JP2764055B2 - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JP2764055B2 JP2764055B2 JP1128633A JP12863389A JP2764055B2 JP 2764055 B2 JP2764055 B2 JP 2764055B2 JP 1128633 A JP1128633 A JP 1128633A JP 12863389 A JP12863389 A JP 12863389A JP 2764055 B2 JP2764055 B2 JP 2764055B2
- Authority
- JP
- Japan
- Prior art keywords
- diamino
- triazine
- fluorine
- coating
- etherified
- 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.)
- Expired - Lifetime
Links
- 239000008199 coating composition Substances 0.000 title claims description 29
- -1 methylene, ethylene, trimethylene Chemical group 0.000 claims description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 50
- 239000011737 fluorine Substances 0.000 claims description 50
- 229910052731 fluorine Inorganic materials 0.000 claims description 50
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019256 formaldehyde Nutrition 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 52
- 238000000576 coating method Methods 0.000 description 52
- 239000000463 material Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 28
- 239000003921 oil Substances 0.000 description 27
- 239000011342 resin composition Substances 0.000 description 27
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910000831 Steel Inorganic materials 0.000 description 20
- 239000011247 coating layer Substances 0.000 description 20
- 239000010959 steel Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000049 pigment Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 229920003180 amino resin Polymers 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 229920006243 acrylic copolymer Polymers 0.000 description 5
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 4
- VLBBMMCEGLPQFY-UHFFFAOYSA-N 6-(4,4,5,5,6,6,7,7,7-nonafluoroheptyl)-1,3,5-triazine-2,4-diamine Chemical compound C(CC1=NC(=NC(=N1)N)N)CC(C(C(C(F)(F)F)(F)F)(F)F)(F)F VLBBMMCEGLPQFY-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QDJAJUWWNQBZBY-UHFFFAOYSA-N 6-(2,2,3,3,3-pentafluoropropyl)-1,3,5-triazine-2,4-diamine Chemical compound C(C1=NC(=NC(=N1)N)N)C(C(F)(F)F)(F)F QDJAJUWWNQBZBY-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- CRHLZRRTZDFDAJ-UHFFFAOYSA-N butoxymethanol Chemical compound CCCCOCO CRHLZRRTZDFDAJ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- VHWYCFISAQVCCP-UHFFFAOYSA-N methoxymethanol Chemical compound COCO VHWYCFISAQVCCP-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-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
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- CTRPRMNBTVRDFH-UHFFFAOYSA-N 2-n-methyl-1,3,5-triazine-2,4,6-triamine Chemical class CNC1=NC(N)=NC(N)=N1 CTRPRMNBTVRDFH-UHFFFAOYSA-N 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- JRJZZNAJSLMWGL-UHFFFAOYSA-N 1-(2-hydroxy-2-methylpropyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC(C)(O)CN1C(C)(C)CC(O)CC1(C)C JRJZZNAJSLMWGL-UHFFFAOYSA-N 0.000 description 1
- QLAFGHVZDNLIDW-UHFFFAOYSA-N 1-[3-(benzotriazol-2-yl)-5-(3-methylbutyl)phenyl]-3-methylbutan-2-ol Chemical compound CC(C)CCC1=CC(CC(O)C(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1 QLAFGHVZDNLIDW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WUHHVDQBQZVSJV-UHFFFAOYSA-N 2,2-dibutylpropanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CCCC WUHHVDQBQZVSJV-UHFFFAOYSA-N 0.000 description 1
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JHDNFMVFXUETMC-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(C=2C=3N=NNC=3C=CC=2)=C1 JHDNFMVFXUETMC-UHFFFAOYSA-N 0.000 description 1
- ONDALFICRVVSFR-UHFFFAOYSA-N 2-(4-tert-butylphenoxy)benzoic acid Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC=C1C(O)=O ONDALFICRVVSFR-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- AYWUWELIMCTKEM-UHFFFAOYSA-N 2-heptyl-1,3,5-triazine Chemical compound CCCCCCCC1=NC=NC=N1 AYWUWELIMCTKEM-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、特定の含フッ素グアナミン誘導体と水酸基
を有する重合体とを必須構成成分とする、防汚性、非粘
着性、撥水撥油性、離型性等が長期にわたり優れた被覆
層の形成に有用な新規な被覆用組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antifouling property, a non-adhesive property, and a water / oil repellency which comprise a specific fluorinated guanamine derivative and a polymer having a hydroxyl group as essential components. The present invention relates to a novel coating composition useful for forming a coating layer having excellent releasability and the like over a long period of time.
従来、含フッ素置換基を側鎖に有する被覆組成物とし
ては、 CH2＝CH−Ｏ−CH2（CF2）l-1CF3 （式中、ｌは１〜12の中から選ばれる整数を示す）、あ
るいは CH2＝CH−COOCH2CH2（CF2）m-1CF3 （式中、ｍは１〜12の中から選ばれる整数を示す）を必
須構成単位として含有する重合体からなる被覆組成物等
が知られている。Conventionally, as a coating composition having a fluorinated substituent on a side chain, CH 2 CHCH—O—CH 2 (CF 2 ) 1 -1 CF 3 (where 1 is an integer selected from 1 to 12) shown), or CH 2 = CH-COOCH 2 CH 2 (CF 2) in m-1 CF 3 (wherein, m is as essential constituent units a represents an integer) selected from 1 to 12 polymer And the like are known.
しかしながら、前者公知の化合物を必須構成単位とす
る重合体は、（メタ）アクリル酸エステル、スチレン、
アクリロニトリル等の汎用モノマーを構成単位として、
含有する汎用共重合体が得難く、重合体の製造方法、重
合体組成に著しい制約があること等の欠陥を有し、また
後者公知の化合物を必須構成単位とする重合体は、含フ
ッ素置換基が加水分解、熱、光等により容易に離脱し、
所期の機能を長期にわたり維持することが困難であるこ
と等の欠陥を有し、これらの公知化合物を必須構成単位
とする重合体を含有する組成物は、製造及び使用にあた
り、技術的、経済的に著しく制限を受けていた。However, the polymer containing the former known compound as an essential structural unit is (meth) acrylate, styrene,
With a general-purpose monomer such as acrylonitrile as a structural unit,
It is difficult to obtain a general-purpose copolymer containing the polymer, the method for producing the polymer, has defects such as a significant restriction on the polymer composition, and the latter polymer having a known compound as an essential constituent unit has a fluorine-containing substitution. The group is easily separated by hydrolysis, heat, light, etc.,
A composition containing a polymer having these known compounds as essential constitutional units has drawbacks such as difficulty in maintaining the intended function for a long period of time. Was severely restricted.
本発明者は、含フッ素置換基を側鎖に有する被覆組成
物における上記欠陥を克服する為鋭意検討した結果、加
水分解、熱、光等による含フッ素置換基の離脱が殆どな
く機能を長期にわたり維持することができ、また水酸基
を有する各種の重合体を用いて容易に含フッ素被覆層を
形成することができ被覆材料の製造、組成の制約が極め
て少なく、防汚塗料、防食塗料、耐候性塗料、着氷防止
塗料、屋根材、道路標識、鉄塔、電線等の積雪防止被覆
材、防湿被覆材、成形金型等の離型被覆材、サッシ等の
防汚潤滑被覆材、撥水撥油材、光学材料、ガス分離膜材
料、紙加工材、繊維加工材、ゴム材料、レジスト材料等
として極めて広汎な用途に有用な材料を提供することが
できる新規な被覆用組成物を見出して、本発明に到達し
た。The present inventor has conducted intensive studies to overcome the above-mentioned defects in the coating composition having a fluorinated substituent in the side chain, and as a result, has been found that the fluorinated substituent is hardly detached due to hydrolysis, heat, light, etc. It can be maintained, and it can easily form a fluorine-containing coating layer using various polymers having a hydroxyl group.Therefore, there are very few restrictions on the production and composition of coating materials, and antifouling paints, anticorrosion paints, and weather resistance Paints, anti-icing paints, roofing materials, road signs, steel towers, electric wires, etc., snow-proofing coating materials, moisture-proof coating materials, mold release coating materials such as molding dies, anti-fouling lubrication coating materials such as sashes, and water and oil repellency A new coating composition that can provide useful materials for a very wide range of applications as materials, optical materials, gas separation membrane materials, paper processing materials, fiber processing materials, rubber materials, resist materials, etc. The invention has been reached.
すなわち、本発明は、 水酸基を有する重合体と硬化剤とを必須構成成分とす
る被覆用組成物において、前記硬化剤が、一般式 ［式中、R1はCF3、C2F5、C3F7、（CF3）2CF、C4F9、（C
F3）2CF−Ｏ基の中から選ばれる１種、R2はＦ原子およ
び／又はCF3基、R3はメチレン、エチレン、トリメチレ
ン、プロピレン基の中から選ばれる１種、ｎは１〜７の
中から選ばれる整数を示す］で表わされる含フッ素グア
ナミン化合物の中から選ばれる少なくとも１種とホルム
アルデヒド類の中から選ばれる少なくとも１種とを反応
させて得られる少なくとも１個のメチロール基を有する
メチロール化含フッ素グアナミン誘導体と、炭素数１〜
20個を有する脂肪族アルコールおよび脂環族アルコール
の中から選ばれる１種とを反応させることにより得られ
る少なくとも１個のR4OCH2基（R4は前記アルコールより
水酸基を除いた残基である）を有するエーテル化含フッ
素グアナミン誘導体を成分として含有することを特徴と
する被覆用組成物である。That is, the present invention provides a coating composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent has a general formula [Wherein, R 1 is CF 3 , C 2 F 5 , C 3 F 7 , (CF 3 ) 2 CF, C 4 F 9 , (C
F 3) 2 CF-O 1 kind selected from among group, R 2 represents F atom and / or a CF 3 group, R 3 is methylene, ethylene, trimethylene, one selected from among propylene group, n represents 1 At least one methylol group obtained by reacting at least one selected from fluorine-containing guanamine compounds represented by the following formulas with at least one selected from formaldehydes: Having a methylolated fluorine-containing guanamine derivative having 1 to 1 carbon atoms
At least one R 4 OCH 2 group (R 4 is a residue obtained by removing a hydroxyl group from the alcohol) obtained by reacting one of aliphatic alcohols and alicyclic alcohols having 20 A coating composition comprising, as a component, an etherified fluorine-containing guanamine derivative having the formula (1).
本発明に係わる水酸基を有する重合体としては、水酸
基を有するものであれば種々の重合体が使用可能であ
り、例えばヒドロキシアルキルビニルエーテル、ヒドロ
キシアルキル（メタ）アクリレート、アリルアルコー
ル、メタアリルアルコール、４−ヒドロキシ−1,1,2−
トリフルオル−ブテン−１、６−ヒドロキシ−1,1,2,3,
3,4,4−ヘプタフルオル−ヘキセン−１等の水酸基含有
単量体を構成単位として有する付加重合体もしくはグラ
フト等により含有せしめた重合体、カルボン酸ビニル、
カルボン酸アリル、ポリオレフィン等の加水分解、加ア
ルコール分解、酸化等により水酸基に転換可能な基を有
する単量体を構成単位として含有せしめた重合体の該部
位を水酸基に転換したもの、多塩基酸と多価アルコール
あるいはこれらの誘導体を縮合重合、又はラクトン類を
開環重合せしめて得られる水酸基を有するポリエステル
重合体、多価アルコール、フェノール類とエピクロルヒ
ドリン等とを反応せしめて得られる水酸基を有するエポ
キシ縮重合体、エチレンオキシド、プロピレンオキシド
等を必須構成単位として有する水酸基を有するアルキレ
ンオキシド重合体、オルガノシロキサノール等の水酸基
を有するシリコーン樹脂、メラミン、グアナミン類、尿
素類、フェノール類とホルムアルデヒド類とを付加縮合
して得られる重合体、多塩基酸、多価アルコール、脂肪
酸とフェノールホルムアルデヒド等を共縮合して得られ
るフェノールアルキッド重合体、更にはイソシアナート
類、ε−カプロラクトン等あるいは前記した重合体等を
用いて変性された重合体等が有用であるが、これらに限
定されるものではない。又、かかる重合体としては、被
覆形成時の反応性の面から、水酸基を１級もしくは２級
の形態で含有する重合体が好ましい。As the polymer having a hydroxyl group according to the present invention, various polymers having a hydroxyl group can be used. For example, hydroxyalkyl vinyl ether, hydroxyalkyl (meth) acrylate, allyl alcohol, methallyl alcohol, Hydroxy-1,1,2-
Trifluoro-butene-1,6-hydroxy-1,1,2,3,
3,4,4-heptafluoro-hexene-1 and the like, a polymer containing a hydroxyl group-containing monomer such as an addition polymer or a graft-containing polymer having a structural unit, vinyl carboxylate,
Allyl carboxylate, polyolefin, etc., a polymer containing a monomer having a group that can be converted to a hydroxyl group by hydrolysis, alcoholysis, oxidation or the like as a constituent unit, in which the site is converted to a hydroxyl group, polybasic acid And polyhydric alcohols or their derivatives by condensation polymerization, or by ring-opening polymerization of lactones.Polyester polymer having hydroxyl group, polyhydric alcohol, epoxy having hydroxyl group obtained by reacting phenols with epichlorohydrin, etc. Condensation polymers, ethylene oxide, alkylene oxide polymers having a hydroxyl group having essential constituent units such as propylene oxide, silicone resins having a hydroxyl group such as organosiloxanol, melamine, guanamines, ureas, phenols and formaldehydes Polymerization obtained by addition condensation , Polybasic acids, polyhydric alcohols, phenol alkyd polymers obtained by co-condensing fatty acids with phenol formaldehyde, etc., and isocyanates, ε-caprolactone, etc. or polymers modified with the above-mentioned polymers, etc. Are useful, but not limited to these. As such a polymer, a polymer containing a hydroxyl group in a primary or secondary form is preferable from the viewpoint of reactivity at the time of coating formation.
