）＝０．２〜５．０であることを特徴とするプライマー組成物、
２． 前記ポリイソシアネート（Ａ２）が、前記ポリイソシアネート（Ｂ）および／またはポリイソシアネート（Ｃ）である１のプライマー組成物、
３． 前記ポリイソシアネート（Ａ２）が、前記ポリイソシアネート（Ｂ）である１または２のプライマー組成物、
４． 前記ポリイソシアネート（Ｂ）が、脂肪族炭化水素系ポリイソシアネートである１〜３のいずれかのプライマー組成物、
５． 前記脂肪族炭化水素系ポリイソシアネートが、イソホロンジイソシアネート、ノルボルナンジイソシアネート、水素添加キシレンジイソシアネート、水素添加トリレンジイソシアネート、および水素添加ジフェニルメタンジイソシアネートから選ばれる少なくとも１種である４のプライマー組成物、
６． 前記ポリイソシアネート（Ｃ）がヘキサメチレンジイソシアネートのイソシアヌレート体、ビュレット体、および各種ポリオールとのアダクト体から選ばれる少なくとも１種である１〜５のいずれかのプライマー組成物、
７． さらにトルエンおよびキシレンを含まない有機溶剤（Ｄ）を含有する１〜６のいずれかのプライマー組成物、
８． さらに有機溶剤中毒予防規則第三種有機溶剤および／または有機溶剤中毒予防規則に規定されていない有機溶剤（Ｄ）を含有する１〜６のいずれかのプライマー組成物、
９． スレート瓦の改修用である１〜８のいずれかのプライマー組成物、
１０． 数平均分子量４，０００〜１２０，０００、水酸基価５〜１５０ｍｇＫＯＨ／ｇのアクリルポリオール（Ａ１）と、イソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）、および／または分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）とを、未反応の前記ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）が残存する割合で反応させることを特徴とする２のプライマー組成物の製造方法、
１１． 数平均分子量４，０００〜１２０，０００、水酸基価５〜１５０ｍｇＫＯＨ／ｇのアクリルポリオール（Ａ１）と、分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）とを、未反応の前記ポリイソシアネート（Ｂ）が残存する割合で反応させた後、得られた反応液と、分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）とを配合する２のプライマー組成物の製造方法、
１２． 前記アクリルポリオール（Ａ１）と前記ポリイソシアネート（Ｂ）とを、前記ポリイソシアネート（Ｂ）のＮＣＯ基モル濃度［ＮＣＯ］と、前記アクリルポリオール（Ａ１）のＯＨ基モル濃度［ＯＨ］との比が［ＮＣＯ］／［ＯＨ］≧２．５となる割合で反応させる１１のプライマー組成物の製造方法
を提供する。
That is, the present invention
1. An acrylic polymer obtained by reacting a polyisocyanate (A2) with an acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value of 5 to 150 mgKOH / g, and having one or more isocyanate groups in the molecule. Modified (poly) isocyanate (A), polyisocyanate (B) having two or more isocyanate groups in the molecule, number average molecular weight of 150 to less than 400, and two or more isocyanate groups in the molecule, number average The polyisocyanate (C) having a molecular weight of 400 to 2,000 is contained, and the acrylic-modified (poly) isocyanate (A) is contained in the acrylic-modified (poly) isocyanate (A), polyisocyanate (B) and polyisocyanate. 20 to 65% by mass with respect to the total mass of (C), and the polyisocyanate Primer compositions containing ratio of over preparative (B) and the polyisocyanate (C), characterized in that a mass ratio (B) / (C) = 0.2 to 5.0,
2. 1 primer composition in which the polyisocyanate (A2) is the polyisocyanate (B) and / or the polyisocyanate (C);
3. The primer composition of 1 or 2, wherein the polyisocyanate (A2) is the polyisocyanate (B),
4). The primer composition according to any one of 1 to 3, wherein the polyisocyanate (B) is an aliphatic hydrocarbon polyisocyanate,
5. 4 primer compositions wherein the aliphatic hydrocarbon polyisocyanate is at least one selected from isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate;
6). The primer composition according to any one of 1 to 5, wherein the polyisocyanate (C) is at least one selected from an isocyanurate body of hexamethylene diisocyanate, a burette body, and an adduct body with various polyols,
7). Furthermore, the primer composition of any one of 1-6 containing the organic solvent (D) which does not contain toluene and xylene,
8). Furthermore, the primer composition according to any one of 1 to 6, further comprising an organic solvent (D) not stipulated in the organic solvent poisoning prevention regulation type 3 organic solvent and / or the organic solvent poisoning prevention regulation,
9. The primer composition according to any one of 1 to 8, which is used for repairing a slate roof tile,
10. An acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000, a hydroxyl value of 5 to 150 mgKOH / g, a polyisocyanate (B) having two or more isocyanate groups and a number average molecular weight of 150 to less than 400, and And / or the ratio of the unreacted polyisocyanate (B) and polyisocyanate (C) remaining in the polyisocyanate (C) having two or more isocyanate groups in the molecule and having a number average molecular weight of 400 to 2,000 The method for producing a primer composition according to 2, wherein the reaction is performed with
11. Acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value of 5 to 150 mgKOH / g, and a polyisocyanate having a number average molecular weight of 150 to less than 400 (B) having two or more isocyanate groups in the molecule ) At a ratio in which the unreacted polyisocyanate (B) remains, then the reaction solution obtained has two or more isocyanate groups in the molecule, and has a number average molecular weight of 400 to 2,000. A method for producing a primer composition according to 2, wherein the polyisocyanate (C) is blended,
12 The acrylic polyol (A1) and the polyisocyanate (B) have a ratio of the NCO group molar concentration [NCO] of the polyisocyanate (B) to the OH group molar concentration [OH] of the acrylic polyol (A1). The manufacturing method of 11 primer compositions made to react by the ratio used as [NCO] / [OH]> = 2.5 is provided.
本発明によれば、所定のアクリル変性（ポリ）イソシアネートと、分子量の異なる２種類のポリイソシアネートとを所定割合で配合してなる組成物であるから、スレート瓦等の建築材の無機質基材に対する浸透固化性能に優れており、プライマー組成物として好適である。
また、本発明のプライマー組成物は、エポキシ／アミンの２液硬化システムと異なり、１液湿気硬化タイプであることから、可使時間が長いだけでなく、調合残といった廃棄物の低減につながる。しかも、エポキシ樹脂に代表される人体へのアレルギー性も大きく低減されているため、環境・人体への負荷が少ない。
According to the present invention, since it is a composition formed by blending a predetermined acrylic-modified (poly) isocyanate and two types of polyisocyanates having different molecular weights in a predetermined ratio, it can be applied to an inorganic base material for building materials such as slate roof tiles. It has excellent osmotic solidification performance and is suitable as a primer composition.
Further, unlike the epoxy / amine two-component curing system, the primer composition of the present invention is a one-component moisture-curing type, so that not only the pot life is long, but also waste such as a preparation residue is reduced. In addition, the allergenicity to the human body represented by epoxy resin is also greatly reduced, so the burden on the environment and human body is small.
以下、本発明についてさらに詳しく説明する。
本発明に係るプライマー組成物は、数平均分子量４，０００〜１２０，０００、水酸基価（固形分換算）５〜１５０ｍｇＫＯＨ／ｇのアクリルポリオール（Ａ１）と、ポリイソシアネート（Ａ２）とを反応させて得られ、分子中にイソシアネート基を１個以上有するアクリル変性（ポリ）イソシアネート（Ａ）、分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）、および分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）を含有するものである。
Hereinafter, the present invention will be described in more detail.
