JPH02102278A - Coating composition for metal surface - Google Patents
Coating composition for metal surfaceInfo
- Publication number
- JPH02102278A JPH02102278A JP25522888A JP25522888A JPH02102278A JP H02102278 A JPH02102278 A JP H02102278A JP 25522888 A JP25522888 A JP 25522888A JP 25522888 A JP25522888 A JP 25522888A JP H02102278 A JPH02102278 A JP H02102278A
- Authority
- JP
- Japan
- Prior art keywords
- group
- monomers
- hydrophilic
- structural units
- weight
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 239000008199 coating composition Substances 0.000 title claims description 9
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 28
- 229920001400 block copolymer Polymers 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 18
- 239000013522 chelant Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- -1 N-(butoxy)methylol, amino Chemical group 0.000 abstract description 40
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001480 hydrophilic copolymer Polymers 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229940094506 lauryl betaine Drugs 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- WDRZVZVXHZNSFG-UHFFFAOYSA-N 1-ethenylpyridin-1-ium Chemical compound C=C[N+]1=CC=CC=C1 WDRZVZVXHZNSFG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MDEDENRMBJWPAU-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;formic acid;octadecanoic acid Chemical compound OC=O.OCCN(CCO)CCO.CCCCCCCCCCCCCCCCCC(O)=O MDEDENRMBJWPAU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QDFKBAKKBVXQFD-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CC(=C)C(O)=O QDFKBAKKBVXQFD-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UMSFRTCUQPFZFA-UHFFFAOYSA-N 3-(3-sulfopropoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCCCS(O)(=O)=O UMSFRTCUQPFZFA-UHFFFAOYSA-N 0.000 description 1
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- SMMIDVLUFMPWFN-UHFFFAOYSA-N 4-nitro-n-[(4-phenyldiazenylphenyl)diazenyl]aniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NN=NC1=CC=C(N=NC=2C=CC=CC=2)C=C1 SMMIDVLUFMPWFN-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- YYCVEQAJBXLGEQ-UHFFFAOYSA-N acetic acid;n,n-diethylethanamine;octadecanamide Chemical compound CC(O)=O.CCN(CC)CC.CCCCCCCCCCCCCCCCCC(N)=O YYCVEQAJBXLGEQ-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種金属材料表面を保護して、永続的に親水
性及び耐蝕性を保持し、かつ塗膜強度の優れた金属表面
用被覆組成物に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention provides a coating for metal surfaces that protects the surfaces of various metal materials, permanently maintains hydrophilicity and corrosion resistance, and has excellent coating strength. The present invention relates to a composition.
［従来の技術］
従来、金属表面を親水化する方法として疎水性アクリル
樹脂塗料等に界面活性剤、シリカ、酸化チタン等を添加
、分散させて被覆する方法が知られている（特開昭５５
−９９９８７号、特開昭５９−１７０１７０号、特開昭
６１−３４３８６５号の各公報）。また、親水性の樹脂
を被覆する方法や親水性単量体と疎水性単量体によるラ
ンダム共重合体を使用する方法も知られている。[Prior Art] Conventionally, as a method of making a metal surface hydrophilic, a method of adding and dispersing a surfactant, silica, titanium oxide, etc. to a hydrophobic acrylic resin paint, etc., and coating the metal surface is known (Japanese Unexamined Patent Application Publication No. 1983-1992).
-99987, JP-A-59-170170, and JP-A-61-343865). Also known are a method of coating with a hydrophilic resin and a method of using a random copolymer of a hydrophilic monomer and a hydrophobic monomer.
［発明が解決しようとする課題］
ところが、上記従来の第１の方法は初期においては添加
剤の効果で優れた親水性能を持つが、添加剤が完全に脱
落した後は疎水性樹脂の表面特性が発現し、親水性が失
われる。また、親水性の樹脂を被覆する方法では、金属
を腐食から保護することができない。さらに、親水性単
量体と疎水性単量体によるランダム共重合体においても
、親水性能と耐蝕性能を両立することは困難である。[Problems to be Solved by the Invention] However, the first conventional method described above has excellent hydrophilic properties due to the effect of the additive in the initial stage, but after the additive has completely fallen off, the surface properties of the hydrophobic resin deteriorate. is expressed and hydrophilicity is lost. Furthermore, the method of coating the metal with a hydrophilic resin cannot protect the metal from corrosion. Furthermore, even in random copolymers of hydrophilic monomers and hydrophobic monomers, it is difficult to achieve both hydrophilicity and corrosion resistance.