更に、かかる水酸基を有する重合体としては、β−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）アクリレート等のヒドロキシアルキル
（メタ）アクリレート、アリルアルコール、メタアリル
アルコールの中から選ばれる少なくとも１種を構成単位
とし、（メタ）アクリル酸、（メタ）アクリル酸エステ
ル類、（メタ）アクリロニトリル、（メタ）アクリルア
ミド、スチレン、ｐ−メチルスチレン、酢酸ビニル、無
水マレイン酸、ブタジェン等、更にはこれらの誘導体等
のその他の構成単位を有するアクリル重合体、フルオロ
オレフィン、シクロヘキシルビニルエーテル、アルキル
ビニルエーテルおよびヒドロキシアルキルビニルエーテ
ルを必須構成単位とし、それぞれ40〜60モル％、５〜45
モル％、５〜45モル％および３〜15モル％の割合で含有
する含フッ素重合体、無水フタル酸、イソフタル酸、テ
レフタル酸、無水トリメリット酸、テトラヒドロ無水フ
タル酸、ヘキサヒドロ無水フタル酸、無水ハイミック
酸、無水コハク酸、アジピン酸、セバシン酸、アゼライ
ン酸、ドデカンジカルボン酸、無水マレイン酸等の多塩
基酸とエチレングリコール、プロピレングリコール、1,
6−ヘキサンジオール、ジエチレングリコール、ネオペ
ンチルグリコール、トリエチレングリコール、ビスフェ
ノールジヒドロキシプロピルエーテル、シクロヘキサン
ジメタノール、グリセリン、トリメチロールエタン、ト
リメチロールプロパン等の多価アルコールあるいはこれ
らの誘導体とを縮重合せしめて得られる水酸基を有する
ポリエステル重合体、ビスフェノールＡ等の２価のフェ
ノールとエピクロルヒドリン等とを縮重合せしめて得ら
れる水酸基を有するエポキシ重合体等が好ましい。Further, the polymer having a hydroxyl group includes at least one selected from hydroxyalkyl (meth) acrylates such as β-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, allyl alcohol, and methallyl alcohol. Using the seed as a structural unit, (meth) acrylic acid, (meth) acrylic esters, (meth) acrylonitrile, (meth) acrylamide, styrene, p-methylstyrene, vinyl acetate, maleic anhydride, butadiene, and the like An acrylic polymer having other structural units such as a derivative of the above, a fluoroolefin, a cyclohexyl vinyl ether, an alkyl vinyl ether and a hydroxyalkyl vinyl ether as essential structural units, each of which is 40 to 60 mol%,
Fluorinated polymer, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, in the proportions of 5 mol%, 5 to 45 mol% and 3 to 15 mol% Polymic acids such as hymic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic anhydride and ethylene glycol, propylene glycol,
It can be obtained by condensation polymerization of polyhydric alcohols such as 6-hexanediol, diethylene glycol, neopentyl glycol, triethylene glycol, bisphenol dihydroxypropyl ether, cyclohexane dimethanol, glycerin, trimethylolethane, trimethylolpropane or derivatives thereof. A polyester polymer having a hydroxyl group, an epoxy polymer having a hydroxyl group obtained by condensation polymerization of a divalent phenol such as bisphenol A with epichlorohydrin, and the like are preferable.
かかる水酸基を有する重合体の具体例としては、トア
アクロン600、同700〔東亜ペイント（株）製〕、マジク
ロン−600〔関西ペイント（株）製〕、アルマテックス7
48−5M、同748−16AE、同781−26、同781−27、同782−
５、同784、同762LV55A、同D104、同D105、同D151、同8
94−２〔三井東圧化学（株）製〕等のアクリル樹脂、オ
レスターQ152、同Q161−45、同Q169〔三井東圧化学
（株）製〕等のポリエステル変性アクリル樹脂、ルミフ
ロンLF100、同LF200、同LF302、同LF400、同LF554、同L
F600〔旭硝子（株）製〕等の含フッ素樹脂、ベッコライ
トＮ−6601−60−Ｓ〔大日本インキ化学工業（株）製〕
の油変性ポリエステル樹脂、アルマテックスＰ−645、
同Ｐ−646、同Ｐ−647BS、同HMP15、同HMP25、同HMP34
〔三井東圧化学（株）製〕、ベッコライトＮ−6602−60
−Ｓ、同Ｍ−6401−50、同Ｍ−6402−50、同Ｍ−6003−
60、同Ｍ−6005−60、同Ｍ−6007−60、同48−312、同4
9−376、同46−169−Ｓ、同Ｍ−6201−40−IM、同Ｍ−6
204−50−Ｓ、同Ｍ−6204−50−Ｓ〔大日本インキ化学
工業（株）製〕、ダイナポール829、同LH790、同LH81
2、同LH821〔ダイナミート・ノーベル社製〕等のオイル
フリーポリエステル樹脂、アロブラッツ1710、同1711、
同7323〔日触アロー化学（株）製〕等のシリコーン変性
ポリエステル樹脂、エピコート1001、同1004、同1007、
同1009、同1010、同OL55−Ｂ−40〔油化シェルエポキシ
社製〕、アラルダイトGY−6071,同GY−6084、同GY−609
7〔チバ・ガイギー社製〕等のエポキシ樹脂、エポキ−8
03〔三井東圧化学（株）製〕、エポトートYD−017、同Y
D−014、同YD−011、同YD−128〔東都化成（株）製〕、
エピクロン4050〔大日本インキ化学工業（株）製〕、エ
ポニックス110、同3100〔大日本塗料（株）製〕等のウ
レタン変性エポキシ樹脂、プラクセルＧ−101、同Ｇ−1
02、同Ｇ−401、同Ｇ−701、同Ｇ−702〔ダイセル化学
工業（株）製〕等のε−カプロラクトン変性エポキシ樹
脂、エポキー701HV〔三井東圧化学（株）製〕等のポリ
エステル変性エポキシ樹脂等が挙げられるが、これらに
限定されるものではない。Specific examples of such a polymer having a hydroxyl group include Toaaclon 600 and 700 (manufactured by Toa Paint Co., Ltd.), Magiclon-600 (manufactured by Kansai Paint Co., Ltd.), Almatex 7
48-5M, 748-16AE, 781-26, 781-27, 782-
5, 784, 762LV55A, D104, D105, D151, 8
Acrylic resin such as 94-2 [manufactured by Mitsui Toatsu Chemical Co., Ltd.]; polyester-modified acrylic resin such as Olester Q152, Q161-45, Q169 [manufactured by Mitsui Toatsu Chemical Co., Ltd.]; Lumiflon LF100; LF200, LF302, LF400, LF554, L
Fluororesin resin such as F600 (manufactured by Asahi Glass Co., Ltd.), Beccolite N-6601-60-S (manufactured by Dainippon Ink and Chemicals, Inc.)
Oil-modified polyester resin, Armatex P-645,
P-646, P-647BS, HMP15, HMP25, HMP34
[Mitsui Toatsu Chemical Co., Ltd.], Beckolite N-6602-60
-S, M-6401-50, M-6402-50, M-6003-
60, M-6005-60, M-6007-60, 48-312, 4
9-376, 46-169-S, M-6201-40-IM, M-6
204-50-S, M-6204-50-S (manufactured by Dainippon Ink and Chemicals, Inc.), Dynapol 829, LH790, LH81
2, oil-free polyester resin such as LH821 (Dynameat Nobel), Allo Bratz 1710, 1711,
Silicone-modified polyester resin such as 7323 (manufactured by Nisshin Arrow Chemical Co., Ltd.), Epicoat 1001, 1004, 1007,
1009, 1010, OL55-B-40 (manufactured by Yuka Shell Epoxy), Araldite GY-6071, GY-6084, GY-609
Epoxy resin such as 7 (manufactured by Ciba-Geigy), Epoxy-8
03 [Mitsui Toatsu Chemical Co., Ltd.], Epotote YD-017, Y
D-014, YD-011, YD-128 (manufactured by Toto Kasei Co., Ltd.),
Urethane-modified epoxy resins such as EPICLON 4050 (manufactured by Dainippon Ink and Chemicals, Inc.), Eponix 110 and 3100 (manufactured by Dainippon Paint Co., Ltd.), Plaxel G-101, and Plaxel G-1
02, ε-caprolactone-modified epoxy resin such as G-401, G-701, and G-702 (manufactured by Daicel Chemical Industries, Ltd.), and polyester-modified such as Epoki 701HV (manufactured by Mitsui Toatsu Chemicals, Inc.) Examples include, but are not limited to, epoxy resins.
本発明に係わる含フッ素グアナミン化合物（Ｉ）にお
いて、R1はCF3、C2F5、C3F7、（CF3）2CF、C4F9、（C
F3）2CF−Ｏ基の中から選ばれる１種であり、R2はＦ原
子および／又はCF3基であるが、原料製造時の反応性等
からR9はＦ原子が特に好ましく、更にR3はメチレン、エ
チレン、トリメチレン、プロピレン基の中から選ばれる
１種であるが、原料、該化合物（Ｉ）の製造の簡便さ等
からメチレン、エチレン基が特に好ましい。In the fluorine-containing guanamine compound (I) according to the present invention, R 1 is CF 3 , C 2 F 5 , C 3 F 7 , (CF 3 ) 2 CF, C 4 F 9 , (C
F 3 ) 2 is a type selected from CF—O groups, and R 2 is an F atom and / or a CF 3 group, and R 9 is particularly preferably an F atom from the viewpoint of reactivity during raw material production, Further, R 3 is one selected from methylene, ethylene, trimethylene and propylene groups, and methylene and ethylene groups are particularly preferred from the viewpoint of the raw material, ease of production of the compound (I) and the like.
また、Ｆ原子と結合した炭素原子数が３個以上である
場合、防汚性、撥水撥油性、潤滑性、非粘着性等の表面
特性が優れ特に有用である。When the number of carbon atoms bonded to the F atom is 3 or more, the surface properties such as antifouling property, water / oil repellency, lubricity, and non-adhesion are excellent and particularly useful.