The primer composition according to the present invention is obtained by reacting an acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value (solid content conversion) of 5 to 150 mgKOH / g with a polyisocyanate (A2). An acrylic-modified (poly) isocyanate (A) having one or more isocyanate groups in the molecule, a polyisocyanate (B) having two or more isocyanate groups in the molecule and a number average molecular weight of 150 to less than 400, and It contains two or more isocyanate groups in the molecule and contains a polyisocyanate (C) having a number average molecular weight of 400 to 2,000.
本発明において、アクリルポリオール（Ａ１）の数平均分子量が、４，０００未満であると、塗膜の初期硬化が遅くなり、長時間にわたりタック感が残る虞があり、一方、１２０，０００を超えると、他のプライマー成分との相溶性が不足し、造膜性が悪化する虞がある。好ましくは数平均分子量６，０００〜９０，０００、より好ましくは、８，０００〜６０，０００である。
なお、数平均分子量は、示差屈折率計検出によるゲルパーミェーションクロマトグラフィー（以下、ＧＰＣと略称する）測定による測定値（ポリスチレン換算値）である。
また、アクリルポリオール（Ａ１）の水酸基価（固形分換算）が、５ｍｇＫＯＨ／ｇ未満であると、他成分との架橋が少なくなり、プライマー強度、接着性が悪化する虞があり、１５０ｍｇＫＯＨ／ｇを超えると、アクリル変性（ポリ）イソシアネートの１分子中の官能基数が増えることから、プライマーの安定性が悪化し、貯蔵中の粘度上昇やゲル化の虞がある。好ましくは水酸基価５〜１００ｍｇＫＯＨ／ｇである。
In the present invention, when the number average molecular weight of the acrylic polyol (A1) is less than 4,000, the initial curing of the coating film is delayed, and there is a possibility that a tacky feeling may remain for a long time, whereas it exceeds 120,000. And there is a possibility that the compatibility with other primer components is insufficient and the film-forming property is deteriorated. The number average molecular weight is preferably 6,000 to 90,000, more preferably 8,000 to 60,000.
The number average molecular weight is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC) by differential refractometer detection (polystyrene conversion value).
Further, when the hydroxyl value (in terms of solid content) of the acrylic polyol (A1) is less than 5 mgKOH / g, there is a possibility that the crosslinking with other components is reduced and the primer strength and adhesiveness are deteriorated, and 150 mgKOH / g is reduced. If it exceeds, the number of functional groups in one molecule of the acrylic-modified (poly) isocyanate increases, so that the stability of the primer is deteriorated, and there is a risk of viscosity increase or gelation during storage. The hydroxyl value is preferably 5 to 100 mgKOH / g.
アクリルポリオール（Ａ１）としては、上記数平均分子量および水酸基価の範囲を満たすものであれば特に限定されるものではなく、水酸基を有するアクリルモノマーと、不飽和二重結合を有するその他の重合性モノマーとをラジカル共重合して得られる各種アクリルポリオールを用いることができる。
水酸基を有するアクリルモノマーの具体例としては、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、３−ヒドロキシブチル（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、Ｎ−メチロール化アクリルアミド、ε−カプロラクトン変性ヒドロキシ（メタ）アクリレート、カーボネート変性メタクリレート（ダイセル化学工業株式会社製、ＨＥＭＡＣ）等が挙げられ、これらは１種単独で用いても、２種以上組み合わせて用いてもよい。
The acrylic polyol (A1) is not particularly limited as long as it satisfies the above range of the number average molecular weight and the hydroxyl value. The acrylic monomer having a hydroxyl group and other polymerizable monomers having an unsaturated double bond And various acrylic polyols obtained by radical copolymerization.
Specific examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxy. Examples include butyl (meth) acrylate, N-methylol acrylamide, ε-caprolactone-modified hydroxy (meth) acrylate, carbonate-modified methacrylate (manufactured by Daicel Chemical Industries, Ltd., HEMAC), and the like. Two or more kinds may be used in combination.
不飽和二重結合を有する重合性モノマーの具体例としては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸等のカルボン酸基含有モノマー、グリシジル（メタ）アクリレート等のエポキシ基含有モノマー、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有モノマー、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ―ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デカニル（メタ）アクリレート、ウンデカニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等のＣ１〜Ｃ２４のアルキル（メタ）アクリレートモノマー、スチレン、α−メチルスチレン、ビニルトルエン等の芳香族炭化水素系モノマー、メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル系モノマー、酢酸ビニル、プロピオン酸ビニル、（メタ）アクリロニトリル、Ｎ−ビニルピロリドン等が挙げられ、これらは１種単独で用いても、２種以上組み合わせて用いてもよい。特に、不飽和二重結合を有する重合性モノマーとして、アルキル（メタ）アクリレートモノマーを用いることが好ましい。 Specific examples of the polymerizable monomer having an unsaturated double bond include carboxylic acid group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, and epoxy group-containing monomers such as glycidyl (meth) acrylate, Amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, pentyl (meth A) C1-C24 alkyl (meth) acrylate monomers such as relate, hexyl (meth) acrylate, octyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Aromatic hydrocarbon monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinyl pyrrolidone, etc. These may be used alone or in combination of two or more. In particular, an alkyl (meth) acrylate monomer is preferably used as the polymerizable monomer having an unsaturated double bond.
上記ラジカル共重合は、無溶剤または適当な有機溶媒存在下、重合開始剤を用いて行われる。
有機溶媒としては、反応に悪影響を及ぼさないものであれば任意であり、例えば、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、シクロヘキサン、シクロペンタン等の脂肪族または脂環族炭化水素；トルエン、キシレン、エチルベンゼン、低沸点芳香族ナフサ、高沸点芳香族ナフサ等の芳香族炭化水素；酢酸エチル、酢酸ｎ−ブチル、酢酸ｎ−アミル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、３−メトキシブチルアセテート等のエステル類；メタノール、エタノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｉｓｏ−ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ−ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノ−ｎ−プロピルエーテル、ジエチレングリコールモノブチルエーテル等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルｎ−アミルケトン、シクロヘキサノン等のケトン類；ジメトキシエタン、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル等のエーテル類；Ｎ−メチルピロリドン、ジメチルフォルムアミド、ジメチルアセトアミド、エチレンカーボネート等が挙げられる。これらは１種単独で用いても、２種以上組み合わせて用いてもよい。
重合開始剤としては、公知のラジカル重合開始剤から適宜選択することができ、例えば、２，２′−アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル、ｔ−ブチルパーオキシド、クメンハイドロパーオキシドなどが挙げられる。これらは１種単独で用いても、２種以上組み合わせて用いてもよい。
反応温度は、通常、６０〜１５０℃程度である。反応時間は、通常、１〜１２時間程度である。
The radical copolymerization is performed using a polymerization initiator in the absence of a solvent or in the presence of a suitable organic solvent.
Any organic solvent may be used as long as it does not adversely influence the reaction. For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, low boiling aromatic naphtha, high boiling aromatic naphtha, etc .; ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3 Esters such as methoxybutyl acetate; methanol, ethanol, iso-propanol, n-butanol, iso-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono Alcohols such as n-propyl ether and diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; dimethoxyethane, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol Dimethyl ether, diethylene glycol Ethers such as call dibutyl ether; N- methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, and the like. These may be used alone or in combination of two or more.