本発明の目的は、充分な持続性のある親水性を有すると
ともに、耐蝕性、金属表面に対する密着性、摩耗性に優
れた金属表面用被覆組成物を提供することにある。An object of the present invention is to provide a coating composition for metal surfaces that has sufficient long-lasting hydrophilicity and is excellent in corrosion resistance, adhesion to metal surfaces, and abrasion resistance.
［課題を解決するための手段］
本発明者らは、持続性のある親水性を有し、かつ高分子
材料表面に対する密着性もある組成物として、既に親水
性重合体部分と疎水性重合体部分から成るブロック共重
合体（特開昭５９−２０２２６１号公報）を提案してい
る。[Means for Solving the Problems] The present inventors have already developed a composition that has long-lasting hydrophilicity and also has adhesion to the surface of a polymeric material by combining a hydrophilic polymer portion and a hydrophobic polymer. proposed a block copolymer (Japanese Unexamined Patent Publication No. 59-202261).
この組成物を金属表面に被覆したところ、金属に対して
も優れた密着性を有し、耐蝕性もあることが確認された
。その後さらに鋭意検討を行った結果、特定の架橋性官
能基を導入した親水性共重合体部分と特定の架橋性官能
基を導入した疎水性共重合体部分からなるブロック又は
グラフト共重合体に界面活性剤を併用し、かつ金属キレ
ート型架橋剤を添加することにより、その組成物から金
属材料表面に形成される被膜が従来の技術では予想され
なかった程飛躍的に持続性の高い親水性を有し、かつ金
属材料表面に対する密着性、摩耗性にも優れ、前記従来
の問題点が大幅に改善されることを見出し本発明を完成
するに至った。When this composition was coated on a metal surface, it was confirmed that it had excellent adhesion to metal and also had corrosion resistance. After that, as a result of further intensive studies, we found that a block or graft copolymer consisting of a hydrophilic copolymer part into which a specific crosslinkable functional group was introduced and a hydrophobic copolymer part into which a specific crosslinkable functional group was introduced was created. By using an activator in combination and adding a metal chelate type crosslinking agent, the coating formed on the surface of the metal material from the composition has a dramatically more sustainable hydrophilicity than expected with conventional technology. The present inventors have found that the present invention is excellent in adhesion to the surface of metal materials and wear resistance, and that the above-mentioned conventional problems can be significantly improved.
即ち本発明の金属表面用被覆組成物は、下記の自己架橋
性を有するブロック又はグラフト共重合体、界面活性剤
及び金属キレート型架橋剤を含有するという手段を採用
している。That is, the coating composition for metal surfaces of the present invention employs a means of containing a block or graft copolymer having self-crosslinking properties, a surfactant, and a metal chelate type crosslinking agent as described below.
ブロック又はグラフト共重合体：グリシジル基、Ｎ−メ
チロール基、Ｎ−ブトキシメチロール基、アミン基、カ
ルボン酸基、スルホン酸基のいずれかの官能基を有する
ラジカル重合性の単量体からなる群（以下Ａ群という）
から選ばれる単量体の１種又は２種以上に基づく構造単
位５〜３５重量％及び上記Ａ群の単量体と共重合性を有
する親水性単量体の１種又は２種以上に基づく構造単位
６５〜９５重量％よりなる親水性重合体部分と、上記Ａ
群の単量体から選ばれる単量体の１種又は２種以上に基
づく構造単位５〜３０重量％及び上記Ａ群の単量体と共
重合性を有する疎水性単量体の１種又は２種以上に基づ
（構造単位７０〜９５重量％よりなる疎水性重合体部分
からなるブロック又はグラフト共重合体。Block or graft copolymer: a group consisting of radically polymerizable monomers having a functional group of glycidyl group, N-methylol group, N-butoxymethylol group, amine group, carboxylic acid group, or sulfonic acid group ( (hereinafter referred to as group A)
5 to 35% by weight of structural units based on one or more monomers selected from and one or more hydrophilic monomers copolymerizable with the monomers of Group A above. A hydrophilic polymer portion consisting of 65 to 95% by weight of structural units, and the above A
5 to 30% by weight of structural units based on one or more monomers selected from the monomers of Group A and one or more hydrophobic monomers copolymerizable with the monomers of Group A above. A block or graft copolymer consisting of a hydrophobic polymer portion based on two or more types (70 to 95% by weight of structural units).