かかる含フッ素グアナミン化合物（Ｉ）の具体例とし
ては、2,4−ジアミノ−６−（2,2,2−トリフルオルエチ
ル）−ｓ−トリアジン、2,4−ジアミノ−６−（2,2,3,
3,3−ペンタフルオルプロピル）−ｓ−トリアジン、2,4
−ジアミノ−６−（1H,1H−ヘプタフルオルブチル）−
ｓ−トリアジン、2,4−ジアミノ−６−（1H,1H−ノナフ
ルオルペンチル）−ｓ−トリアジン、2,4−ジアミノ−
６−（1H,1H−ウンデカフルオルヘキシル）−ｓ−トリ
アジン、2,4−ジアミノ−６−（1H,1H−トリデカフルオ
ルヘプチル）−ｓ−トリアジン、2,4−ジアミノ−６−
（1H,1H−ペンタデカフルオルオクチル）−ｓ−トリア
ジン、2,4−ジアミノ−６−（1H,1H−ヘプタデカフルオ
ルノニル）−ｓ−トリアジン、2,4−ジアミノ−６−（1
H,1H−ノナデカフルオルデシル）−ｓ−トリアジン、2,
4−ジアミノ−６−（1H,1H−ヘンヘイコサフルオルウン
デシル）−ｓ−トリアジン、2,4−ジアミノ−６−（1H,
1H−ペンタコサフルオルトリデシル）−ｓ−トリアジ
ン、2,4−ジアミノ−６−（1H,1H−ノナコサフルオルペ
ンタデシル）−ｓ−トリアジン、2,4−ジアミノ−６−
（1H,1H−トリトリアコンタフルオルヘプタデシル）−
ｓ−トリアジン、2,4−ジアミノ−６−（3,3,3−トリフ
ルオルプロピル）−ｓ−トリアジン、2,4−ジアミノ−
６−（3,3,4,4,4−ペンタフルオルブチル）−ｓ−トリ
アジン、2,4−ジアミノ−６−（3,3,4,4,5,5,5−ヘプタ
フルオルペンチル）−ｓ−トリアジン、2,4−ジアミノ
−６−（3,3,4,4,5,5,6,6,6−ノナフルオルヘキシル）
−ｓ−トリアジン、2,4−ジアミノ−６−（1H,1H,2H,2H
−ウンデカフルオルヘプチル）−ｓ−トリアジン、2,4
−ジアミノ−６−（1H,1H,2H,2H−トリデカフルオルオ
クチル）−ｓ−トリアジン、2,4−ジアミノ−６−（1H,
1H,2H,2H−ペンタデカフルオルノニル）−ｓ−トリアジ
ン、2,4−ジアミノ−６−（1H,1H,2H,2H−ヘプタデカフ
ルオルデシル）−ｓ−トリアジン、2,4−ジアミノ−６
−（1H,1H,2H,2H−ノナデカフルオルウンデシル）−ｓ
−トリアジン、2,4−ジアミノ−６−（1H,1H,2H,2H−ヘ
ンエイコサフルオルドデシル）−ｓ−トリアジン、2,4
−ジアミノ−６−（1H,1H,2H,2H−トリコサフルオルト
リデシル）−ｓ−トリアジン、2,4−ジアミノ−６−（1
H,1H,2H,2H−ペンタコサフルオルテトラデシル）−ｓ−
トリアジン、2,4−ジアミノ−６−（1H,1H,2H,2H−ヘプ
タコサフルオルペンタデシル）−ｓ−トリアジン、2,4
−ジアミノ−６−（1H,1H,2H,2H−ノナコサフルオルヘ
キサデシル）−ｓ−トリアジン、2,4−ジアミノ−６−
（1H,1H,2H,2H−ヘントリアコンタフルオルヘプタデシ
ル）−ｓ−トリアジン、2,4−ジアミノ−６−（1H,1H,2
H,2H−トリトリアコンタフルオルオクタデシル）−ｓ−
トリアジン、2,4−ジアミノ−６−（4,4,5,5,5−ペンタ
フルオルペンチル）−ｓ−トリアジン、2,4−ジアミノ
−６−（4,4,5,5,6,6,7,7,7−ノナフルオルヘプチル）
−ｓ−トリアジン、2,4−ジアミノ−６−（1H,1H,2H,2
H,3H,3H−トリデカフルオルノニル）−ｓ−トリアジ
ン、2,4−ジアミノ−６−（1H,1H,2H,2H,3H,3H−ペンタ
デカフルオルデシル）−ｓ−トリアジン、2,4−ジアミ
ノ−６−（1H,1H,2H,2H,3H,3H−ヘプタデカフルオルウ
ンデシル）−ｓ−トリアジン、2,4−ジアミノ−６−（1
H,1H,2H,2H,3H,3H−ノナデカフルオルドデシル）−ｓ−
トリアジン、2,4−ジアミノ−６−（1H,1H,2H,2H,3H,3H
−ノナコサフルオルヘプタデシル）−ｓ−トリアジン、
2,4−ジアミノ−６−（１−メチル−1H,2H,2H−ヘプタ
デカフルオルデシル）−ｓ−トリアジン、2,4−ジアミ
ノ−６−〔３−（トリフルオルメチル）−3,4,4,4−テ
トラフルオルブチル〕−ｓ−トリアジン、2,4−ジアミ
ノ−６−〔５−（トリフルオルメチル）−1H,1H,2H,2H
−オクタフルオルヘキシル〕−ｓ−トリアジン、2,4−
ジアミノ−６−〔７−（トリフルオルメチル）−1H,1H,
2H,2H−ドデカフルオルオクチル〕−ｓ−トリアジン、
2,4−ジアミノ−６−〔９−（トリフルオルメチル）−1
H,1H,2H,2H−ヘキサデカフルオルデシル〕−ｓ−トリア
ジン、2,4−ジアミノ−６−〔11−（トリフルオルメチ
ル）−1H,1H,2H,2H−エイコサフルオルドデシル〕−ｓ
−トリアジン、2,4−ジアミノ−６−〔15−（トリフル
オルメチル）−1H,1H,2H,2H−オクタコサフルオルヘキ
サデシル〕−ｓ−トリアジン、2,4−ジアミノ−６−
〔４−（トリフルオルメチル）−1H,1H−オクタフルオ
ルペンチル〕−ｓ−トリアジン、2,4−ジアミノ−６−
〔６−（トリフルオルメチル）−1H,1H−ドデカフルオ
ルヘプチル〕−ｓ−トリアジン、2,4−ジアミノ−６−
〔８−（トリフルオルメチル）−1H,1H−ヘキサデカフ
ルオルノニル〕−ｓ−トリアジン、2,4−ジアミノ−６
−〔12−（トリフルオルメチル）−1H,1H−テトラコサ
フルオルトリデシル〕−ｓ−トリアジン、2,4−ジアミ
ノ−６−〔４−（トリフルオルメチル）−4,5,5,5−テ
トラフルオルペンチル〕−ｓ−トリアジン、2,4−ジア
ミノ−６−〔８−（トリフルオルメチル）−1H,1H,2H,2
H,3H,3H−ドデカフルオルノニル〕−ｓ−トリアジン、
2,4−ジアミノ−６−〔２−（ペルフルオルイソプロポ
キシ）−エチル〕−ｓ−トリアジン、2,4−ジアミノ−
６−〔3,3,4,4−テトラフルオル−４−（ペルフルオル
イソプロポキシ）−ブチル〕−ｓ−トリアジン、2,4−
ジアミノ−６−〔６−（ペルフルオルイソプロポキシ）
−1H,1H,2H,2H−オクタフルオルヘキシル〕−ｓ−トリ
アジン、2,4−ジアミノ−６−〔８−（ペルフルオルイ
ソプロポキシ）−1H,1H,2H,2H−ドデカフルオルオクチ
ル〕−ｓ−トリアジン、2,4−ジアミノ−６−〔12−
（ペルフルオルイソプロポキシ）−1H,1H,2H,2H−エイ
コサフルオルドデシル〕−ｓ−トリアジン、2,4−ジア
ミノ−６−〔14−（ペルフルオルイソプロポキシ）−1
H,1H,2H,2H−テトラコサフルオルテトラデシル〕−ｓ−
トリアジン、2,4−ジアミノ−６−〔７−（ペルフルオ
ルイソプロポキシ）−1H,1H−ドデカフルオルヘプチ
ル〕−ｓ−トリアジン、2,4−ジアミノ−６−〔11−
（ペルフルオルイソプロポキシ）−1H,1H−エイコサフ
ルオルウンデシル〕−ｓ−トリアジン、2,4−ジアミノ
−６−〔９−（ペルフルオルイソプロポキシ）−1H,1H,
2H,2H,3H,3H−ドデカフルオルノニル〕−ｓ−トリアジ
ン、2,4−ジアミノ−６−〔３−（トリフルオルメチ
ル）−1H,1H,2H,2H−ヘキサフルオルペンチル〕−ｓ−
トリアジン、2,4−ジアミノ−６−〔３−（トリフルオ
ルメチル）−1H,1H,2H,2H−オクタフルオルヘキシル〕
−ｓ−トリアジン、2,4−ジアミノ−６−〔３−（トリ
フルオルメチル）−1H,1H,2H,2H−デカフルオルヘプチ
ル〕−ｓ−トリアジン、2,4−ジアミノ−６−〔3,5−ビ
ス（トリフルオルメチル）−1H,1H,2H,2H−ヘプタフル
オルヘキシル〕−ｓ−トリアジン、2,4−ジアミノ−６
−〔３−（トリフルオルメチル）−1H,1H,2H,2H−ドデ
カフルオルオクチル〕−ｓ−トリアジン、2,4−ジアミ
ノ−６−〔３−（トリフルオルメチル）−４−（ペルフ
ルオルイソプロポキシ）−トリフルオルブチル〕−ｓ−
トリアジン、2,4−ジアミノ−６−〔3,5−ビス（トリフ
ルオルメチル）−1H,1H,2H,2H−ウンデカフルオルオク
チル〕−ｓ−トリアジン、2,4−ジアミノ−６−〔3,5,7
−トリス（トリフルオルメチル）−1H,1H,2H,2H−デカ
フルオルオクチル〕−ｓ−トリアジン、2,4−ジアミノ
−６−〔2,4−ビス（トリフルオルメチル）−1H,1H−ペ
ンタデカフルオルノニル〕−ｓ−トリアジン、2,4−ジ
アミノ−６−〔3,5−ビス（トリフルオルメチル）−６
−（ペルフルオルイソプロポキシ）−1H,1H,2H,2H−ヘ
キサフルオルヘキシル〕−ｓ−トリアジン、2,4−ジア
ミノ−６−〔７−（トリフルオルメチル）−1H,1H,2H,2
H−ヘキサデカフルオルデシル〕−ｓ−トリアジン、2,4
−ジアミノ−６−〔11,13−ビス（トリフルオルメチ
ル）−1H,1H,2H,2H−トリコサフルオルテトラデシル〕
−ｓ−トリアジン等が挙げられるが、これらの化合物に
限定されるものではない。Specific examples of such a fluorine-containing guanamine compound (I) include 2,4-diamino-6- (2,2,2-trifluoroethyl) -s-triazine and 2,4-diamino-6- (2,2 , 3,
3,3-pentafluoropropyl) -s-triazine, 2,4
-Diamino-6- (1H, 1H-heptafluorobutyl)-
s-Triazine, 2,4-diamino-6- (1H, 1H-nonafluoropentyl) -s-triazine, 2,4-diamino-
6- (1H, 1H-undecafluorohexyl) -s-triazine, 2,4-diamino-6- (1H, 1H-tridecafluoroheptyl) -s-triazine, 2,4-diamino-6
(1H, 1H-pentadecafluorooctyl) -s-triazine, 2,4-diamino-6- (1H, 1H-heptadecafluorononyl) -s-triazine, 2,4-diamino-6- (1
H, 1H-nonadecafluorodecyl) -s-triazine, 2,
4-diamino-6- (1H, 1H-Henheicosafluoroundecyl) -s-triazine, 2,4-diamino-6- (1H,
1H-pentacosafluorotridecyl) -s-triazine, 2,4-diamino-6- (1H, 1H-nonacosafluoropentadecyl) -s-triazine, 2,4-diamino-6
(1H, 1H-tritriacontafluoroheptadecyl)-
s-triazine, 2,4-diamino-6- (3,3,3-trifluoropropyl) -s-triazine, 2,4-diamino-
6- (3,3,4,4,4-pentafluorobutyl) -s-triazine, 2,4-diamino-6- (3,3,4,4,5,5,5-heptafluoropentyl ) -S-Triazine, 2,4-diamino-6- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)
-S-triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H
-Undecafluoroheptyl) -s-triazine, 2,4
-Diamino-6- (1H, 1H, 2H, 2H-tridecafluorooctyl) -s-triazine, 2,4-diamino-6- (1H,
1H, 2H, 2H-pentadecafluorononyl) -s-triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H-heptadecafluorodecyl) -s-triazine, 2,4-diamino -6
-(1H, 1H, 2H, 2H-nonadecafluoroundecyl) -s
-Triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H-heneicosafluordodecyl) -s-triazine, 2,4
-Diamino-6- (1H, 1H, 2H, 2H-tricosafluorotridecyl) -s-triazine, 2,4-diamino-6- (1
H, 1H, 2H, 2H-pentacosafluorotetradecyl) -s-
Triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H-heptacosafluoropentadecyl) -s-triazine, 2,4
-Diamino-6- (1H, 1H, 2H, 2H-nonacosafluorohexadecyl) -s-triazine, 2,4-diamino-6
(1H, 1H, 2H, 2H-hentriacontafluoroheptadecyl) -s-triazine, 2,4-diamino-6- (1H, 1H, 2
H, 2H-tritriacontafluorooctadecyl) -s-
Triazine, 2,4-diamino-6- (4,4,5,5,5-pentafluoropentyl) -s-triazine, 2,4-diamino-6- (4,4,5,5,6, 6,7,7,7-nonafluoroheptyl)
-S-triazine, 2,4-diamino-6- (1H, 1H, 2H, 2
H, 3H, 3H-tridecafluorononyl) -s-triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H, 3H, 3H-pentadecafluorodecyl) -s-triazine, 2 , 4-Diamino-6- (1H, 1H, 2H, 2H, 3H, 3H-heptadecafluoroundecyl) -s-triazine, 2,4-diamino-6- (1
H, 1H, 2H, 2H, 3H, 3H-nonadecafluorodecyl) -s-
Triazine, 2,4-diamino-6- (1H, 1H, 2H, 2H, 3H, 3H
-Nonacosafluoroheptadecyl) -s-triazine,
2,4-diamino-6- (1-methyl-1H, 2H, 2H-heptadecafluorodecyl) -s-triazine, 2,4-diamino-6- [3- (trifluoromethyl) -3,4 , 4,4-Tetrafluorobutyl] -s-triazine, 2,4-diamino-6- [5- (trifluoromethyl) -1H, 1H, 2H, 2H
-Octafluorohexyl] -s-triazine, 2,4-
Diamino-6- [7- (trifluoromethyl) -1H, 1H,
2H, 2H-dodecafluorooctyl] -s-triazine,
2,4-diamino-6- [9- (trifluoromethyl) -1
H, 1H, 2H, 2H-hexadecafluorodecyl] -s-triazine, 2,4-diamino-6- [11- (trifluoromethyl) -1H, 1H, 2H, 2H-eicosafluorodecyl]- s
-Triazine, 2,4-diamino-6- [15- (trifluoromethyl) -1H, 1H, 2H, 2H-octacosafluorohexadecyl] -s-triazine, 2,4-diamino-6
[4- (Trifluoromethyl) -1H, 1H-octafluoropentyl] -s-triazine, 2,4-diamino-6
[6- (trifluoromethyl) -1H, 1H-dodecafluoroheptyl] -s-triazine, 2,4-diamino-6
[8- (trifluoromethyl) -1H, 1H-hexadecafluorononyl] -s-triazine, 2,4-diamino-6
-[12- (trifluoromethyl) -1H, 1H-tetracosafluorotridecyl] -s-triazine, 2,4-diamino-6- [4- (trifluoromethyl) -4,5,5,5 -Tetrafluoropentyl] -s-triazine, 2,4-diamino-6- [8- (trifluoromethyl) -1H, 1H, 2H, 2
H, 3H, 3H-dodecafluornonyl] -s-triazine,
2,4-diamino-6- [2- (perfluoroisopropoxy) -ethyl] -s-triazine, 2,4-diamino-
6- [3,3,4,4-tetrafluoro-4- (perfluoroisopropoxy) -butyl] -s-triazine, 2,4-
Diamino-6- [6- (perfluoroisopropoxy)
-1H, 1H, 2H, 2H-octafluorohexyl] -s-triazine, 2,4-diamino-6- [8- (perfluoroisopropoxy) -1H, 1H, 2H, 2H-dodecafluorooctyl] -S-triazine, 2,4-diamino-6- [12-
(Perfluoroisopropoxy) -1H, 1H, 2H, 2H-eicosafluorodecyl] -s-triazine, 2,4-diamino-6- [14- (perfluoroisopropoxy) -1
H, 1H, 2H, 2H-tetracosafluorotetradecyl] -s-
Triazine, 2,4-diamino-6- [7- (perfluoroisopropoxy) -1H, 1H-dodecafluoroheptyl] -s-triazine, 2,4-diamino-6- [11-
(Perfluoroisopropoxy) -1H, 1H-eicosafluoroundecyl] -s-triazine, 2,4-diamino-6- [9- (perfluoroisopropoxy) -1H, 1H,
2H, 2H, 3H, 3H-dodecafluorononyl] -s-triazine, 2,4-diamino-6- [3- (trifluoromethyl) -1H, 1H, 2H, 2H-hexafluoropentyl] -s −
Triazine, 2,4-diamino-6- [3- (trifluoromethyl) -1H, 1H, 2H, 2H-octafluorohexyl]
-S-triazine, 2,4-diamino-6- [3- (trifluoromethyl) -1H, 1H, 2H, 2H-decafluoroheptyl] -s-triazine, 2,4-diamino-6- [3 , 5-Bis (trifluoromethyl) -1H, 1H, 2H, 2H-heptafluorohexyl] -s-triazine, 2,4-diamino-6
-[3- (trifluoromethyl) -1H, 1H, 2H, 2H-dodecafluorooctyl] -s-triazine, 2,4-diamino-6- [3- (trifluoromethyl) -4- (perfluoro Orthoisopropoxy) -trifluorobutyl] -s-
Triazine, 2,4-diamino-6- [3,5-bis (trifluoromethyl) -1H, 1H, 2H, 2H-undecafluorooctyl] -s-triazine, 2,4-diamino-6- [ 3,5,7
-Tris (trifluoromethyl) -1H, 1H, 2H, 2H-decafluorooctyl] -s-triazine, 2,4-diamino-6- [2,4-bis (trifluoromethyl) -1H, 1H- Pentadecafluorononyl] -s-triazine, 2,4-diamino-6- [3,5-bis (trifluoromethyl) -6
-(Perfluoroisopropoxy) -1H, 1H, 2H, 2H-hexafluorohexyl] -s-triazine, 2,4-diamino-6- [7- (trifluoromethyl) -1H, 1H, 2H, 2
H-hexadecafluorodecyl] -s-triazine, 2,4
-Diamino-6- [11,13-bis (trifluoromethyl) -1H, 1H, 2H, 2H-tricosafluorotetradecyl]
-S-triazine and the like, but are not limited to these compounds.