The polymerization initiator can be appropriately selected from known radical polymerization initiators, such as 2,2′-azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl peroxide, Examples include cumene hydroperoxide. These may be used alone or in combination of two or more.
The reaction temperature is usually about 60 to 150 ° C. The reaction time is usually about 1 to 12 hours.
上記アクリルポリオール（Ａ１）と反応させるポリイソシアネート（Ａ２）は任意であり、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、２，４′−ジフェニルメタンジイソシアネート、２，２′−ジフェニルメタンジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート；ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、２−メチル−ペンタン−１，５−ジイソシアネート、３−メチル−ペンタン−１，５−ジイソシアネート、リジンジイソシアネート、トリオキシエチレンジイソシアネート等の脂肪族ジイソシアネート；キシリレン−１，４−ジイソシアネート、キシリレン−１，３−ジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート；イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の脂環族ジイソシアネート等の各種ポリイソシアネートや、それらのヌレート体、ビュレット体などを、１種単独で、または２種以上組み合わせて用いることができる。 The polyisocyanate (A2) to be reacted with the acrylic polyol (A1) is arbitrary, and examples thereof include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- Aromatic diisocyanates such as diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate; hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane- Aliphatic diisocyanates such as 1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate; xylylene-1,4-diisocyanate, xylylene-1,3- Aromatic polyisocyanates such as isocyanate and tetramethylxylylene diisocyanate; various polyisocyanates such as alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate and hydrogenated tetramethylxylene diisocyanate These nurate bodies and burette bodies can be used alone or in combination of two or more.
アクリルポリオール（Ａ１）と、ポリイソシアネート（Ａ２）との反応条件は特に限定されるものではなく、例えば、ウレタン化触媒の存在下、２０〜１５０℃でアクリルポリオール（Ａ１）と、過剰量のポリイソシアネート（Ａ２）とを反応させて、アクリルポリオールの全水酸基をイソシアネート基で封止する手法が挙げられる。
特に、ポリイソシアネート（Ａ２）として、プライマー組成物の構成成分であるポリイソシアネート（Ｂ）および／またはポリイソシアネート（Ｃ）に相当するポリイソシアネートを用いることが好ましく、特に、ポリイソシアネート（Ｂ）に相当するポリイソシアネートを用いることが好適である。これらのポリイソシアネートを用いることで、未反応のポリイソシアネートを除去する必要がなくなるため、プライマー組成物の製造工程が簡略化でき、さらにポリイソシアネート（Ｂ）を用いる場合、アクリル変性（ポリ）イソシアネート（Ａ）の高分子量化を抑制でき、プライマーの貯蔵安定性が高まるという利点がある。
The reaction conditions of the acrylic polyol (A1) and the polyisocyanate (A2) are not particularly limited. For example, the acrylic polyol (A1) and an excess amount of polyisocyanate at 20 to 150 ° C. in the presence of a urethanization catalyst. A method of reacting isocyanate (A2) to seal all hydroxyl groups of acrylic polyol with isocyanate groups can be mentioned.
In particular, as the polyisocyanate (A2), it is preferable to use a polyisocyanate corresponding to the polyisocyanate (B) and / or polyisocyanate (C), which is a constituent component of the primer composition, and particularly, it corresponds to the polyisocyanate (B). It is preferable to use a polyisocyanate. By using these polyisocyanates, it is not necessary to remove unreacted polyisocyanates, so the production process of the primer composition can be simplified. Furthermore, when polyisocyanate (B) is used, acrylic-modified (poly) isocyanate ( The high molecular weight of A) can be suppressed, and the storage stability of the primer is increased.
なお、上記ウレタン化触媒は公知のものから適宜選択することができ、例えば、ジブチル錫ラウレート、ジオクチル錫ラウレートなどが挙げられる。
また、ウレタン化反応の際に、後に詳述するプライマー組成物の任意構成成分である有機溶剤（Ｄ）に相当する溶媒を反応溶媒として用いてもよい。
In addition, the said urethanization catalyst can be suitably selected from a well-known thing, For example, a dibutyl tin laurate, a dioctyl tin laurate, etc. are mentioned.
In the urethanization reaction, a solvent corresponding to the organic solvent (D), which is an optional component of the primer composition described in detail later, may be used as the reaction solvent.
本発明のプライマー組成物を構成するポリイソシアネート（Ｂ）は、分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネートである。その具体例としては、４，４′−ジフェニルメタンジイソシアネート、２，４′−ジフェニルメタンジイソシアネート、２，２′−ジフェニルメタンジイソシアネート、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート、２−ニトロジフェニル−４，４′−ジイソシアネート、２，２′−ジフェニルプロパン−４，４′−ジイソシアネート、３，３′−ジメチルジフェニルメタン−４，４′−ジイソシアネート、４，４′−ジフェニルプロパンジイソシアネート、１，２−フェニレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、１，４−ナフタレンジイソシアネート、１，５−ナフタレンジイソシアネート、３，３′−ジメトキシジフェニル−４，４′−ジイソシアネート等の芳香族ジイソシアネート、１，６−ヘキサメチレンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、水素添加トルエンジイソシアネート、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の脂肪族ジイソシアネート等が挙げられ、これらは１種単独で、または２種以上組み合わせて用いることができる。特に、プライマーの無機質基材への含浸性を向上させることを考慮すると、脂肪族炭化水素系ポリイソシアネートが好ましく、中でも、イソホロンジイソシアネート、ノルボルナンジイソシアネート、水素添加キシレンジイソシアネートが好適である。 The polyisocyanate (B) constituting the primer composition of the present invention is a polyisocyanate having two or more isocyanate groups in the molecule and having a number average molecular weight of 150 or more and less than 400. Specific examples thereof include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenyl ether. Diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenyl Propane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3, Aromatic diisocyanates such as 3'-dimethoxydiphenyl-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetra Examples thereof include aliphatic diisocyanates such as methylxylene diisocyanate, and these can be used alone or in combination of two or more. In particular, in consideration of improving the impregnation property of the primer to the inorganic base material, aliphatic hydrocarbon polyisocyanate is preferable, and among them, isophorone diisocyanate, norbornane diisocyanate, and hydrogenated xylene diisocyanate are preferable.