金属キレート型架橋剤ニ一般式ＡｌＸｎＹ３ｎ〔式中Ｘ
は炭素原子数１〜５のアルコキシ基、ＹはＲＩ ＣＯＣ
Ｈ２Ｃ０Ｒ２又はＲ３ＣＯＣＨ２Ｃ０ＯＲ’を示し、Ｒ
１、Ｒ２、Ｒ３、Ｒ４は炭素原子数１〜１０のアルキル
基であり、ｎはＯｌｌ又は２である〕又は一般式ＴｉＸ
ｎＹ４−ｎ （式中Ｘは炭素原子数１〜５のアルコキシ
基又は水酸基、ＹはＱＣ（ＣＨ３）ＣＨＣＯＣＨ３、Ｑ
Ｃ２Ｈ４Ｎ （Ｃ２Ｈ４ＯＨ） 、ＯＣＨ（ＣＨ３）Ｃ
００Ｉ］であり、ｎは０又は１〜４までの整数である〕
で表される化合物。The metal chelate type crosslinking agent has the general formula AlXnY3n [in the formula
is an alkoxy group having 1 to 5 carbon atoms, Y is RI COC
H2C0R2 or R3COCH2C0OR', R
1, R2, R3, R4 are alkyl groups having 1 to 10 carbon atoms, and n is Oll or 2] or the general formula TiX
nY4-n (wherein X is an alkoxy group or hydroxyl group having 1 to 5 carbon atoms, Y is QC(CH3)CHCOCH3, Q
C2H4N (C2H4OH), OCH(CH3)C
00I], and n is 0 or an integer from 1 to 4]
A compound represented by
［手段の詳細な説明］
本発明におけるブロック又はグラフト共重合体の一方の
分子鎖を構成する親水性重合体部分は、親水特性と耐蝕
特性を良好に維持するために、前記Ａ群から選ばれる単
量体の１種又は２種以上に基づく構造単位５〜３５重量
％及び上記Ａ群の単量体と共重合性を有する親水性単量
体の１種又は２種以上に基づく構造単位６５〜９５重量
％よりなることが必要である。Ａ群から選ばれる単量体
に基づく構造単位が５重量％未満又は親水性単量体に基
づく構造単位が９５重量％を超えると耐蝕性が低下し、
Ａ群から選ばれる単量体に基づく構造単位が３５重量％
を超えるか又は親水性単量体に基づく構造単位が６５重
量％未満では架橋性が強すぎて親水性と密着性が低下す
る。[Detailed Description of Means] The hydrophilic polymer moiety constituting one molecular chain of the block or graft copolymer in the present invention is selected from the above group A in order to maintain good hydrophilic properties and corrosion resistance properties. 5 to 35% by weight of structural units based on one or more monomers and structural units 65 based on one or more hydrophilic monomers copolymerizable with the monomers of Group A above. 95% by weight. If the structural unit based on the monomer selected from Group A is less than 5% by weight or the structural unit based on the hydrophilic monomer exceeds 95% by weight, the corrosion resistance will decrease,
35% by weight of structural units based on monomers selected from Group A
or less than 65% by weight of structural units based on hydrophilic monomers, the crosslinkability is too strong and hydrophilicity and adhesion are reduced.
上記Ａ群の架橋性官能基を有する単量体としては、例え
ば（メタ）アクリル酸グリシジル〔以下アクリルとメタ
クリルを（メタ）アクリルと総称する。〕、〕Ｎ−メチ
ロールメタ）アクリルアミド、Ｎ−ブトキシメチロール
（メタ）アクリルアミド、Ｎ、Ｎ−ジメチルアミノエチ
ル（メタ）アクリレート、（メタ）アクリル酸、２−ア
クリルアミド−２−メチルプロパンスルホン酸、イタコ
ン酸等があげられる。Examples of the monomer having a crosslinkable functional group in Group A include glycidyl (meth)acrylate [hereinafter, acrylic and methacrylic are collectively referred to as (meth)acrylic. ],]N-methylolmeth)acrylamide, N-butoxymethylol(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylate, (meth)acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, itaconic acid etc. can be mentioned.