かかるホルムアルデヒド類としては、例えばホルムア
ルデヒド、ホルマリン、パラホルム、ヘキサメチレンテ
トラミン、メチルヘミホルマール、ブチルヘミホルマー
ル、ホルムアルデヒド重亜硫酸ソーダ付加物等が挙げら
れるが、ホルムアルデヒド源として作用するものであれ
ばよく、これらの化合物に限定されるものではない。Examples of such formaldehydes include formaldehyde, formalin, paraform, hexamethylenetetramine, methylhemiformal, butylhemiformal, formaldehyde sodium bisulfite adduct, and the like. It is not limited to compounds.
また、かかる含フッ素グアナミン化合物（Ｉ）とホル
ムアルデヒド類との反応において、水、メタノール、エ
タノール、ブタノール、シクロヘキサノール等のアルコ
ール類、エステル、ケトン、エーテル、カルボン酸アミ
ド等の溶媒中にて、場合により水酸化カリウム、ナトリ
ウムメチラート、アミン等の塩基性化合物存在下、pH7.
0〜13.0、更にはpH7.5〜11.0の条件下で、反応温度30℃
〜120℃にて行わしめることにより少なくとも１個のメ
チロール基を有するメチロール化含フッ素グアナミン誘
導体を得ることができるが、これらの方法に限定される
ものではない。In the reaction of the fluorinated guanamine compound (I) with formaldehydes, the reaction is carried out in a solvent such as water, alcohols such as methanol, ethanol, butanol and cyclohexanol, esters, ketones, ethers and carboxylic amides. PH 7 in the presence of basic compounds such as potassium hydroxide, sodium methylate and amines.
Under the conditions of 0 to 13.0, and furthermore, pH 7.5 to 11.0, the reaction temperature is 30 ° C.
By performing the reaction at -120 ° C, a methylolated fluorine-containing guanamine derivative having at least one methylol group can be obtained, but the method is not limited to these methods.
又、本発明に係わる炭素数１〜20個を有する脂肪族ア
ルコールおよび脂環族アルコールにおいて、炭素数１〜
20個を有する直鎖又は側鎖を有する飽和脂肪族アルコー
ル、不飽和脂肪族アルコールおよび分枝鎖を有すること
もある飽和脂環族アルコール、不飽和脂環族アルコール
が有用であり、更に、製造の簡便さ、該含フッ素グアナ
ミン誘導体の有用性、反応性等から炭素数１〜６個を有
する飽和脂肪族アルコールおよびシクロヘキシルアルコ
ールが特に好ましい。Further, in the aliphatic alcohol and alicyclic alcohol having 1 to 20 carbon atoms according to the present invention, 1 to 1 carbon atoms
Saturated aliphatic alcohols having a linear or side chain having 20, unsaturated aliphatic alcohols and saturated alicyclic alcohols, which may have a branched chain, unsaturated alicyclic alcohols are useful, and Saturated aliphatic alcohols having 1 to 6 carbon atoms and cyclohexyl alcohol are particularly preferred from the viewpoints of simplicity, usefulness and reactivity of the fluorine-containing guanamine derivative.
かかる炭素数１〜20個を有する脂肪族アルコールおよ
び脂環族アルコールの具体例として、メタノール、エタ
ノール、ｎ−プロパノール、iso−プロパノール、アリ
ルアルコール、ｎ−ブチルアルコール、iso−ブチルア
ルコール、tert−ブチルアルコール、プロパギルアルコ
ール、ネオペンチルアルコール、ｎ−ヘキシルアルコー
ル、ｎ−オクチルアルコール、２−エチル−ヘキシルア
ルコール、ｎ−ノニルアルコール、ｎ−ドデシルアルコ
ール、ｎ−ヘキサデシルアルコール、ｎ−オクタデシル
アルコール、ｎ−エイコシルアルコール等の脂肪族アル
コール、シクロヘキシルアルコール、シクロヘキセニル
アルコール、４−メチルシクロヘキシルアルコール、３
−メチルシクロヘキシルアルコール、シクロヘキシルメ
タノール、４−エチルシクロヘキシルアルコール、４−
ヘキシルシクロヘキシルアルコール、3,5−ジｎ−ヘキ
シルシクロヘキシルアルコール等が挙げられるが、これ
らに限定されるものではない。Specific examples of such aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, allyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl. Alcohol, propargyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethyl-hexyl alcohol, n-nonyl alcohol, n-dodecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n- Aliphatic alcohols such as eicosyl alcohol, cyclohexyl alcohol, cyclohexenyl alcohol, 4-methylcyclohexyl alcohol, 3
-Methylcyclohexyl alcohol, cyclohexylmethanol, 4-ethylcyclohexyl alcohol, 4-
Examples include, but are not limited to, hexylcyclohexyl alcohol, 3,5-di-n-hexylcyclohexyl alcohol, and the like.
また、かかるメチロール化含フッ素グアナミン誘導体
と炭素数１〜20個を有する脂肪族アルコールおよび脂環
族アルコールの中から選ばれる１種との反応において、
かかるメチロール化含フッ素グアナミン誘導体を分離す
るか、あるいは水分20％以下であるメチロール化含フッ
素グアナミン誘導体とかかる脂肪族アルコールおよび脂
環族アルコールの中から選ばれる１種とを用い、酸性条
件下、好ましくはpH1.0〜5.0にて、反応温度50〜100℃
にて、場合に応じて適宜に溶媒あるいは上記した脂肪族
アルコールあるいは脂環族アルコールを過剰に用いて、
溶媒あるいは懸濁液にてエーテル化反応を行わしめるこ
とにより少なくとも１個のR4OCH2基（R4は前記アルコー
ルより水酸基を除いた残基である）を有するエーテル化
含フッ素グアナミン誘導体を得ることができるが、これ
らの方法に限定されるものではない。Further, in the reaction of the methylolated fluorine-containing guanamine derivative and one selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms,
Separating such a methylolated fluorine-containing guanamine derivative, or using a methylolated fluorine-containing guanamine derivative having a water content of 20% or less and one selected from such aliphatic alcohols and alicyclic alcohols under acidic conditions, Preferably at pH 1.0-5.0, reaction temperature 50-100 ° C
In an appropriate amount of a solvent or an aliphatic alcohol or an alicyclic alcohol as described above, if necessary,
An etherified fluorine-containing guanamine derivative having at least one R 4 OCH 2 group (R 4 is a residue obtained by removing a hydroxyl group from the alcohol) by performing an etherification reaction in a solvent or a suspension is obtained. However, the present invention is not limited to these methods.
本発明に係わる被覆用組成物において、上記したエー
テル化含フッ素グアナミン誘導体を成分として含有する
硬化剤とともに、必要に応じて通常用いられている硬化
剤を併用することができ、例えばブトキシ化メチルメラ
ミン、エトキシ化メチルメラミン、メトキシ化メチルメ
ラミン、エポキシ変性メラミン等のメラミン硬化剤、ブ
トキシ化メチル尿素、メトキシ化メチル尿素等の尿素樹
脂硬化剤、長鎖脂肪族ジカルボン酸類、芳香族多価カル
ボン酸類あるいはその無水物等の多塩基酸硬化剤、多価
イソシアネート類、ブロック多価イソシアネート類等の
硬化剤が有用であり、市販品としては、サイメル300、
同301、同303、同325、同370、同1130−266J〔三井サイ
アナミッド（株）製〕、ユーバン20SE−60、同28−60
〔三井東圧化学（株）製〕、ニカラックMV−30M、同MV
−30、同MX−40、同MX−485、同MV−22、同MS−15〔三
和ケミカル（株）製〕、スミマールＭ−100C、同Ｍ−5
5、同Ｍ−40S〔住友化学（株）製〕、レジミン745、同7
47、同753、同755〔モンサント（株）製〕等が挙げられ
るが、これらに限定されるものではない。尚、かかる硬
化剤は１種もしくは２種以上を使用することができ、硬
化剤の種類、配合量も適宜選択することができる。In the coating composition according to the present invention, together with the curing agent containing the etherified fluorine-containing guanamine derivative as a component, a commonly used curing agent can be used in combination as necessary, for example, butoxylated methylmelamine Melamine curing agents such as ethoxylated methyl melamine, methoxylated methyl melamine, epoxy-modified melamine, urea resin curing agents such as butoxylated methyl urea, methoxylated methyl urea, long-chain aliphatic dicarboxylic acids, aromatic polycarboxylic acids or Polybasic acid curing agents such as anhydrides, polyvalent isocyanates, curing agents such as block polyvalent isocyanates are useful, and as commercial products, Cymel 300,
301, 303, 325, 370, 1130-266J [Mitsui Cyanamid Co., Ltd.], U-Van 20SE-60, 28-60
[Mitsui Toatsu Chemical Co., Ltd.], Nikarac MV-30M, MV
-30, MX-40, MX-485, MV-22, MS-15 (manufactured by Sanwa Chemical Co., Ltd.), Sumimar M-100C, M-5
5, M-40S (manufactured by Sumitomo Chemical Co., Ltd.), Regin 745, 7
47, 753, and 755 (manufactured by Monsanto Co., Ltd.), but are not limited thereto. One or more of such curing agents can be used, and the type and amount of the curing agent can be appropriately selected.
本発明に係わる被覆用組成物において、水酸基を有す
る重合体と上記したエーテル化含フッ素グアナミン誘導
体を成分として含有する硬化剤との量比、更に、水酸基
を有する重合体と上記したエーテル化含フッ素グアナミ
ン誘導体との量比は、組成、硬化条件、用途等により適
宜選択することができる。In the coating composition according to the present invention, the ratio of the polymer having a hydroxyl group to the curing agent containing the above-mentioned etherified fluorine-containing guanamine derivative as a component, and further, the polymer having a hydroxyl group and the above-mentioned etherified fluorine-containing guanamine derivative The quantitative ratio with the guanamine derivative can be appropriately selected depending on the composition, curing conditions, application, and the like.
又、本発明に係わる被覆用組成物において、被覆層の
形成は、無触媒下で加熱等により硬化させて得られ、ま
た必要に応じてｐ−トルエンスルホン酸、ドデシルベン
ゼンスルホン酸等の酸性触媒等の硬化促進剤を適宜選択
して添加し硬化させて得られるが、これらの方法に限定
されるものではない。In the coating composition according to the present invention, the formation of the coating layer is obtained by curing by heating or the like in the absence of a catalyst, and if necessary, an acidic catalyst such as p-toluenesulfonic acid or dodecylbenzenesulfonic acid. The curing agent is obtained by appropriately selecting and adding a curing accelerator such as the above, followed by curing. However, the present invention is not limited to these methods.
本発明に係わる被覆用組成物において、随意に顔料を
含有してもよく、かかる顔料はそれ自体公知の着色顔
料、体質顔料、防錆顔料など無機顔料、有機顔料が使用
でき特に制限はなく、例えば二酸化チタン、カーボンブ
ラック、黒鉛、黒酸化鉄、カドミウムレッド、ベンガ
ラ、カドミウムイエロー、ストロンチウムクロメート、
アルミニウム粉、アルミナ、フタロシアニンブルー、キ
ナクリドン系レッド、アゾ系レッド等の着色顔料、クレ
ー、タルク、アスベスト、沈降性硫酸バリウム、ベント
ナイト等の体質顔料、クロメート系顔料、縮合リン酸塩
系顔料、モリブデン酸塩系顔料、ホウ酸塩系顔料、亜酸
化鉛、酸化マグネシウム等の防錆顔料等が挙げられ、単
独もしくは２種以上使用することができる。In the coating composition according to the present invention, a pigment may be optionally added, and such a pigment may be a known coloring pigment, an extender pigment, an inorganic pigment such as a rust preventive pigment, or an organic pigment, and there is no particular limitation. For example, titanium dioxide, carbon black, graphite, black iron oxide, cadmium red, red iron, cadmium yellow, strontium chromate,
Color pigments such as aluminum powder, alumina, phthalocyanine blue, quinacridone red, azo red, etc., extenders such as clay, talc, asbestos, precipitated barium sulfate, bentonite, chromate pigments, condensed phosphate pigments, molybdic acid Examples include salt pigments, borate pigments, rust-preventive pigments such as lead oxide and magnesium oxide, and they can be used alone or in combination of two or more.
又、かかる被覆用組成物において、紫外線吸収剤、光
安定剤、酸化防止剤等の樹脂劣化防止剤を含有させるこ
とにより被覆層の紫外線による経時的劣化を防止するこ
とができる。Further, by including a resin deterioration inhibitor such as an ultraviolet absorber, a light stabilizer and an antioxidant in such a coating composition, it is possible to prevent the coating layer from being deteriorated with time due to ultraviolet rays.