本発明のプライマー組成物を構成するもう一方のポリイソシアネート（Ｃ）は、分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネートである。その具体例としては、４，４′−ジフェニルメタンジイソシアネート、２，４′−ジフェニルメタンジイソシアネート、２，２′−ジフェニルメタンジイソシアネート、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート、２−ニトロジフェニル−４，４′−ジイソシアネート、２，２′−ジフェニルプロパン−４，４′−ジイソシアネート、３，３′−ジメチルジフェニルメタン−４，４′−ジイソシアネート、４，４′−ジフェニルプロパンジイソシアネート、１，２−フェニレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、１，４−ナフタレンジイソシアネート、１，５−ナフタレンジイソシアネート、３，３′−ジメトキシジフェニル−４，４′−ジイソシアネート等の芳香族ジイソシアネート、１，６−ヘキサメチレンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、水素添加トルエンジイソシアネート、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の脂肪族ジイソシアネートのビュレット体、イソシアヌレート体、ウレトンイミン体、ウレトジオン体、カルボジイミド体などの変性ポリイソシアネートや、上記脂肪族イソシアネートと、グリセロール、トリメチロールプロパン、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールなどのポリオールとを反応させてなるアダクト体、さらにポリフェニレンポリメチレンポリイソシアネート、クルードトルエンジイソシアネート等のポリメリックイソシアネートなどが挙げられ、これらは１種単独で、または２種以上組み合わせて用いることができる。特に、当該プライマーから形成される塗膜の強度を高めることから、ヘキサメチレンジイソシアネートのヌレート体、ビュレット体、アダクト体を用いることが好ましい。
なお、上記脂肪族イソシアネートの変性体は、従来公知の各種手法で製造することができる。また、ヘキサメチレンジイソシアネートの変性体は、市販品としても入手可能であり、例えば、コロネートＨＸＲ（日本ポリウレタン工業株式会社製ヌレート体）、デュラネートＤ２４Ａ−１００（旭化成ケミカルズ株式会社製ビュレット体）、デュラネートＴＳＳ−１００（旭化成ケミカルズ株式会社製アダクト体）等がある。
The other polyisocyanate (C) constituting the primer composition of the present invention is a polyisocyanate having two or more isocyanate groups in the molecule and having a number average molecular weight of 400 to 2,000. Specific examples thereof include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenyl ether. Diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenyl Propane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3, Aromatic diisocyanates such as 3'-dimethoxydiphenyl-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetra Modified polyisocyanates such as a buret body, isocyanurate body, uretonimine body, uretdione body, carbodiimide body of aliphatic diisocyanates such as methyl xylene diisocyanate, the above aliphatic isocyanates, glycerol, trimethylolpropane, polyether polyol, polyester polyol, Adduct bodies obtained by reacting with polyols such as polycarbonate polyol, and Polyphenylene polymethylene polyisocyanates, such as polymeric isocyanates such crude toluene diisocyanate and the like, which can be used singly or in combination of two or more. In particular, in order to increase the strength of the coating film formed from the primer, it is preferable to use a hexamethylene diisocyanate nurate body, a burette body, or an adduct body.
In addition, the modified body of the said aliphatic isocyanate can be manufactured by conventionally well-known various methods. The modified product of hexamethylene diisocyanate is also available as a commercial product, for example, Coronate HXR (Nurate manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate D24A-100 (Bullet manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate TSS. -100 (Adduct body manufactured by Asahi Kasei Chemicals Corporation).
さらに、本発明のプライマー組成物には、必要に応じて有機溶剤（Ｄ）を配合してもよい。有機溶剤（Ｄ）としては、従来、プライマーに用いられる各種溶剤を用いることができるが、プライマーの臭気を少なくし、人体や環境への負荷を低減させることを考慮すると、トルエンおよびキシレンを含まない有機溶剤や、有機溶剤中毒予防規則（以下、有規則という）第三種有機溶剤および／または有規則に規定されていない有機溶剤が最適である。 Furthermore, you may mix | blend the organic solvent (D) with the primer composition of this invention as needed. As the organic solvent (D), various solvents conventionally used for primers can be used. However, in consideration of reducing the odor of the primer and reducing the load on the human body and the environment, toluene and xylene are not included. Organic solvents, organic solvent poisoning prevention regulations (hereinafter referred to as “regulated rules”), third-class organic solvents and / or organic solvents that are not defined in the regulations are optimal.
有規則第三種有機溶剤の具体例としては、低沸点芳香族ナフサ、高沸点芳香族ナフサ、ミネラルスピリット等が挙げられ、これらの市販品としては、ミネラルスピリットＡ（アニリン点＝４３℃）、ホワイトスピリット、ミネラルターペン、イソパラフィン、ソルベント灯油、芳香族ナフサ、ＶＭ＆Ｐナフサ、ソルベントナフサなどがある。これらの市販品としては、ソルベッソ１００、ソルベッソ１５０、ソルベッソ２００、エッソナフサＮｏ．６（アニリン点＝４３℃）（以上、エッソ石油株式会社製）；スワゾール１０００、スワゾール１５００（以上、コスモ石油株式会社製）；イプゾール１００（アニリン点＝１２．４℃、出光興産株式会社製）；ＨＡＷＳ（アニリン点＝１５℃）、ＬＡＷＳ（アニリン点＝４３℃）（以上、シェルケミカルズジャパン株式会社製）；Ａソルベント（アニリン点＝４４．５℃、日本石油株式会社製）などが挙げられる。
有規則に規定されていない有機溶剤の具体例としては、メチルシクロヘキサン、エチルシクロヘキサン、ジメチルシクロヘキサン等のＣ９〜Ｃ１２のアルキルシクロヘキサン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等のエーテル、エステル系溶剤が挙げられる。
上記各有機溶剤は、１種単独で、または２種以上組み合わせて用いることができる。
Specific examples of the regular third-class organic solvent include low-boiling aromatic naphtha, high-boiling aromatic naphtha, mineral spirit, etc., and these commercial products include mineral spirit A (aniline point = 43 ° C.), There are white spirit, mineral turpentine, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, solvent naphtha and the like. As these commercial products, Solvesso 100, Solvesso 150, Solvesso 200, Esso Naphusa No. 6 (aniline point = 43 ° C.) (Esso Oil Co., Ltd.); Swazol 1000, Swazol 1500 (Cosmo Oil Co., Ltd.); Ipsol 100 (aniline point = 12.4 ° C., Idemitsu Kosan Co., Ltd.) HAWS (aniline point = 15 ° C.), LAWS (aniline point = 43 ° C.) (above, manufactured by Shell Chemicals Japan Co., Ltd.); A solvent (aniline point = 44.5 ° C., manufactured by Nippon Oil Co., Ltd.) .
Specific examples of organic solvents that are not regulated are: C9-C12 alkylcyclohexane such as methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether Examples include ethers such as acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ester solvents.
Each said organic solvent can be used individually by 1 type or in combination of 2 or more types.
本発明のプライマー組成物は、上述したアクリル変性（ポリ）イソシアネート（Ａ）を、（Ａ）、（Ｂ）および（Ｃ）成分の合計質量に対して２０〜６５質量％、好ましくは３０〜６０質量％、より好ましくは４０〜６０質量％含有する。
ここで、アクリル変性（ポリ）イソシアネート（Ａ）の含有量が、２０質量％未満であると、塗膜の初期硬化性が低下するとともに、上塗り塗料への適合性が低下する虞があり、一方、６５質量％を超えると、得られる塗膜と、下地である無機質基材との付着強度が低下するとともに、この場合も上塗り塗料への適合性が低下する虞がある。
In the primer composition of the present invention, the above-mentioned acrylic-modified (poly) isocyanate (A) is 20 to 65% by mass, preferably 30 to 60%, based on the total mass of the components (A), (B) and (C). It is contained by mass%, more preferably 40-60 mass%.
Here, when the content of the acrylic-modified (poly) isocyanate (A) is less than 20% by mass, the initial curability of the coating film may be lowered and the compatibility with the top coating may be lowered. When the content exceeds 65% by mass, the adhesion strength between the obtained coating film and the inorganic base material as a base is lowered, and in this case, the compatibility with the top coating material may be lowered.
また、本発明のプライマー組成物は、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）を、質量比で（Ｂ）／（Ｃ）＝０．２〜５．０、好ましくは０．３〜４．０、より好ましくは０．５〜３．５の割合で含有する。
ここで、（Ｂ）／（Ｃ）の含有比が、０．２未満であると、得られる塗膜と、下地である無機質基材との付着強度が低下するとともに、上塗り塗料への適合性が低下する虞があり、一方、５．０を超えると、塗膜の初期硬化性が低下するとともに、この場合も上塗り塗料への適合性が低下する虞がある。
すなわち、本発明では、（Ａ）〜（Ｃ）の各成分を上記割合で配合してプライマーとすることで、無機質基材への含浸性、塗膜の初期硬化性、塗膜と基材との付着強度、上塗り塗料への適合性などの諸特性を向上し得るものである。
In the primer composition of the present invention, the polyisocyanate (B) and the polyisocyanate (C) are (B) / (C) = 0.2 to 5.0, preferably 0.3 to 4. 0, more preferably 0.5 to 3.5.