また、上記Ａ群の単量体と、共重合性を有する親水性単
量体は、Ａ群から選ばれた架橋性官能基の架橋反応に全
く関係しないか、又は反応性が格段に落ちる単量体の中
から選ぶ必要がある。これらの単量体として例えば、（
メタ）アクリル酸、イタコン酸、クロトン酸等のラジカ
ル重合性不飽和カルボン酸、及びそれら不飽和カルボン
酸アルカリ金属塩、アンモニウム塩、有機アミン塩、ス
チレンスルホン酸やスルホプロピル（メタ）アクリル酸
エステル、スルホプロピルイタコン酸エステルのような
スルホン酸基を有するラジカル重合性不飽和単量体、及
びそれらのアルカリ金属塩、アンモニウム塩、有機アミ
ン塩、メタクリロイルオキシエチルトリメチルアンモニ
ウムクロライド、２−ヒドロキシ−３−メタクリルオキ
シプロピルトリメチルアンモニウムクロライドのような
（メタ）アクリル酸から誘導される第四級アンモニウム
塩、（メタ）アクリル酸ジエチルアミノエステルのよう
な第三級アミン基を有するアルコールの（メタ）アクリ
ル酸エステル、及びそれらの第四級アンモニウム塩、（
メタ）アクリルアミド、ジメチルアクリルアミド、アク
リロイルモルフォリン等、アミド基を有するラジカル重
合性不飽和単量体、（メタ）アクリル酸とジアミンから
得られるアミドアミンから誘導される第四級アンモニウ
ム塩、（メタ）アクリル酸ヒドロキシルエチルエステル
、（メタ）アクリル酸ヒドロキシプロピルエステル、（
メタ）アクリル酸−３−クロル−２＝ヒドロキシプロピ
ルエステルのような（メタ）アクリル酸のヒドロキシエ
ステル、（メタ）アクリル酸トリエチレングリコールエ
ステル、（メタ）アクリル酸ジプロピレングリコールエ
ステルのような（メタ）アクリル酸のポリエチレングリ
コールやポリプロピレングリコールのエステル、（メタ
）アクリル酸モノグリセライドのような（メタ）アクリ
ル酸の多価アルコールエステル、モノ（２−ヒドロキシ
ルエチルアクリレート）アシッドフォスフェートのよう
な（メタ）アクリル酸の燐酸塩、Ｎ−（３−スルホプロ
ピル）−Ｎ−メタクロイロキシエチル−Ｎ、Ｎ−ジメチ
ルアンモニウムベタイン、Ｎ−（３−スルホプロピル）
−Ｎメタクロイルアミドプロピル−Ｎ、Ｎ−ジメチルア
ンモニウムベタイン、１−（３−スルホプロピル）−２
−ビニルピリジニウムベタインのようなベタイン型のラ
ジカル重合性不飽和単量体、ビニルピリジン、及びその
塩、ビニルピロリドン等があげられる。In addition, the hydrophilic monomers having copolymerizability with the monomers of Group A are either not involved at all in the crosslinking reaction of the crosslinkable functional groups selected from Group A, or are monomers with significantly reduced reactivity. You need to choose from among the quantities. For example, these monomers include (
Radically polymerizable unsaturated carboxylic acids such as meth)acrylic acid, itaconic acid, and crotonic acid, and alkali metal salts, ammonium salts, and organic amine salts of these unsaturated carboxylic acids, styrene sulfonic acid and sulfopropyl (meth)acrylic acid esters, Radically polymerizable unsaturated monomers having a sulfonic acid group such as sulfopropyl itaconate, and their alkali metal salts, ammonium salts, organic amine salts, methacryloyloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacrylic Quaternary ammonium salts derived from (meth)acrylic acid such as oxypropyltrimethylammonium chloride, (meth)acrylic acid esters of alcohols having a tertiary amine group such as (meth)acrylic acid diethylamino ester, and Their quaternary ammonium salts, (
Radically polymerizable unsaturated monomers having an amide group such as meth)acrylamide, dimethylacrylamide, and acryloylmorpholine, quaternary ammonium salts derived from amide amine obtained from (meth)acrylic acid and diamine, and (meth)acrylic. Acid hydroxyl ethyl ester, (meth)acrylic acid hydroxypropyl ester, (
Hydroxy esters of (meth)acrylic acid such as meth)acrylic acid-3-chloro-2=hydroxypropyl ester, (meth)acrylic acid triethylene glycol ester, (meth)acrylic acid dipropylene glycol ester, ) Polyethylene glycol and polypropylene glycol esters of acrylic acid, polyhydric alcohol esters of (meth)acrylic acid such as (meth)acrylic acid monoglyceride, and (meth)acrylics such as mono(2-hydroxylethyl acrylate) acid phosphate. Acid phosphate, N-(3-sulfopropyl)-N-methacryloyloxyethyl-N, N-dimethylammonium betaine, N-(3-sulfopropyl)
-N methacroylamidopropyl-N,N-dimethylammonium betaine, 1-(3-sulfopropyl)-2
Examples include betaine-type radically polymerizable unsaturated monomers such as vinylpyridinium betaine, vinylpyridine, salts thereof, and vinylpyrrolidone.