かかる紫外線吸収剤は、紫外線エネルギーを吸収し、
且つかかる組成物と相溶するか均一に分散することがで
き、被覆形成時の焼付温度等で簡単に分解して効力を失
うことがないものであればいずれのものでもよく、例え
ば、ベンゾフェノン、２−ヒドロキシ−４−メトキシベ
ンゾフェノン、2,2′−ジヒドロキシ−4,4′−ジメトキ
シベンゾフェノン、２−ヒドロキシ−４−ドデシロキシ
ベンゾフェノ等のベンゾフェノン系紫外線吸収剤、２−
（２′−ヒドロキシ−５′−メチルフェニル）ベンゾト
リアゾール、２−（２′−ヒドロキシ−３′,5′−ジイ
ソアミルフェニル）ベンゾトリアゾール等のベンゾトリ
アゾール系紫外線吸収剤、４−tert−ブチルフェニルサ
リシレート等のサリチル酸エステル系紫外線吸収剤、２
−エチルヘキシル−２−シアノ−3,3′−ジフェニルア
クリレート等のジフェニルアクリレート系紫外線吸収
剤、ヒドロキシ−５−メトキシ−アセトフェノン等のア
セトフェノン系紫外線吸収剤、蓚酸アニリド系紫外線吸
収剤等があり、これらを単独もしくは２種以上を使用す
ることができ、市販されているものとしては、例えばチ
ヌビン900、チヌビン328（チバ・ガイギー社製）コピヌ
ル400（BASF社製）、サンド3206（サンドボア社製）等
がある。Such UV absorbers absorb UV energy,
In addition, any one can be used as long as it is compatible with the composition or can be uniformly dispersed and does not lose its effectiveness by being easily decomposed at the baking temperature at the time of forming the coating, for example, benzophenone, Benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzopheno,
Benzotriazole ultraviolet absorbers such as (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-diisoamylphenyl) benzotriazole, 4-tert-butylphenyl Salicylic acid ester type ultraviolet absorbers such as salicylate, 2
Diphenyl acrylate UV absorbers such as -ethylhexyl-2-cyano-3,3'-diphenyl acrylate, acetophenone UV absorbers such as hydroxy-5-methoxy-acetophenone, and oxalic anilide UV absorbers. One or more of them can be used. Examples of commercially available ones include Tinuvin 900, Tinuvin 328 (manufactured by Ciba-Geigy), Copinul 400 (manufactured by BASF), Sand 3206 (manufactured by Sandboa), and the like. is there.
又、かかる光安定剤としては、例えばテトラキス（2,
2,6,6−テトラメチル−４−ピペリジル）−1,2,3,4−ブ
タンテトラカルボキシレート、ビス（2,2,6,6−テトラ
メチル−４−ピペリジル）セバケート、ビス（1,2,2,6,
6−ペンタメチル−４−ピペリジル）セバケート、２−
（3,5−ジtertブチル−４−ヒドロキシベンジル）−２
−ｎブチルマロン酸ビス（1,2,2,6−ペンタメチル−４
−ピペリジル）、ジメチル−２−（４−ヒドロキシ−2,
2,6,6−テトラメチル−１−ピペリジル）エタノール縮
合物等が挙げられ、酸化防止剤としては、例えば4,4′
−メチレンビス（2,6−ジtertブチルフェノール）、ジ
ラウリルチオジプロピオネート、テトラキス〔３−（3,
5−ジtertブチル−４−ヒドロキシフェノール）−プロ
ピオネート〕等が挙げられ、これらは単独もしくは２種
以上を使用することができ、前記紫外線吸収剤と併用す
ることが好ましい。As such a light stabilizer, for example, tetrakis (2,
2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,
6-pentamethyl-4-piperidyl) sebacate, 2-
(3,5-ditertbutyl-4-hydroxybenzyl) -2
Bis-n-butylmalonate (1,2,2,6-pentamethyl-4
-Piperidyl), dimethyl-2- (4-hydroxy-2,
2,6,6-tetramethyl-1-piperidyl) ethanol condensate and the like, and as the antioxidant, for example, 4,4 ′
Methylenebis (2,6-ditertbutylphenol), dilaurylthiodipropionate, tetrakis [3- (3,
5-ditertbutyl-4-hydroxyphenol) -propionate], and these can be used alone or in combination of two or more. It is preferable to use them in combination with the ultraviolet absorber.
又、かかる被覆用組成物は、上記成分の他に、種々の
充填剤、潤滑剤、例えばフッ化黒鉛、グラファイト、二
硫化モリブデン、金属石けん、ペルフルオル重合体、ペ
ルフルオルアルキル基含有化合物、シリコーン系化合物
等、可塑剤、例えばジオクチルフタレート、トリクレシ
ルホスフェート、セバシン酸ジブチル等、粘性付与剤、
例えばロジン、クマロン樹脂、エステルガム、低分子量
エポキシ樹脂、ポリオキシテトラメチレングリコール
等、タレ止め剤、例えばアルミニウムステアレート、シ
リカゲル等難燃剤、界面活性剤および他の添加剤を適宜
用いてもよい。In addition, the coating composition may contain, in addition to the above components, various fillers and lubricants such as graphite fluoride, graphite, molybdenum disulfide, metal soap, perfluoropolymer, perfluoroalkyl group-containing compound, and silicone. Plasticizers, such as dioctyl phthalate, tricresyl phosphate, dibutyl sebacate, etc.
For example, rosin, coumarone resin, ester gum, low molecular weight epoxy resin, polyoxytetramethylene glycol, and the like, a sagging agent such as a flame retardant such as aluminum stearate and silica gel, a surfactant, and other additives may be appropriately used.
本発明に係わる被覆用組成物は、常套の方法、例え
ば、非電気泳動法、即ち浸漬塗装、流水塗装およびスプ
レー塗装を用いて塗装してもよい。通常、かかる被覆用
組成物は、いかなる基材、例えば木、金属、ガラス、
布、皮、プラスチック、発泡体に用いてもよく、また、
種々のプライマー上に塗装してもよい。導電性基材、例
えば、金属基材の場合、電着塗装により被覆してもよ
い。The coating composition according to the invention may be applied using conventional methods, for example, non-electrophoretic methods, i.e. dip coating, running water coating and spray coating. Typically, such coating compositions are made of any substrate, such as wood, metal, glass,
May be used on fabrics, leathers, plastics, foams,
It may be painted on various primers. In the case of a conductive substrate, for example, a metal substrate, it may be coated by electrodeposition coating.
本発明に係わる新規な被覆用組成物は、水酸基を有す
る重合体と硬化剤とを必須構成成分とする該組成物にお
いて、前記硬化剤の成分として、活性基を有するかかる
エーテル化含フッ素グアナミン誘導体を含有する為、水
酸基を有する各種の重合体を用いて含フッ素被覆層を形
成することができ、被覆材料の製造、組成の制約が極め
て少なく、且つかかる含フッ素グアナミン誘導体の含フ
ッ素基が加水分解、熱、光等により離脱することが殆ど
なく機能を長期にわたり維持することができる為、公知
の含フッ素重合体では得難い機能性の優れた各種被覆材
料を提供することができ、ゴム材料、フィルムのプロッ
キング防止被覆材、樹脂の摩擦系数低下材、潤滑材、成
形金型等の離型被覆材、テープの背面処理材、静電印刷
用キャリーの非粘着被覆材、凸版印刷の耐刷性向上被覆
材、撥インク被覆材、撥水撥油材、光学材料、ガス分離
膜材料、レジスト材料、家電製品、自動車等の防汚性塗
料、防食性塗料、耐候性塗料、着氷防止塗料、氷結防止
塗料、屋根材、道路標識、鉄塔、電線等の積雪防止塗
料、サッシ等の防汚潤滑被覆材、プリント基板の防湿絶
縁、半導体樹脂の防湿性向上等として電気部品、回路板
等の防湿被覆材、包装用紙の油出にじみ防止、記録紙、
ラベルの汚染防止、剥離紙の非粘着性付与等の紙加工
材、カーテン、ソファー、壁布、カーペット等のインテ
リア製品の防汚加工、繊維の透湿防止加工、吸汗加工、
SR加工等の繊維加工材、皮革処理材、耐熱性樹脂等とし
て極めて広汎な用途に有用な被覆材料を提供することが
できる。The novel coating composition according to the present invention is a composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the etherified fluorine-containing guanamine derivative having an active group as a component of the curing agent. Therefore, the fluorine-containing coating layer can be formed using various polymers having a hydroxyl group, the production material of the coating material, the restrictions on the composition are extremely small, and the fluorine-containing group of the fluorine-containing guanamine derivative is hydrolyzed. Since the function can be maintained for a long time with almost no separation due to decomposition, heat, light, etc., it is possible to provide various types of coating materials having excellent functions which are difficult to obtain with known fluoropolymers, rubber materials, Non-blocking coating material for film blocking, material for reducing the friction coefficient of resin, lubricant, release coating material for molding dies, back surface treatment material for tape, non-adhesive material for electrostatic printing Covering material, Topographic printing durability improvement coating material, ink repellent coating material, water / oil repellent material, optical material, gas separation membrane material, resist material, antifouling paint for home appliances, automobiles, etc., anticorrosive paint, Weather-resistant paint, anti-icing paint, anti-icing paint, roofing materials, road sign, snow-prevention paint such as steel towers and electric wires, anti-fouling lubricating coating materials such as sashes, moisture-proof insulation of printed circuit boards, improvement of moisture resistance of semiconductor resin, etc. Moisture-proof covering materials such as electric parts and circuit boards, oil bleeding prevention of packaging paper, recording paper,
Prevention of label contamination, paper processing materials such as release paper non-adhesiveness, stainproofing of interior products such as curtains, sofas, wall cloths, carpets, etc.
It is possible to provide a coating material useful for a very wide range of uses as a fiber processing material such as SR processing, a leather processing material, a heat resistant resin and the like.
次に、本発明を実施例により詳細に説明する。但し、
これらの実施例記載は、本発明の範囲をこれらのみに限
定するものではない。Next, the present invention will be described in detail with reference to examples. However,
The description of these examples does not limit the scope of the present invention only to them.
参考例１ 2,4−ジアミノ−６−（2,2,3,3,3−ペンタフルオルプ
ロピル）−ｓ−トリアジンのエーテル化誘導体の製造： 2,4−ジアミノ−６−（2,2,3,3,3−ペンタフルオルプ
ロピル）−ｓ−トリアジン12.2g（0.05モル）にメチル
ヘミホルマール16.1g（0.26モル）とメタノール200gを
加え、30％苛性ソーダ水溶液にてpH10.0に調整し、ゆる
やかに還流させながら30分間反応させた。Reference Example 1 Production of an etherified derivative of 2,4-diamino-6- (2,2,3,3,3-pentafluoropropyl) -s-triazine: 2,4-diamino-6- (2,2 To 12.3 g (0.05 mol) of 1,3,3,3-pentafluoropropyl) -s-triazine were added 16.1 g (0.26 mol) of methylhemiformal and 200 g of methanol, and the pH was adjusted to 10.0 with a 30% aqueous sodium hydroxide solution. The reaction was carried out for 30 minutes while gently refluxing.
次に、この反応溶液を、濃硝酸にてpH3.5に調整し、
ゆるやかに還流させながら30分間反応させた。この反応
混合物を冷却後、30％苛性ソーダ水溶液にてpH7.5に調
整後、減圧濾過にて沈殿物を除去し、透明な液を得た。
これを分析した結果、2,4−ジアミノ−６−（2,2,3,3,3
−ペンタフルオルプロピル）−ｓ−トリアジン１モルに
対し全ホルムアルデヒド結合量3.72当量、メチルエーテ
ル基3.37当量、メチロール基0.35当量が結合した該化合
物のエーテル化誘導体であった。Next, the reaction solution was adjusted to pH 3.5 with concentrated nitric acid,
The reaction was allowed to proceed for 30 minutes with gentle reflux. After cooling the reaction mixture, the pH was adjusted to 7.5 with a 30% aqueous sodium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid.
As a result of analyzing this, 2,4-diamino-6- (2,2,3,3,3
-Pentafluoropropyl) -s-triazine was an etherified derivative of the compound in which 3.72 equivalents of total formaldehyde, 3.37 equivalents of methyl ether groups and 0.35 equivalents of methylol groups were bonded to 1 mol of the compound.
参考例２ 2,4−ジアミノ−６−〔６−（ペルフルオルイソプロ
ポキシ）−1H,1H,2H,2H−オクタフルオルヘキシル〕−
ｓ−トリアジンのエーテル化誘導体の製造： 2,4−ジアミノ−６−〔６−（ペルフルオルイソプロ
ポキシ）−1H,1H,2H,2H−オクタフルオルヘキシル〕−
ｓ−トリアジン26.2g（0.05モル）にブチルヘミホルマ
ール31.2g（0.30モル）とｎ−ブタノール300gを加え、3
0％苛性カリ水溶液にてpH11.0に調整し、温度70℃にて3
0分間反応させた。Reference Example 2 2,4-diamino-6- [6- (perfluoroisopropoxy) -1H, 1H, 2H, 2H-octafluorohexyl]-
Preparation of etherified derivative of s-triazine: 2,4-diamino-6- [6- (perfluoroisopropoxy) -1H, 1H, 2H, 2H-octafluorohexyl]-
To 26.2 g (0.05 mol) of s-triazine, 31.2 g (0.30 mol) of butyl hemiformal and 300 g of n-butanol were added.
Adjust the pH to 11.0 with a 0% aqueous solution of potassium hydroxide,
The reaction was performed for 0 minutes.