Here, when the content ratio of (B) / (C) is less than 0.2, the adhesion strength between the obtained coating film and the inorganic base material as the base is lowered, and compatibility with the top coating material is also achieved. On the other hand, if it exceeds 5.0, the initial curability of the coating film is lowered, and also in this case, the compatibility with the top coat may be lowered.
That is, in the present invention, by blending the components (A) to (C) in the above proportions to make a primer, impregnation into an inorganic substrate, initial curability of the coating film, coating film and substrate, It is possible to improve various properties such as adhesion strength and compatibility with top coating.
さらに、本発明のプライマー組成物が有機溶剤（Ｄ）を含有する場合、その含有量は、プライマー全体中において、９９〜３０質量％が好ましく、９８〜４０質量％であることが好ましい。
なお、本発明のプライマー組成物は、上記各必須成分（Ａ）〜（Ｃ）および任意成分（Ｄ）の他に、必要に応じて、無機充填剤、表面調整剤、消泡剤、増粘剤、沈降防止剤、紫外線吸収剤、光安定剤、触媒等の各種添加剤を含んでいてもよい。
Furthermore, when the primer composition of this invention contains the organic solvent (D), 99-30 mass% is preferable in the whole primer, and it is preferable that it is 98-40 mass%.
In addition to the above essential components (A) to (C) and the optional component (D), the primer composition of the present invention may contain an inorganic filler, a surface conditioner, an antifoaming agent, a thickening agent as necessary. Various additives such as an agent, an anti-settling agent, an ultraviolet absorber, a light stabilizer, and a catalyst may be included.
本発明のプライマー組成物の製造法は特に限定されるものではなく、（Ａ）〜（Ｄ）成分を任意の順序で混合して調製することができるが、特に、ポリイソシアネート（Ａ２）として、ポリイソシアネート（Ｂ）および／または（Ｃ）に相当するものを使用する場合は、上記アクリルポリオール（Ａ１）と、上記ポリイソシアネート（Ｂ）および／またはポリイソシアネート（Ｃ）とを、未反応のポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）が残存する割合で反応させてアクリル変性（ポリ）イソシアネート（Ａ）、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）を含む組成物とする手法や、上記アクリルポリオール（Ａ１）と、上記ポリイソシアネート（Ｂ）とを、未反応のポリイソシアネート（Ｂ）が残存する割合で反応させてアクリル変性（ポリ）イソシアネート（Ａ）およびポリイソシアネート（Ｂ）との混合物とし、この混合物と、ポリイソシアネート（Ｃ）とを配合してアクリル変性ポリイソシアネート（Ａ）、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）を含む組成物とする手法が最適である。なお、イソシアネート化反応の詳細については上述のとおりである。
ただし、ポリイソシアネート（Ｂ）および／またはポリイソシアネート（Ｃ）を２種類以上含むプライマーとする場合、アクリルポリオール（Ａ１）とポリイソシアネート（Ｂ）および／またはポリイソシアネート（Ｃ）の全種類とを反応させてプライマーとしても、それらの特定種類をアクリルポリオール（Ａ１）と反応させた後に、その他の種類のポリイソシアネートを加えてプライマーとしてもよい。
The production method of the primer composition of the present invention is not particularly limited and can be prepared by mixing the components (A) to (D) in an arbitrary order. In particular, as the polyisocyanate (A2), When using the thing corresponding to polyisocyanate (B) and / or (C), said acrylic polyol (A1) and said polyisocyanate (B) and / or polyisocyanate (C) are made into unreacted polyisocyanate. A method in which an isocyanate (B) and a polyisocyanate (C) are reacted in a remaining ratio to form a composition containing acrylic-modified (poly) isocyanate (A), polyisocyanate (B) and polyisocyanate (C), and the acrylic The unreacted polyisocyanate (B) remains in the polyol (A1) and the polyisocyanate (B). A mixture of acrylic modified (poly) isocyanate (A) and polyisocyanate (B) is reacted at a ratio, and this mixture is mixed with polyisocyanate (C) to prepare acrylic modified polyisocyanate (A), polyisocyanate ( The method of using a composition containing B) and polyisocyanate (C) is optimal. The details of the isocyanate reaction are as described above.
However, when a primer containing two or more types of polyisocyanate (B) and / or polyisocyanate (C) is used, the acrylic polyol (A1) reacts with all types of polyisocyanate (B) and / or polyisocyanate (C). Even if it is made to make it a primer, after reacting those specific kinds with acrylic polyol (A1), it is good also as a primer by adding another kind of polyisocyanate.
アクリルポリオール（Ａ１）と、ポリイソシアネート（Ｂ）とを反応させる場合、それらの反応割合は、ポリイソシアネート（Ｂ）のＮＣＯ基モル濃度とアクリルポリオール（Ａ１）のＯＨ基モル濃度［ＯＨ］との比［ＮＣＯ］／［ＯＨ］が２．５以上となる割合が好ましく、４．０以上となる割合がより好ましい。
なお、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）の使用量は、上述したアクリル変性（ポリ）イソシアネート（Ａ）の含有量および、（Ｂ）／（Ｃ）比を満たす量とすればよい。
また、プライマー組成物が有機溶剤（Ｄ）含む場合、イソシアネート化反応の溶媒として有機溶剤（Ｄ）を用いても、（Ａ）〜（Ｃ）の混合組成物中に有機溶剤（Ｄ）を加えても、それらを併用してもよい。
When the acrylic polyol (A1) is reacted with the polyisocyanate (B), the reaction ratio between the NCO group molar concentration of the polyisocyanate (B) and the OH group molar concentration [OH] of the acrylic polyol (A1). The ratio that the ratio [NCO] / [OH] is 2.5 or more is preferable, and the ratio that the ratio [NCO] / [OH] is 4.0 or more is more preferable.
In addition, what is necessary is just to let the usage-amount of polyisocyanate (B) and polyisocyanate (C) satisfy | fill the content of acrylic-modified (poly) isocyanate (A) mentioned above, and (B) / (C) ratio.
Further, when the primer composition contains an organic solvent (D), the organic solvent (D) is added to the mixed composition of (A) to (C) even if the organic solvent (D) is used as a solvent for the isocyanate reaction. Or they may be used in combination.
以上説明したプライマー組成物は、無機質基材に対する浸透固化性能に優れているため、スレート瓦や、壁材などの補修や改修に好適に用いることができる。
その使用法としては、例えば、スレート瓦などの被改修材の塗装面の洗浄、および旧塗膜の除去後、本発明のプライマー組成物を塗布し、これを常温にて放置または加熱して乾燥し、さらに上塗り塗料を塗布する手法が挙げられる。
この場合、塗布法は特に限定されるものではなく、刷毛塗り、ローラ塗りなどの公知の手法から適宜選択すればよい。また、塗布量、塗膜の厚み、乾燥時間などは、被塗装面の材質や、上塗り塗料の種類などに応じて適宜なものとすればよい。
Since the primer composition demonstrated above is excellent in the permeation | solidification solidification performance with respect to an inorganic base material, it can be used suitably for repair and repair of a slate roof tile, a wall material, etc.
As its usage, for example, after cleaning the coated surface of the material to be repaired such as slate roof tiles and removing the old paint film, the primer composition of the present invention is applied, and this is left to stand or heated at room temperature and dried. In addition, there is a method of applying a top coat.
In this case, the coating method is not particularly limited, and may be appropriately selected from known methods such as brush coating and roller coating. Moreover, what is necessary is just to make an application quantity, the thickness of a coating film, a drying time, etc. appropriate according to the material of the surface to be coated, the kind of top coat, and the like.
以下、合成例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は、下記の実施例に限定されるものではない。以下の説明において、「部」は質量部を意味する。
なお、以下において、粘度は、Ｂ型回転粘度計による測定値であり、数平均分子量は、示差屈折率計検出によるＧＰＣ測定値（ポリスチレン換算値）である（装置：東ソー株式会社製ＨＬＣ−８１２０ＧＰＣ、分離カラム：東ソーＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＭ−Ｍのミックスカラム）。
EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In the following description, “parts” means parts by mass.
In the following, the viscosity is a value measured by a B-type rotational viscometer, and the number average molecular weight is a GPC measured value (polystyrene conversion value) detected by a differential refractometer (apparatus: HLC-8120GPC manufactured by Tosoh Corporation). Separation column: Tosoh TSKgel Super HM-M mix column).
［１］アクリルポリオール樹脂の合成
［合成例１］アクリルポリオール樹脂１の合成
攪拌機、温度計、冷却管、窒素ガス導入管、および滴下装置を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、商品名：イプゾール１００）を３６０部仕込み、攪拌しながら１２０℃まで昇温した。そこに、メチルメタアクリレート１４４部、ｔｅｒｔ−ブチルメタアクリレート１４４部、２−ヒドロキシエチルメタアクリレート３２部、２，２′−アゾビスイソブチロニトリル６部、低沸点芳香族ナフサ４０部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、２，２′−アゾビスイソブチロニトリル２部、低沸点芳香族ナフサ８０部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分４０．６％、粘度５００ｍＰａ・ｓ（２５℃）、数平均分子量３００００、水酸基価４２ｍｇＫＯＨ／ｇ（固形分）の透明なアクリルポリオール樹脂１を得た。
[1] Synthesis of Acrylic Polyol Resin [Synthesis Example 1] Synthesis of Acrylic Polyol Resin 1 A low boiling point aromatic naphtha (Idemitsu Kosan Co., Ltd.) was added to a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a dropping device. 360 parts made by Co., Ltd., trade name: IPZOL 100) were charged and heated to 120 ° C. while stirring. A mixture comprising 144 parts of methyl methacrylate, 144 parts of tert-butyl methacrylate, 32 parts of 2-hydroxyethyl methacrylate, 6 parts of 2,2'-azobisisobutyronitrile and 40 parts of low-boiling aromatic naphtha. Was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture comprising 2 parts of 2,2′-azobisisobutyronitrile and 80 parts of low-boiling aromatic naphtha was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours to obtain a transparent acrylic polyol resin 1 having a solid content of 40.6%, a viscosity of 500 mPa · s (25 ° C.), a number average molecular weight of 30000, and a hydroxyl value of 42 mgKOH / g (solid content). Obtained.
［合成例２］アクリルポリオール樹脂２の合成
攪拌機、温度計、冷却管、窒素ガス導入管、および滴下装置を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、商品名：イプゾール１００）を３６０部仕込み、攪拌しながら１２０℃まで昇温した。そこに、メチルメタアクリレート１６８部、シクロヘキシルメタクリレート８８部、２−ヒドロキシエチルメタアクリレート６４部、２，２′−アゾビスイソブチロニトリル１２部、低沸点芳香族ナフサ４０部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、２，２′−アゾビスイソブチロニトリル２部、低沸点芳香族ナフサ８０部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分４１．０％、粘度１６００ｍＰａ・ｓ（２５℃）、数平均分子量１８０００、水酸基価８３ｍｇＫＯＨ／ｇ（固形分）の透明なアクリルポリオール樹脂２を得た。
Synthesis Example 2 Synthesis of Acrylic Polyol Resin 2 A low boiling point aromatic naphtha (made by Idemitsu Kosan Co., Ltd., trade name: IPZOL) was added to a reactor equipped with a stirrer, thermometer, cooling pipe, nitrogen gas introduction pipe, and dropping device. 100) was charged and heated to 120 ° C. while stirring. A mixture of 168 parts of methyl methacrylate, 88 parts of cyclohexyl methacrylate, 64 parts of 2-hydroxyethyl methacrylate, 12 parts of 2,2'-azobisisobutyronitrile and 40 parts of low-boiling aromatic naphtha was added for 4 hours. It was dripped over. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture comprising 2 parts of 2,2′-azobisisobutyronitrile and 80 parts of low-boiling aromatic naphtha was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours to obtain a transparent acrylic polyol resin 2 having a solid content of 41.0%, a viscosity of 1600 mPa · s (25 ° C.), a number average molecular weight of 18000, and a hydroxyl value of 83 mgKOH / g (solid content). Obtained.
［合成例３］アクリルポリオール樹脂３の合成
攪拌機、温度計、冷却管、窒素ガス導入管、および滴下装置を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、商品名：イプゾール１００）を３６０部仕込み、攪拌しながら１２０℃まで昇温した。そこに、メチルメタアクリレート１９６部、ｉｓｏ−ブチルメタアクリレート６０部、２−ヒドロキシエチルメタアクリレート３２部、γ−２，２′−アゾビスイソブチロニトリル８部、低沸点芳香族ナフサ４０部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、２，２′−アゾビスイソブチロニトリル２部、低沸点芳香族ナフサ８０部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分４０．７％、粘度３６０ｍＰａ・ｓ（２５℃）、数平均分子量２００００、水酸基価４２ｍｇＫＯＨ／ｇ（固形分）の透明なアクリルポリオール樹脂３を得た。
[Synthesis Example 3] Synthesis of acrylic polyol resin 3 A low boiling point aromatic naphtha (manufactured by Idemitsu Kosan Co., Ltd., trade name: IPZOL) was added to a reactor equipped with a stirrer, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a dropping device. 100) was charged and heated to 120 ° C. while stirring. From there, 196 parts of methyl methacrylate, 60 parts of iso-butyl methacrylate, 32 parts of 2-hydroxyethyl methacrylate, 8 parts of γ-2,2'-azobisisobutyronitrile, 40 parts of low boiling aromatic naphtha The resulting mixture was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture comprising 2 parts of 2,2′-azobisisobutyronitrile and 80 parts of low-boiling aromatic naphtha was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours to obtain a transparent acrylic polyol resin 3 having a solid content of 40.7%, a viscosity of 360 mPa · s (25 ° C.), a number average molecular weight of 20000, and a hydroxyl value of 42 mgKOH / g (solid content). Obtained.