次に、この反応溶液を、濃硝酸にてpH4.0に調整し、
温度70℃にて30分間反応させた。この反応混合物を冷却
後、30％苛性カリ水溶液にてpH8.0に調整後、減圧濾過
にて沈殿物を除去し、透明な液を得た。これを分析した
結果、2,4−ジアミノ−６−〔６−ペルフルオルイソプ
ロポキシ）−1H,1H,2H,2H−オクタフルオルヘキシル〕
−ｓ−トリアジン１モルに対し全ホルムアルデヒド結合
量3.61当量、ブチルエーテル基3.08当量、メチロール基
0.53当量が結合した該化合物のエーテル化誘導体であっ
た。Next, the reaction solution was adjusted to pH 4.0 with concentrated nitric acid,
The reaction was carried out at a temperature of 70 ° C. for 30 minutes. After cooling the reaction mixture, the pH was adjusted to 8.0 with a 30% aqueous potassium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid. As a result of analyzing this, 2,4-diamino-6- [6-perfluoroisopropoxy) -1H, 1H, 2H, 2H-octafluorohexyl]
3.61 equivalents of total formaldehyde bond, 3.08 equivalents of butyl ether group, methylol group per 1 mol of -s-triazine
0.53 equivalents were the linked etherified derivative of the compound.
参考例３ 2,4−ジアミノ−６−（1H,1H,2H,2H−ヘプタデカフル
オルデシル）−ｓ−トリアジンのエーテル化誘導体の製
造： 2,4−ジアミノ−６−（1H,1H,2H,2H−ヘプタデカフル
オルデシル）−ｓ−トリアジン27.9g（0.05モル）にブ
チルヘミホルマール27.1g（0.26モル）とｎ−ブタノー
ル300gを加え、30％苛性カリ水溶液にてpH10.0に調整
し、温度70℃にて30分間反応させた。Reference Example 3 Production of an etherified derivative of 2,4-diamino-6- (1H, 1H, 2H, 2H-heptadecafluorodecyl) -s-triazine: 2,4-diamino-6- (1H, 1H, To 27.9 g (0.05 mol) of 2H, 2H-heptadecafluorodecyl) -s-triazine were added 27.1 g (0.26 mol) of butylhemiformal and 300 g of n-butanol, and the pH was adjusted to 10.0 with a 30% aqueous solution of potassium hydroxide. The reaction was carried out at a temperature of 70 ° C. for 30 minutes.
次に、この反応溶液を、濃硝酸にてpH3.0に調整し、
温度60℃にて30分間反応させた。この反応混合物を冷却
後、30％苛性カリ水溶液にてpH7.0に調整後、減圧濾過
にて沈殿物を除去し、透明な液を得た。これを分析した
結果、2,4−ジアミノ−６−（1H,1H,2H,2H−ヘプタデカ
フルオルデシル）−ｓ−トリアジン１モルに対し全ホル
ムアルデヒド結合量3.52当量、ブチルエーテル基3.15当
量、メチロール基0.37当量が結合した該化合物のエーテ
ル化誘導体であった。Next, the reaction solution was adjusted to pH 3.0 with concentrated nitric acid,
The reaction was performed at a temperature of 60 ° C. for 30 minutes. After cooling the reaction mixture, the pH was adjusted to 7.0 with a 30% aqueous potassium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid. As a result of the analysis, it was found that the total amount of formaldehyde bonds was 3.52 equivalents, the butyl ether group was 3.15 equivalents, and the 0.37 equivalents of the group was the linked etherified derivative of the compound.
参考例４ 2,4−ジアミノ−６−（4,4,5,5,6,6,7,7,7−ノナフル
オルヘプチル）−ｓ−トリアジンのエーテル化誘導体の
製造： 2,4−ジアミノ−６−（4,4,5,5,6,6,7,7,7−ノナフル
オルヘプチル）−ｓ−トリアジン18.6g（0.05モル）
に、10％苛性カリ水溶液でpH10.0に調整した37％ホルマ
リン17.8g（ホルムアルデヒド0.22モル）を加えた。こ
の混合物を温度70〜75℃にて30分間反応させた。Reference Example 4 Production of an etherified derivative of 2,4-diamino-6- (4,4,5,5,6,6,7,7,7-nonafluoroheptyl) -s-triazine: 2,4- 18.6 g (0.05 mol) of diamino-6- (4,4,5,5,6,6,7,7,7-nonafluoroheptyl) -s-triazine
Then, 17.8 g (0.22 mol of formaldehyde) of 37% formalin adjusted to pH 10.0 with a 10% aqueous potassium hydroxide solution was added thereto. This mixture was reacted at a temperature of 70 to 75 ° C. for 30 minutes.
次に、この反応溶液を、50℃以下の温度にて減圧濃縮
を行った。これにメタノール200gを加えて溶液とし、濃
硝酸にてpH4.0に調整し、ゆるやかに還流させながら30
分間反応させた。この反応混合物を冷却後、30％苛性カ
リ水溶液にてpH8.0に調整後、減圧濾過にて沈殿物を除
去し、透明な液を得た。これを分析した結果、2,4−ジ
アミノ−６−（4,4,5,5,6,6,7,7,7−ノナフルオルヘプ
チル）−ｓ−トリアジン１モルに対し全ホルムアルデヒ
ド結合量3.58当量、メチルエーテル基2.96当量、メチロ
ール基0.62当量が結合した該化合物のエーテル化誘導体
であった。Next, this reaction solution was concentrated under reduced pressure at a temperature of 50 ° C. or lower. To this was added 200 g of methanol to form a solution, which was adjusted to pH 4.0 with concentrated nitric acid.
Allowed to react for minutes. After cooling the reaction mixture, the pH was adjusted to 8.0 with a 30% aqueous potassium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid. As a result of analyzing this, it was found that the total amount of formaldehyde binding was based on 1 mol of 2,4-diamino-6- (4,4,5,5,6,6,7,7,7-nonfluoroheptyl) -s-triazine. It was an etherified derivative of the compound bound with 3.58 equivalents, 2.96 equivalents of methyl ether groups, and 0.62 equivalents of methylol groups.
参考例５ 2,4−ジアミノ−６−（1H,1H−トリデカフルオルヘプ
チル）−ｓ−トリアジンのエーテル化誘導体の製造： 2,4−ジアミノ−６−（1H,1H−トリデカフルオルヘプ
チル）−ｓ−トリアジン22.2g（0.05モル）に、10％苛
性カリ水溶液でpH10.5に調整した37％ホルマリン24.4g
（ホルムアルデヒド0.30モル）を加えた。この混合物を
温度70〜75℃にて30分間反応させた。Reference Example 5 Production of etherified derivative of 2,4-diamino-6- (1H, 1H-tridecafluoroheptyl) -s-triazine: 2,4-diamino-6- (1H, 1H-tridecafluoro) (Heptyl) -s-triazine (22.2 g, 0.05 mol) and 37% formalin (24.4 g) adjusted to pH 10.5 with a 10% aqueous potassium hydroxide solution
(0.30 mol of formaldehyde) was added. This mixture was reacted at a temperature of 70 to 75 ° C. for 30 minutes.
次に、この反応溶液を、50℃以下の温度にて減圧濃縮
を行った。これにメタノール200gを加えて溶液とし、濃
硝酸にてpH5.5に調整し、ゆるやかに還流させながら30
分間反応させた。この反応混合物を冷却後、30％苛性カ
リ水溶液にてpH8.0に調整後、減圧濾過にて沈殿物を除
去し、透明な液を得た。これを分析した結果、2,4−ジ
アミノ−６−（1H,1H−トリデカフルオルヘプチル）−
ｓ−トリアジン１モルに対し全ホルムアルデヒド結合量
3.72当量、メチルエーテル基3.13当量、メチロール基0.
59当量が結合した該化合物のエーテル化誘導体であっ
た。Next, this reaction solution was concentrated under reduced pressure at a temperature of 50 ° C. or lower. To this was added 200 g of methanol to form a solution, which was adjusted to pH 5.5 with concentrated nitric acid.
Allowed to react for minutes. After cooling the reaction mixture, the pH was adjusted to 8.0 with a 30% aqueous potassium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid. As a result of analyzing this, 2,4-diamino-6- (1H, 1H-tridecafluoroheptyl)-
Total amount of formaldehyde bound to 1 mole of s-triazine
3.72 equivalent, methyl ether group 3.13 equivalent, methylol group 0.
59 equivalents were linked etherified derivatives of the compound.
参考例６ 2,4−ジアミノ−６−（1H,1H,2H,2H−トリデカフルオ
ルオクチル）−ｓ−トリアジンのエーテル化誘導体の製
造： 2,4−ジアミノ−６−（1H,1H,2H,2H−トリデカフルオ
ルオクチル）−ｓ−トリアジン22.9g（0.05モル）にメ
チルヘミホルマール18.6g（0.30モル）とメタノール300
gを加え、30％苛性ソーダ水溶液にてpH11.0に調整し、
ゆるやかに還流させながら30分間反応させた。Reference Example 6 Production of an etherified derivative of 2,4-diamino-6- (1H, 1H, 2H, 2H-tridecafluorooctyl) -s-triazine: 2,4-diamino-6- (1H, 1H, To 22.9 g (0.05 mol) of 2H, 2H-tridecafluorooctyl) -s-triazine, 18.6 g (0.30 mol) of methylhemiformal and 300 ml of methanol
g, adjust to pH 11.0 with 30% aqueous sodium hydroxide solution,
The reaction was allowed to proceed for 30 minutes with gentle reflux.
次に、この反応溶液を、濃硝酸にてpH5.5に調整し、
ゆるやかに還流させながら１時間反応させた。この反応
混合物を冷却後、30％苛性ソーダ水溶液にてpH7.5に調
整後、減圧濾過にて沈殿物を除去し、透明な液を得た。
これを分析した結果、2,4−ジアミノ−６−（1H,1H,2H,
2H−トリデカフルオルオクチル）−ｓ−トリアジン１モ
ルに対し全ホルムアルデヒド結合量3.68当量、メチルエ
ーテル基3.27当量、メチロール基0.41当量が結合した該
化合物のエーテル化誘導体であった。Next, the reaction solution was adjusted to pH 5.5 with concentrated nitric acid,
The reaction was allowed to proceed for 1 hour with gentle reflux. After cooling the reaction mixture, the pH was adjusted to 7.5 with a 30% aqueous sodium hydroxide solution, and the precipitate was removed by filtration under reduced pressure to obtain a transparent liquid.
As a result of analyzing this, 2,4-diamino-6- (1H, 1H, 2H,
It was an etherified derivative of the compound in which 3.68 equivalents of the total formaldehyde bond, 3.27 equivalents of the methyl ether group, and 0.41 equivalents of the methylol group were bonded to 1 mol of (2H-tridecafluorooctyl) -s-triazine.
参考例７ ２−ペルフルオルオクチルエチルメタクリレートを構
成単位として含有する重合体の製造： 酢酸ブチル40g及びトルエン40gの混合溶媒を加熱還流
させ、２−ペルフルオルオクチルエチルメタクリレート
25g、スチレン20g、ｎ−ブチルメタクリレート39g、２
−ヒドロキシエチルメタクリレート15g、アクリル酸1g
及び重合開始剤2,2′−アゾビスイソブチロニトリル2g
からなる混合液を３時間で滴下し、更に２時間加熱し
て、不揮発分55％、重合平均分子量14000の含フッ素重
合体溶液を得た。Reference Example 7 Production of a polymer containing 2-perfluorooctylethyl methacrylate as a constituent unit: A mixed solvent of 40 g of butyl acetate and 40 g of toluene was heated to reflux, and 2-perfluorooctylethyl methacrylate was heated.
25 g, styrene 20 g, n-butyl methacrylate 39 g, 2
-Hydroxyethyl methacrylate 15 g, acrylic acid 1 g
And polymerization initiator 2,2'-azobisisobutyronitrile 2 g
Was added dropwise over 3 hours, and the mixture was further heated for 2 hours to obtain a fluoropolymer solution having a nonvolatile content of 55% and a polymerization average molecular weight of 14,000.
参考例８ アクリル共重合体の製造： 参考例７における２−ペルフルオルオクチルエチルメ
タクリレート25gの代わりに、２−エチルヘキシルメタ
クリレート25gにする以外は、参考例７と同様の手順で
反応を行い、不揮発分55％、重合平均分子量14000のア
クリル共重合体溶液を得た。Reference Example 8 Production of Acrylic Copolymer: A reaction was carried out in the same manner as in Reference Example 7, except that 25 g of 2-ethylhexyl methacrylate was used instead of 25 g of 2-perfluorooctylethyl methacrylate in Reference Example 7. An acrylic copolymer solution having a polymerization average molecular weight of 14000 was obtained at a rate of 55%.
実施例１ アクリル樹脂及びエーテル化含フッ素グアナミン誘導
体からなる樹脂組成物の硬化性及び撥水撥油性試験： 参考例１の方法で得られた2,4−ジアミノ−６−（2,
2,3,3,3−ペンタフルオルプロピル）−ｓ−トリアジン
のエーテル化含フッ素グアナミン誘導体5g（固形分）の
50重量％溶液〔ｎ−ブタノール−メチルイソブチルケト
ン混合溶媒（重量比50/50）〕を、アクリル樹脂「アル
マテックスD104」〔三井東圧化学（株）製、不揮発分50
重量％〕30gに加え、ミキサーにてよく攪拌して樹脂組
成物を調整した。次に、この樹脂組成物を亜鉛メッキ鋼
板に塗布後、160℃−20分の条件で加熱硬化させた。Example 1 Curability and water / oil repellency test of resin composition comprising acrylic resin and etherified fluorine-containing guanamine derivative: 2,4-diamino-6- (2,
Etherification of 2,3,3,3-pentafluoropropyl) -s-triazine 5 g (solid content) of a fluorinated guanamine derivative
A 50% by weight solution [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50/50)] was mixed with an acrylic resin “Almatex D104” (manufactured by Mitsui Toatsu Chemicals, Inc., having a nonvolatile content of 50%).
% By weight] and stirred well with a mixer to prepare a resin composition. Next, after applying this resin composition to a galvanized steel sheet, it was cured by heating at 160 ° C. for 20 minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、硬化性及
び撥水撥油性の試験を行った。Using the heat-treated coated steel plate coating film, a test of curability and water / oil repellency was conducted.