［比較合成例１］アクリルポリオール樹脂４の合成
攪拌機、温度計、冷却管、窒素ガス導入管、および滴下装置を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、商品名：イプゾール１００）を３６０部仕込み、攪拌しながら１２０℃まで昇温した。そこに、メチルメタアクリレート１６０部、ｔｅｒｔ−ブチルメタアクリレート１６０部、２，２′−アゾビスイソブチロニトリル６部、低沸点芳香族ナフサ４０部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、２，２′−アゾビスイソブチロニトリル２部、低沸点芳香族ナフサ８０部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分４０．６％、粘度３００ｍＰａ・ｓ（２５℃）、数平均分子量３００００、水酸基価０ｍｇＫＯＨ／ｇ（固形分）の透明なアクリルポリオール樹脂４を得た。
[Comparative Synthesis Example 1] Synthesis of acrylic polyol resin 4 A low-boiling aromatic naphtha (manufactured by Idemitsu Kosan Co., Ltd., trade name: a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a dropping device). 360 parts of ipsol 100) were charged and the temperature was raised to 120 ° C. with stirring. A mixture comprising 160 parts of methyl methacrylate, 160 parts of tert-butyl methacrylate, 6 parts of 2,2′-azobisisobutyronitrile and 40 parts of low-boiling aromatic naphtha was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture comprising 2 parts of 2,2′-azobisisobutyronitrile and 80 parts of low-boiling aromatic naphtha was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours to obtain a transparent acrylic polyol resin 4 having a solid content of 40.6%, a viscosity of 300 mPa · s (25 ° C.), a number average molecular weight of 30000, and a hydroxyl value of 0 mgKOH / g (solid content). Obtained.
［比較合成例２］アクリルポリオール樹脂５の合成
攪拌機、温度計、冷却管、窒素ガス導入管、および滴下装置を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、商品名：イプゾール１００）を３６０部仕込み、攪拌しながら１２０℃まで昇温した。そこに、メチルメタアクリレート１４４部、ｔｅｒｔ−ブチルメタアクリレート１４４部、２−ヒドロキシエチルメタアクリレート３２部、２，２′−アゾビスイソブチロニトリル１部、低沸点芳香族ナフサ４０部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、２，２′−アゾビスイソブチロニトリル２部、低沸点芳香族ナフサ８０部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分４０．２％、粘度５００ｍＰａ・ｓ（２５℃）、数平均分子量１５００００、水酸基価４３ｍｇＫＯＨ／ｇ（固形分）の透明なアクリルポリオール樹脂５を得た。
[Comparative Synthesis Example 2] Synthesis of acrylic polyol resin 5 A low-boiling aromatic naphtha (manufactured by Idemitsu Kosan Co., Ltd., trade name: a reactor equipped with a stirrer, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a dropping device was used. 360 parts of ipsol 100) were charged and the temperature was raised to 120 ° C. with stirring. A mixture comprising 144 parts of methyl methacrylate, 144 parts of tert-butyl methacrylate, 32 parts of 2-hydroxyethyl methacrylate, 1 part of 2,2'-azobisisobutyronitrile and 40 parts of low-boiling aromatic naphtha. Was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture comprising 2 parts of 2,2′-azobisisobutyronitrile and 80 parts of low-boiling aromatic naphtha was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours to obtain a transparent acrylic polyol resin 5 having a solid content of 40.2%, a viscosity of 500 mPa · s (25 ° C.), a number average molecular weight of 150,000 and a hydroxyl value of 43 mgKOH / g (solid content) Obtained.
［２］プライマー組成物の調製
［実施例１］アクリルウレタン系プライマー溶液の調製
攪拌機、温度計、冷却管、および窒素ガス導入管を備えた反応器に、低沸点芳香族ナフサ（出光興産株式会社製、イプゾール１００）２４０部、プロピレングリコールモノメチルエーテルアセテート１００部、アクリルポリオール樹脂１ １００部（固形分換算４０部）、イソホロンジイソシアネート（住友バイエルウレタン株式会社製、商品名：デスモジュールＩ）３０部、ジブチル錫ジラウレート０．１部を仕込み、８０℃で４時間反応させた。さらにヘキサメチレンジイソシアネートのヌレート体（日本ポリウレタン工業株式会社製、商品名：コロネートＨＸＲ）３０部を仕込み同温度で１時間混合後、固形分２０％、ＮＣＯ含量３．３％のアクリルウレタン系プライマー溶液を得た。
[2] Preparation of primer composition [Example 1] Preparation of acrylic urethane primer solution A low-boiling aromatic naphtha (Idemitsu Kosan Co., Ltd.) was added to a reactor equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas introduction pipe. Manufactured by Ipsol 100) 240 parts, propylene glycol monomethyl ether acetate 100 parts, acrylic polyol resin 1 100 parts (solid content conversion 40 parts), isophorone diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Desmodur I), 0.1 part of dibutyltin dilaurate was added and reacted at 80 ° C. for 4 hours. Furthermore, 30 parts of hexamethylene diisocyanate nurate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Coronate HXR) was added and mixed at the same temperature for 1 hour, and then an acrylic urethane primer solution having a solid content of 20% and an NCO content of 3.3%. Got.
［実施例２〜１１，比較例１〜６］アクリルウレタン系プライマー溶液の調製
各成分を表１，２に示される組成に変更した以外は、実施例１と同様の方法でアクリルウレタン系プライマー溶液を得た。
[Examples 2 to 11, Comparative Examples 1 to 6] Preparation of acrylic urethane primer solution Acrylic urethane primer solution in the same manner as in Example 1 except that each component was changed to the composition shown in Tables 1 and 2. Got.
［比較例７］エポキシ／アミン系プライマー溶液の調製
エポキシ樹脂（大日本インキ化学工業製、エピクロン５９００−６０）１００部、アミン樹脂（大日本インキ化学工業製、ラッカマイドＢ−２１００−４０ＥＳ）１００部、低沸点芳香族ナフサ（出光興産株式会社製、イプゾール１００）２００部、プロピレングリコールモノメチルエーテルアセテート１００部を混合容器に加え、攪拌機で３０００ｒｐｍ×１分間攪拌し、固形分２０質量％のエポキシ／アミン系プライマー溶液を調製した。
[Comparative Example 7] Preparation of epoxy / amine-based primer solution 100 parts of epoxy resin (Dainippon Ink Chemical Co., Ltd., Epicron 5900-60), 100 parts of amine resin (Dainippon Ink Chemical Co., Ltd., racamide B-2100-40ES) , 200 parts of low boiling point aromatic naphtha (Idemitsu Kosan Co., Ltd., Ipsol 100) and 100 parts of propylene glycol monomethyl ether acetate were added to a mixing container, stirred with a stirrer at 3000 rpm × 1 minute, and epoxy / amine having a solid content of 20% by mass. A system primer solution was prepared.
上記各実施例および比較例で調製した各プライマーを、埼玉県久喜市において、南面３０°で１０年間暴露した基材（株式会社クボタ製（現クボタ松下電工外装株式会社製）スレート瓦）に、塗布量０．４ｋｇ／ｍ2でローラにて塗布し、試験片とした。
作製した試験片について、下記の手法により、造膜性、初期硬化性、下地の補強強度、上塗り適合性、および環境・人体への負荷の評価を行った。評価結果を表１，２に示す。
Each primer prepared in each of the above Examples and Comparative Examples was applied to a base material (manufactured by Kubota Corporation (currently Kubota Matsushita Electric Works Co., Ltd.) slate tile) that was exposed for 10 years at 30 ° south surface in Kuki City, Saitama Prefecture. It apply | coated with the roller with the application quantity of 0.4 kg / m < 2 >, and was set as the test piece.
About the produced test piece, film forming property, initial stage sclerosis | hardenability, the reinforcement | strengthening strength of the foundation | substrate, topcoat compatibility, and the load to an environment and a human body were evaluated with the following method. The evaluation results are shown in Tables 1 and 2.
（１）造膜性
プライマー乾燥時の造膜状態を目視で評価した。
○：クリヤーな連続膜を形成している
△：クリヤーではないが、連続膜を形成している
×：連続膜を形成していない
（２）初期硬化性
プライマー塗布後、２３℃×１ｈ後のタック感を指触で評価した。
○：タック感なし
△：ややタック感あり
×：タック感あり
（３）下地の補強強度
プライマー塗布後、２３℃で２４時間養生し、２３℃の水に７日間浸漬した後、太平理化工業株式会社製 ｅｌｃｏｍｅｔｅｒ Ｆ１０６−２で接着力を測定した。
○：１．５Ｎ／ｍｍ2以上
△：１．５Ｎ／ｍｍ2未満１．０Ｎ／ｍｍ2以上
×：１．０Ｎ／ｍｍ2未満
（４）上塗り適合性
プライマー塗布後、２３℃で７２時間養生し、上塗り（弱溶剤ウレタン塗料）０．２ｋｇをローラで塗装し、２３℃×１日養生後、２３℃の水に７日間浸漬した。その後、ＪＩＳ Ｋ５６００−５−６クロスカット法により付着性を評価した。
○：分類０
△：分類１または２
×：分類３以上
（５）環境・人体への負荷
○：比較的環境に対する負荷が少なく、また人体に対してもアレルギー等を引き起こす可能性が少ないもの
×：環境に対する負荷が大きく、また人体に対してもアレルギー等を引き起こす可能性が高いもの
(1) Film-forming property The film-forming state when the primer was dried was visually evaluated.
○: A clear continuous film is formed. Δ: A clear film is formed, but a continuous film is formed. ×: A continuous film is not formed. (2) Initial curing property After applying primer, 23 ° C. × 1 hour later Tack feeling was evaluated by finger touch.
○: No tackiness △: Slightly tackiness ×: Tackiness (3) Reinforcement strength of the primer After applying primer, cured at 23 ° C for 24 hours, immersed in 23 ° C water for 7 days, then Taihei Rika Kogyo Co., Ltd. The adhesive force was measured with elcomator F106-2 manufactured by the company.
○: 1.5N / mm 2 or more △: 1.5N / mm 2 lower than 1.0 N / mm 2 or more ×: less than 1.0N / mm 2 (4) after overcoatability primer coating, 72 hours aging at 23 ° C. Then, 0.2 kg of top coat (weak solvent urethane paint) was applied with a roller, cured at 23 ° C. for 1 day, and then immersed in water at 23 ° C. for 7 days. Then, adhesiveness was evaluated by JIS K5600-5-6 crosscut method.
○: Classification 0
Δ: Classification 1 or 2
×: Classification 3 or higher (5) Environmental and human load ○: Relatively low environmental load and less likely to cause allergies to the human body ×: High environmental load and also on the human body Those that are highly likely to cause allergies
表１，２に示されるように、実施例１〜１１で得られたアクリルウレタン系のプライマー組成物は、成分や組成比が本発明の範囲外である比較例１〜６のアクリルウレタン系のプライマー組成物に比べ、各性能のバランスが良好であることがわかる。また、アクリルウレタン系のプライマーでありながら、無機質基材への浸透固化性に優れていることから従来汎用されているエポキシ／アミンの２液硬化システム（比較例７）と同様の浸透性、表面残存性、初期硬化性、接着性を有していることがわかる。さらにはエポキシ樹脂が有する人体へのアレルギー性も、大きく低減されていることがわかる。 As shown in Tables 1 and 2, the acrylic urethane-based primer compositions obtained in Examples 1 to 11 are of the acrylic urethane type of Comparative Examples 1 to 6 whose components and composition ratios are outside the scope of the present invention. It can be seen that the balance of each performance is better than that of the primer composition. In addition, since it is an acrylic urethane primer, it has excellent penetrability and solidification into inorganic substrates, so that it has the same penetrability and surface as the conventional two-component epoxy / amine two-component curing system (Comparative Example 7). It turns out that it has persistence, initial curing property, and adhesiveness. Furthermore, it can be seen that the allergenicity of the epoxy resin to the human body is greatly reduced.
Claims (12)
分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）、および
分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）を含有し、
前記アクリル変性（ポリ）イソシアネート（Ａ）の含有量が、前記アクリル変性（ポリ）イソシアネート（Ａ）、ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）の合計質量に対して２０〜６５質量％であり、かつ、前記ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）の含有比が、質量比で（Ｂ）／（Ｃ）＝０．２〜５．０であることを特徴とするプライマー組成物。 An acrylic polymer obtained by reacting a polyisocyanate (A2) with an acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value of 5 to 150 mgKOH / g, and having one or more isocyanate groups in the molecule. Modified (poly) isocyanate (A),
Polyisocyanate (B) having two or more isocyanate groups in the molecule and having a number average molecular weight of 150 to less than 400, and polyisocyanate having two or more isocyanate groups in the molecule and having a number average molecular weight of 400 to 2,000 Containing (C),
Content of the said acrylic modification (poly) isocyanate (A) is 20-65 mass% with respect to the total mass of the said acrylic modification (poly) isocyanate (A), polyisocyanate (B), and polyisocyanate (C). And the content ratio of the said polyisocyanate (B) and polyisocyanate (C) is (B) / (C) = 0.2-5.0 by mass ratio, The primer composition characterized by the above-mentioned.
イソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）、および／または分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）とを、
未反応の前記ポリイソシアネート（Ｂ）およびポリイソシアネート（Ｃ）が残存する割合で反応させることを特徴とする請求項２記載のプライマー組成物の製造方法。 An acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value of 5 to 150 mgKOH / g;
Polyisocyanate (B) having two or more isocyanate groups and having a number average molecular weight of 150 or more and less than 400, and / or polyisocyanate having two or more isocyanate groups in the molecule and having a number average molecular weight of 400 to 2,000 ( C)
The method for producing a primer composition according to claim 2, wherein the unreacted polyisocyanate (B) and polyisocyanate (C) are reacted in a remaining ratio.
分子中にイソシアネート基を２個以上有し、数平均分子量１５０以上４００未満のポリイソシアネート（Ｂ）とを、未反応の前記ポリイソシアネート（Ｂ）が残存する割合で反応させた後、
得られた反応液と、分子中にイソシアネート基を２個以上有し、数平均分子量４００〜２，０００のポリイソシアネート（Ｃ）とを配合する請求項２記載のプライマー組成物の製造方法。 An acrylic polyol (A1) having a number average molecular weight of 4,000 to 120,000 and a hydroxyl value of 5 to 150 mgKOH / g;
After reacting the polyisocyanate (B) having two or more isocyanate groups in the molecule and having a number average molecular weight of 150 or more and less than 400 in a ratio in which the unreacted polyisocyanate (B) remains,
The manufacturing method of the primer composition of Claim 2 which mix | blends the obtained reaction liquid and the polyisocyanate (C) which has two or more isocyanate groups in a molecule | numerator, and whose number average molecular weights are 400-2,000.
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| JP2011225774A (en) * | 2010-04-22 | 2011-11-10 | Yokohama Rubber Co Ltd:The | Primer composition |
| JP2015096930A (en) * | 2013-11-17 | 2015-05-21 | 槌屋ティスコ株式会社 | Meandering prevention member and manufacturing method of the same |
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| JP2015096930A (en) * | 2013-11-17 | 2015-05-21 | 槌屋ティスコ株式会社 | Meandering prevention member and manufacturing method of the same |
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