尚、比較例として、上記のエーテル化含フッ素グアナ
ミン誘導体50％溶液の代わりに、アミノ樹脂「ユーバン
20SE−60」〔三井東圧化学（株）製、不揮発分60重量
％〕6.3gを用い、同条件にて硬化を行い、該塗膜の試験
を行った。As a comparative example, instead of the above-mentioned 50% solution of the etherified fluorine-containing guanamine derivative, the amino resin “Uban
Using 6.3 g of “20SE-60” [manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 60% by weight], curing was performed under the same conditions, and the coating film was tested.
実施例および比較例において、該塗膜の硬化性試験
は、キシロールを含浸させた布で塗膜表面を50回払拭し
た後、該塗膜の状態を目視観察し、下記の判定を行っ
た。 In Examples and Comparative Examples, in the curability test of the coating film, the surface of the coating film was wiped 50 times with a cloth impregnated with xylol, and then the state of the coating film was visually observed, and the following judgment was made.
◎：塗膜の剥れ殆どなし △：塗膜が少し剥れた ×：塗膜が多く剥れた 又、該塗膜の撥水撥油性試験は、該塗膜の表面張力
（dyne/cm）によって表わした。表面張力の値が小さい
ほど、大きな撥水性または撥油性を示している。：: Almost no peeling of the coating film △: A little peeling of the coating film ×: A large amount of the coating film was peeled off Further, the water / oil repellency test of the coating film was conducted by examining the surface tension (dyne / cm) of the coating film. ). The smaller the value of the surface tension, the greater the water repellency or oil repellency.
実施例２ アクリル樹脂及びエーテル化含フッ素グアナミン誘導
体からなる樹脂組成物の硬化性及び撥水撥油性試験： 参考例２の方法で得られた、2,4−ジアミノ−６−
〔６−（ペルフルオルイソプロポキシ）−1H,1H,2H,2H
−オクタフルオルヘキシル〕−ｓ−トリアジンのエーテ
ル化含フッ素グアナミン誘導体5g（固形分）の50重量％
溶液〔ｎ−ブタノール−メチルイソブチルケトン混合溶
媒（重量比50/50）〕を、アクリル樹脂「アルマテック
ス785−５」〔三井東圧化学（株）製、不揮発分50重量
％〕30gに加え、ミキサーにてよく攪拌して樹脂組成物
を調整した。次に、この樹脂組成物を亜鉛メッキ鋼板に
塗布後、160℃−20分の条件で加熱硬化させた。Example 2 Curability and water / oil repellency test of resin composition comprising acrylic resin and etherified fluorine-containing guanamine derivative: 2,4-diamino-6 obtained by the method of Reference Example 2.
[6- (Perfluoroisopropoxy) -1H, 1H, 2H, 2H
-Octafluorohexyl] -etherified s-triazine 50% by weight of 5 g (solid content) of a fluorine-containing guanamine derivative
The solution [n-butanol-methyl isobutyl ketone mixed solvent (50/50 by weight)] was added to 30 g of an acrylic resin “Almatex 785-5” (manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 50% by weight), The resin composition was prepared by sufficiently stirring with a mixer. Next, after applying this resin composition to a galvanized steel sheet, it was cured by heating at 160 ° C. for 20 minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、硬化性及
び撥水撥油性の試験を行った。（試験方法は実施例１と
同じである） 尚、比較例として、上記のエーテル化含フッ素グアナ
ミン誘導体50％溶液の代わりに、アミノ樹脂「ユーバン
20SE−60」〔三井東圧化学（株）製、不揮発分60重量
％〕6.3gを用い、同条件にて硬化を行い、該塗膜の試験
を行った。Using the heat-treated coated steel plate coating film, a test of curability and water / oil repellency was conducted. (The test method is the same as in Example 1.) As a comparative example, the amino resin “Uban” was used instead of the 50% solution of the above-mentioned etherified fluorine-containing guanamine derivative.
Using 6.3 g of “20SE-60” [manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 60% by weight], curing was performed under the same conditions, and the coating film was tested.
実施例３ ポリエステル樹脂及びエーテル化含フッ素グアナミン
誘導体からなる樹脂組成物の硬化性及び撥水撥油性試
験： 参考例３の方法で得られた2,4−ジアミノ−６−（1H,
1H,2H,2H−ヘプタデカフルオルデシル）−ｓ−トリアジ
ンのエーテル化含フッ素グアナミン誘導体5g（固形分）
の50上重量％溶液〔ｎ−ブタノール−メチルセロソルブ
混合溶媒（重量比50/50）〕を、ポリエステル樹脂「ア
ルマテックスp646」〔三井東圧化学（株）製、不揮発分
60重量％〕25gに加え、ミキサーにてよく攪拌して樹脂
組成物を調整した。次に、この樹脂組成物を亜鉛メッキ
鋼板に塗布後、160℃−20分の条件で加熱硬化させた。 Example 3 Curability and water / oil repellency test of resin composition comprising polyester resin and etherified fluorine-containing guanamine derivative: 2,4-diamino-6- (1H,
1H, 2H, 2H-heptadecafluorodecyl) -s-triazine etherified fluorine-containing guanamine derivative 5g (solid content)
Of a 50% by weight solution of n-butanol-methyl cellosolve (weight ratio: 50/50) with a polyester resin “Almatex p646” [manufactured by Mitsui Toatsu Chemicals, Inc.
60% by weight] and stirred well with a mixer to prepare a resin composition. Next, after applying this resin composition to a galvanized steel sheet, it was cured by heating at 160 ° C. for 20 minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、硬化性及
び撥水撥油性の試験を行った。（試験方法は実施例１と
同じである） 尚、比較例として、上記のエーテル化含フッ素グアナ
ミン誘導体50％溶液の代わりに、アミノ樹脂「ユーバン
20SE−60」〔三井東圧化学（株）製、不揮発分60重量
％〕6.3gを用い、同条件にて硬化を行い、該塗膜の試験
を行った。Using the heat-treated coated steel plate coating film, a test of curability and water / oil repellency was conducted. (The test method is the same as in Example 1.) As a comparative example, the amino resin “Uban” was used instead of the 50% solution of the above-mentioned etherified fluorine-containing guanamine derivative.
Using 6.3 g of “20SE-60” [manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 60% by weight], curing was performed under the same conditions, and the coating film was tested.
実施例４ 含フッ素樹脂及びエーテル化含フッ素グアナミン誘導
体からなる樹脂組成物の硬化性及び撥水撥油性試験： 参考例３の方法で得られた2,4−ジアミノ−６−（1H,
1H,2H,2H−ヘプタデカフルオルデシル）−ｓ−トリアジ
ンのエーテル化含フッ素グアナミン誘導体5.7g（固形
分）の50重量％溶液〔ｎ−ブタノール−メチルイソブチ
ルケトン混合溶媒（重量比50/50）〕を、含フツ素樹脂
「ルミフロンLF400」〔旭硝子（株）製、不揮発分50重
量％〕30gに加え、ミキサーにてよく攪拌して樹脂組成
物を調整した。次に、この樹脂組成物を亜鉛メッキ鋼板
に塗布後、160℃−20分の条件で加熱硬化させた。 Example 4 Curability and water / oil repellency test of a resin composition comprising a fluorine-containing resin and an etherified fluorine-containing guanamine derivative: 2,4-diamino-6- (1H,
1H, 2H, 2H-heptadecafluorodecyl) -s-triazine etherified fluorinated guanamine derivative 5.7 g (solid content) 50% by weight solution [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50/50) )] Was added to 30 g of a fluorine-containing resin "Lumiflon LF400" (manufactured by Asahi Glass Co., Ltd., nonvolatile content 50% by weight), and the mixture was thoroughly stirred with a mixer to prepare a resin composition. Next, after applying this resin composition to a galvanized steel sheet, it was cured by heating at 160 ° C. for 20 minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、硬化性及
び撥水撥油性の試験を行った。（試験方法は実施例１と
同じである） 尚、比較例として、上記のエーテル化含フッ素グアナ
ミン誘導体50％溶液の代わりに、アミノ樹脂「ユーバン
20SE−60」〔三井東圧化学（株）製、不揮発分60重量
％〕4.9gを用い、同条件にて硬化を行い、該塗膜の試験
を行った。Using the heat-treated coated steel plate coating film, a test of curability and water / oil repellency was conducted. (The test method is the same as in Example 1.) As a comparative example, the amino resin “Uban” was used instead of the 50% solution of the above-mentioned etherified fluorine-containing guanamine derivative.
Using 4.9 g of “20SE-60” [manufactured by Mitsui Toatsu Chemicals, Inc., nonvolatile content 60% by weight], curing was performed under the same conditions, and the coating film was tested.
実施例５ アルキッド樹脂、エーテル化含フッ素グアナミン誘導
体及び他の硬化剤からなる樹脂組成物の硬化性及び撥水
撥油性試験： 参考例４の方法で得られた2,4−ジアミノ−６−（4,
4,5,5,6,6,7,7,7−ノナフルオルヘプチル）−ｓ−トリ
アジンのエーテル化含フッ素グアナミン誘導体18g（固
形分）の50重量％溶液（メタノール溶媒）を、アルキッ
ド樹脂「ユリックス210S」〔三井東圧化学（株）製、不
揮発分70重量％〕30gに加え、更に、アミノ樹脂「ユー
バン136」〔三井東圧化学（株）製、ブチル化尿素−メ
ラミン共縮合樹脂、不揮発分60重量％〕15g、ｐ−トル
エンスルホン酸50重量％溶液（イソプロパノール溶媒）
6gを加えて、ミキサーにてよく攪拌して樹脂組成物を調
整した。次に、この樹脂組成物を梨地鋼板に塗布後、25
℃−５時間の条件で硬化させた。 Example 5 Curability and water / oil repellency test of resin composition comprising alkyd resin, etherified fluorine-containing guanamine derivative and other curing agent: 2,4-diamino-6- (obtained by the method of Reference Example 4) Four,
4,5,5,6,6,7,7,7-Nonafluoroheptyl) -s-triazine etherified fluorine-containing guanamine derivative 18 g (solid content) of a 50% by weight solution (methanol solvent) was added to an alkyd resin. In addition to 30 g of "ULIX 210S" (manufactured by Mitsui Toatsu Chemicals, nonvolatile content 70% by weight), amino resin "Uban 136" [manufactured by Mitsui Toatsu Chemicals, butylated urea-melamine co-condensation resin 15%, p-toluenesulfonic acid 50% by weight solution (isopropanol solvent)
6 g was added, and the mixture was stirred well with a mixer to prepare a resin composition. Next, after applying this resin composition to the matte steel plate,
The composition was cured at a temperature of 5 ° C. for 5 hours.
かかる処理をした塗装鋼板の塗膜を用い、硬化性及び
撥水撥油性の試験を行った。（試験方法は実施例１と同
じである） 尚、比較例として、上記のエーテル化含フッ素グアナ
ミン誘導体50％溶液の代わりに、アミノ樹脂「ユーバン
136」15gを用い、同条件にて硬化を行い、該塗膜の試験
を行った。Using the coating film of the coated steel sheet treated as described above, tests of curability and water / oil repellency were performed. (The test method is the same as in Example 1.) As a comparative example, the amino resin “Uban” was used instead of the 50% solution of the above-mentioned etherified fluorine-containing guanamine derivative.
136 "(15 g) was cured under the same conditions, and the coating film was tested.
実施例１〜５に示した如く、本発明に係わる被覆用組
成物は、水酸基を有する各種の重合体を用いて容易に含
フッ素被覆層の形成を行うことができ被覆材料の製造、
組成の制約が極めて少なく、且つ該被覆層は非常に優れ
た撥水撥油性を有する為広汎に有用な被覆材料を提供す
ることができ、極めて有用な被覆用組成物であった。 As shown in Examples 1 to 5, the coating composition according to the present invention can easily form a fluorine-containing coating layer using various polymers having a hydroxyl group, and can produce a coating material.
The coating layer has very few restrictions on the composition, and the coating layer has extremely excellent water and oil repellency, so that it is possible to provide a widely useful coating material, and it is a very useful coating composition.
実施例６ エーテル化含フッ素グアナミン誘導体を成分として含
有する樹脂組成物から得られる被覆層における撥水撥油
性の保持性試験： 参考例５の方法で得られた2,4−ジアミノ−６−（1H,
1H−トリデカフルオルヘプチル）−ｓ−トリアジンのエ
ーテル化含フッ素グアナミン誘導体5g（固形分）の50重
量％溶液〔ｎ−ブタノール−メチルイソブチルケトン混
合溶媒（重量比50/50）〕を参考例８の方法で得られた
アクリル共重合体溶液（不揮発分55重量％）27.3gに加
え、ミキサーにてよく攪拌して樹脂組成物を調整した。
次に、この樹脂組成物を梨地鋼板に塗布後、160℃−20
分の条件で加熱硬化させた。Example 6 Retention test of water / oil repellency of a coating layer obtained from a resin composition containing an etherified fluorine-containing guanamine derivative as a component: 2,4-diamino-6- (obtained by the method of Reference Example 5) 1H,
Reference Example A 50% by weight solution of 5 g (solid content) of an etherified fluorine-containing guanamine derivative of 1H-tridecafluoroheptyl) -s-triazine [n-butanol-methyl isobutyl ketone mixed solvent (weight ratio 50/50)] The resin composition was added to 27.3 g of the acrylic copolymer solution (non-volatile content 55% by weight) obtained by the method of No. 8 and stirred well with a mixer to prepare a resin composition.
Next, after applying this resin composition to the matte steel plate,
The composition was cured by heating under the conditions of minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、硬化性試
験及びウエザ−Ｏ−メーター曝露試験（1000時間）前、
後の撥水撥油性試験を行った。（試験方法は実施例１と
同じである） 実施例７ エーテル化含フッ素グアナミン誘導体を成分として含
有する樹脂組成物から得られる被覆層における撥水撥油
性の保持性試験： 実施例６における2,4−ジアミノ−６−（1H,1H−トリ
デカフルオルヘプチル）−ｓ−トリアジンのエーテル化
含フッ素グアナミン誘導体5g（固形分）の代わりに、参
考例３の方法で得られた2,4−ジアミノ−６−（1H,1H,2
H,2H−ペプタデカフルオルデシル）−ｓ−トリアジンの
エーテル化含フッ素グアナミン誘導体5g（固形分）にす
る以外は、実施例６と同様の手順で樹脂調整及び塗膜作
成を行い、かかる加熱処理した塗装鋼板の塗膜を用いて
硬化性及び撥水撥油性の試験を行った。Using the coating film of the coated steel sheet subjected to the heat treatment, before the curing test and the weather O-meter exposure test (1000 hours),
A later water / oil repellency test was performed. (The test method is the same as that of Example 1.) Example 7 Retention test of water / oil repellency in a coating layer obtained from a resin composition containing an etherified fluorine-containing guanamine derivative as a component: Etherification of 4-diamino-6- (1H, 1H-tridecafluoroheptyl) -s-triazine Instead of 5 g (solid content) of a fluorinated guanamine derivative obtained in the method of Reference Example 3, 2,4- Diamino-6- (1H, 1H, 2
Resin preparation and coating film formation were carried out in the same manner as in Example 6, except that the etherified fluorine-containing guanamine derivative of (H, 2H-peptadecafluorodecyl) -s-triazine was changed to 5 g (solid content). A test of curability and water / oil repellency was performed using the coating film of the heat-treated coated steel sheet.
比較例６ 含フッ素メタクリレートを構成単位として有する含フ
ッ素重合体を成分とする樹脂組成物から得られる被覆層
における撥水撥油性の保持性試験： 参考例７の方法で得られた含フッ素重合体溶液（不揮
発分55重量％）27.3gに、アミノ樹脂「ユーバン20SE−6
0」〔三井東圧化学（株）製、不揮発分60重量％〕6.3g
を加え、ミキサーにてよく攪拌して樹脂組成物を調整し
た。次に、この樹脂組成物を梨地鋼板に塗布後、160℃
−20分の条件で加熱硬化させた。Comparative Example 6 Water / Oil Repellency Retention Test of Coating Layer Obtained from Resin Composition Containing Fluoropolymer Having Fluorine-Containing Methacrylate as Constituent Unit: Fluoropolymer Obtained by Method of Reference Example 7 To 27.3 g of the solution (non-volatile content 55% by weight), amino resin “Uban 20SE-6” was added.
0 "[manufactured by Mitsui Toatsu Chemicals, nonvolatile content 60% by weight] 6.3 g
Was added and the mixture was stirred well with a mixer to prepare a resin composition. Next, after applying this resin composition to the matte steel plate,
The composition was cured by heating under the condition of -20 minutes.
かかる加熱処理した塗装鋼板の塗膜を用い、実施例６
と同様にして硬化性及び撥水撥油性の試験を行った。Example 6 using such a heat-treated coated steel plate coating film
In the same manner as in the above, tests of curability and water / oil repellency were conducted.
比較例７ アクリル共重合体を成分とする樹脂組成物から得られ
る被覆層における撥水撥油性の保持性試験： 比較例６における参考例７の方法で得られた含フッ素
重合体溶液（不揮発分55重量％）27.3gの代わりに、参
考例８の方法で得られたアクリル共重合体溶液（不揮発
分55重量％）27.3gにする以外は、比較例６と同様の手
順で樹脂調整及び塗膜作成を行った。Comparative Example 7 Retention test of water / oil repellency of a coating layer obtained from a resin composition containing an acrylic copolymer as a component: The fluorine-containing polymer solution (non-volatile content) obtained by the method of Reference Example 7 in Comparative Example 6 Resin preparation and coating were performed in the same manner as in Comparative Example 6, except that 27.3 g of the acrylic copolymer solution (non-volatile content 55% by weight) obtained by the method of Reference Example 8 was used instead of 27.3 g of 55% by weight. A film was prepared.
かかる加熱処理した塗装鋼板の塗膜を用い、実施例６
と同様にして硬化性及び撥水撥油性の試験を行った。Example 6 using such a heat-treated coated steel plate coating film
In the same manner as in the above, tests of curability and water / oil repellency were conducted.
実施例６、同７、比較例６、同７における試験結果を
第１表に示した。Table 1 shows the test results in Examples 6, 7 and Comparative Examples 6, 7.
第１表に示した如く、本発明に係わる被覆用組成物か
ら得られた被覆層は、公知の被覆組成物から得られる被
覆層に比し、極めて優れた撥水撥油性を有し、且つ所期
機能を長期にわたり保持することができ、該被覆用組成
物は広汎に有用な被覆材料を提供することができるもの
であった。As shown in Table 1, the coating layer obtained from the coating composition according to the present invention has extremely excellent water and oil repellency as compared with the coating layer obtained from the known coating composition, and The desired function could be maintained for a long time, and the coating composition could provide a widely useful coating material.
実施例８ エーテル化含フッ素グアナミン誘導体を成分として含
有する樹脂組成物から得られる被覆層における着氷性試
験： 実施例７にて得られた加熱処理した塗装鋼板の塗膜を
用い、後記の試験方法により−10℃に２時間凍結させた
時の着氷剪断破壊強度（kg/cm2）を測定した。 Example 8 Icing Test on Coating Layer Obtained from Resin Composition Containing Etherified Fluorinated Guanamine Derivative as a Component: The test described below was carried out using the coated film of the heat-treated coated steel sheet obtained in Example 7. The icing shear breaking strength (kg / cm 2 ) when frozen at −10 ° C. for 2 hours was measured by the method.
尚、比較例として、比較例７における加熱処理した塗
装鋼板の塗膜を用い、上記と同様にして試験を行った。As a comparative example, a test was performed in the same manner as described above, using the coating film of the coated steel sheet subjected to the heat treatment in Comparative Example 7.
上記に示した如く、本発明に係わる被覆用組成物から
得られた被覆層は、公知の被覆組成物から得られる被覆
層に比し着氷剪断破壊強度が著しく小さく、着氷防止性
が極めて優れたものであった。 As described above, the coating layer obtained from the coating composition according to the present invention has an extremely small icing shear breaking strength and extremely low icing prevention properties as compared with the coating layer obtained from the known coating composition. It was excellent.
第１図に示す如く、塗装鋼板の塗膜（１）上にステン
レス製リング（内径25mm）（２）を置き、これを冷凍恒
温機（−10℃）にて１時間冷却する。次に、５℃に保た
れた脱イオン水2gをリング（２）中に注ぎ試験塗膜に着
氷させ、直ちに上記恒温機（−10℃）内にて２時間冷却
する。この冷却されたリング（２）に動力により駆動す
る金属棒（３）により衝撃を与えて、氷（４）を剥離さ
せる剪断破壊強度（kg/cm2）を測定した。該強度が小さ
いほど、小さな着氷性を示す。As shown in FIG. 1, a stainless steel ring (inner diameter: 25 mm) (2) is placed on the coating film (1) of the coated steel sheet, and this is cooled for 1 hour in a freezer and thermostat (-10 ° C.). Next, 2 g of deionized water kept at 5 ° C. is poured into the ring (2) to allow the test coating film to be iced, and immediately cooled in the above thermostat (−10 ° C.) for 2 hours. An impact was applied to the cooled ring (2) with a metal rod (3) driven by power, and the shear breaking strength (kg / cm 2 ) at which the ice (4) was peeled was measured. The smaller the strength, the smaller the icing properties.
実施例９ 2,4−ジアミノ−６−（1H,1H,2H,2H−トリデカフルオ
ルオクチル）−ｓ−トリアジンのエーテル化含フッ素グ
アナミン誘導体における含フッ素置換基の安定性試験： 参考例６の方法で得られた2,4−ジアミノ−６−（1H,
1H,2H,2H−トリデカフルオルオクチル）−ｓ−トリアジ
ンのエーテル化含フッ素グアナミン誘導体5g（固形分）
の50重量％溶液（エタノール溶媒）を、アクリル樹脂
「アルマテックス781−26」〔三井東圧化学（株）製、
不揮発分50重量％〕40gに加え、ミキサーにてよく攪拌
して樹脂組成物を調整した。次に、この樹脂組成物を亜
鉛メッキ鋼板に塗布後、150℃−30分の条件で加熱硬化
させた。Example 9 Stability test of fluorine-containing substituent in fluorine-containing guanamine derivative etherified with 2,4-diamino-6- (1H, 1H, 2H, 2H-tridecafluorooctyl) -s-triazine: Reference Example 6 2,4-diamino-6- (1H,
1H, 2H, 2H-tridecafluorooctyl) -s-triazine etherified fluorine-containing guanamine derivative 5g (solid content)
Of a 50% by weight solution (ethanol solvent) of an acrylic resin “Almatex 781-26” [manufactured by Mitsui Toatsu Chemicals, Inc.
Nonvolatile content 50% by weight] and stirred well with a mixer to prepare a resin composition. Next, after applying this resin composition to a galvanized steel sheet, it was heated and cured at 150 ° C. for 30 minutes.
この塗装鋼板を用い、ウエザ−Ｏ−メーターにて600
時間の曝露試験を行った。該試験鋼板の塗膜を剥離し元
素分析を行った結果、Ｆ含有量8.1％（試験前測定値Ｆ
含有量8.3％）であった。Using this painted steel plate, 600 with a weather O-meter
A time exposure test was performed. The coating on the test steel sheet was peeled off and subjected to elemental analysis. As a result, the F content was 8.1% (measured value F before the test).
Content 8.3%).
上記に示した如く、本発明に係わる被覆用組成物から
得られた被覆層の含フッ素置換基は、紫外線、水等で脱
離し難く、極めて優れた安定性、耐久性を有するもので
あり、該被覆用組成物は所期機能を長期にわたり維持す
ることができる極めて優れた被覆材料を提供することが
できるものであった。As shown above, the fluorine-containing substituents of the coating layer obtained from the coating composition according to the present invention are hardly detached by ultraviolet rays, water, etc., and have extremely excellent stability and durability. The coating composition was able to provide an extremely excellent coating material capable of maintaining the desired function for a long period of time.
本発明に係わる被覆用組成物は、エーテル化含フッ素
グアナミン誘導体を必須構成成分として含有しているた
め、水酸基を有する各種の重合体を用いて容易に含フッ
素被覆層を形成することができ被覆材料の製造、組成の
制約が極めて少なく、得られた該被覆層は撥水撥油性、
着氷防止性等の表面特性に著しく優れ、且つ該含フッ素
置換基の安定性、耐久性に優れ、公知の被覆組成物から
は得難い被覆材料を提供することができる、広汎な産業
分野に適用され、産業上極めて優れた発明である。Since the coating composition according to the present invention contains an etherified fluorine-containing guanamine derivative as an essential component, a fluorine-containing coating layer can be easily formed using various polymers having a hydroxyl group. The production of the material, there are very few restrictions on the composition, the obtained coating layer is water- and oil-repellent,
Applicable to a wide range of industrial fields that can provide coating materials that are remarkably excellent in surface properties such as anti-icing properties, and have excellent stability and durability of the fluorine-containing substituents, and can provide coating materials that are difficult to obtain from known coating compositions. This is an industrially excellent invention.
第１図は塗装鋼板上の着氷剪断破壊強度試験方法を図示
したものである。 （１）：塗膜 （２）：ステンレス製リング （３）：金属棒 （４）：氷FIG. 1 illustrates a test method of icing shear fracture strength on a coated steel plate. (1): coating film (2): stainless steel ring (3): metal bar (4): ice
Claims (1)
成成分とする被覆用組成物において、前記硬化剤が、一
般式 ［式中、R1はCF3、C2F5、（CF3）2CF、C4F9、（CF3）2C
F−Ｏ基の中から選ばれる１種、R2はＦ原子および／又
はCF3基、R3はメチレン、エチレン、トリメチレン、プ
ロピレン基の中から選ばれる１種、ｎは１〜７の中から
選ばれる整数を示す］で表わされる含フッ素グアナミン
化合物の中から選ばれる少なくとも１種とホルムアルデ
ヒド類の中から選ばれる少なくとも１種とを反応させて
得られる少なくとも１個のメチロール基を有するメチロ
ール化含フッ素グアナミン誘導体と、炭素数１〜20個を
有する脂肪族アルコールおよび脂環族アルコールの中か
ら選ばれる１種とを反応させることにより得られる少な
くとも１個のR4OCH2基（R4は前記アルコールより水酸基
を除いた残基である）を有するエーテル化含フッ素グア
ナミン誘導体を成分として含有することを特徴とする被
覆用組成物。1. A coating composition comprising a polymer having a hydroxyl group and a curing agent as essential components, wherein the curing agent has a general formula [Wherein R 1 is CF 3 , C 2 F 5 , (CF 3 ) 2 CF, C 4 F 9 , (CF 3 ) 2 C
One selected from FO groups, R 2 is an F atom and / or a CF 3 group, R 3 is one selected from methylene, ethylene, trimethylene, and propylene groups; Which is an integer selected from the group consisting of a fluorinated guanamine compound and at least one methylol group obtained by reacting at least one selected from formaldehydes. At least one R 4 OCH 2 group (R 4 is obtained by reacting a fluorine-containing guanamine derivative with one selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms; A coating composition comprising an etherified fluorine-containing guanamine derivative having a residue obtained by removing a hydroxyl group from the alcohol).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1128633A JP2764055B2 (en) | 1989-05-24 | 1989-05-24 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1128633A JP2764055B2 (en) | 1989-05-24 | 1989-05-24 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02308874A JPH02308874A (en) | 1990-12-21 |
| JP2764055B2 true JP2764055B2 (en) | 1998-06-11 |
Family
ID=14989641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1128633A Expired - Lifetime JP2764055B2 (en) | 1989-05-24 | 1989-05-24 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764055B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2764054B2 (en) * | 1989-05-24 | 1998-06-11 | 三井化学株式会社 | Composition for coating formation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2764054B2 (en) * | 1989-05-24 | 1998-06-11 | 三井化学株式会社 | Composition for coating formation |
-
1989
- 1989-05-24 JP JP1128633A patent/JP2764055B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02308874A (en) | 1990-12-21 |
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