本発明におけるブロック又はグラフト共重合体の一方の
分子鎖を構成する疎水性重合体部分は良好な耐蝕性と、
密着性を発現するために、前記Ａ群から選ばれる単量体
の１種または２種以上に基づく構造単位５〜３０重量％
及び前記Ａ群の単量体と共重合性を有する疎水性単量体
の１種又は２種以上に基づく構造単位７０〜９５重量％
よりなることが不可欠である。The hydrophobic polymer portion constituting one molecular chain of the block or graft copolymer in the present invention has good corrosion resistance,
In order to develop adhesion, 5 to 30% by weight of structural units based on one or more monomers selected from Group A
and 70 to 95% by weight of structural units based on one or more hydrophobic monomers copolymerizable with the Group A monomers.
It is essential that we become more
またこの場合、親水性重合体部分に導入された官能基と
良好な反応性を有するものを選択するのが好ましい。例
えば、親水性重合体部分にグリシジル基が存在する場合
は、カルボン酸基やスルホン酸基が導入されることが好
ましい。逆に、親水性重合体部分にカルボン酸基やスル
ホン酸基が存在する場合は、疎水性重合体部分には、グ
リシジル基が存在することが好ましい。また、Ｎ−メチ
ロール基のように自己架橋性の強い官能基が親水性重合
体部分に存在する場合は、この疎水性重合体部分にはＮ
−メチロール基が存在してもよいし、カルボン酸基やス
ルホン酸基があってもよい。Further, in this case, it is preferable to select a material that has good reactivity with the functional group introduced into the hydrophilic polymer portion. For example, when a glycidyl group is present in the hydrophilic polymer portion, it is preferable to introduce a carboxylic acid group or a sulfonic acid group. Conversely, when a carboxylic acid group or a sulfonic acid group is present in the hydrophilic polymer portion, it is preferable that a glycidyl group is present in the hydrophobic polymer portion. Additionally, if a functional group with strong self-crosslinking properties such as an N-methylol group is present in a hydrophilic polymer portion, this hydrophobic polymer portion has N
- A methylol group may be present, or a carboxylic acid group or a sulfonic acid group may be present.
前記Ａ群から選ばれる単量体に基づく構造単位が５重量
％未満又は疎水性単量体に基づく構造単位が９５重量％
を超えると耐蝕性が低下し、Ａ群から選ばれる単量体に
基づく構造単位が３０重量％を超えるか又は疎水性単量
体に基づく構造単位が７０重量％未満では金属との密着
性が低下する。Structural units based on monomers selected from Group A are less than 5% by weight or structural units based on hydrophobic monomers are 95% by weight
If the content exceeds 30% by weight of the structural unit based on the monomer selected from Group A, or if the content of the structural unit based on the hydrophobic monomer is less than 70% by weight, the adhesion to the metal will deteriorate. descend.
前記Ａ群の単量体と共重合性を有する疎水性単量体は、
対象となる金属材料に対しての密着性、耐蝕性を考慮し
て、適宜選ばれる。例えば、（メタ）アクリル酸メチル
、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−
プロピル、（メタ）アクリル酸イソプロピル、（メタ）
アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル
、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アク
リル酸−２−エチルヘキシル、（メタ）アクリル酸オク
チル、（メタ）アクリル酸ラウリル、（メタ）アクリル
酸ステアリル等の（メタ）アクリル酸エステル、スチレ
ン、ビニルトルエン、α−メチルスチレン等の芳香族ビ
ニル型単量体、蟻酸ビニル、酢酸ビニル、プロピオン酸
ビニル、ステアリン酸ビニル等カルボン酸ビニルエステ
ル、ブタジェン、塩化ビニル、塩化ビニリデン、（メタ
）アクリロニトリル、（メタ）アクリルグリシジルエー
テル等が使用される。The hydrophobic monomer having copolymerizability with the monomer of Group A is:
It is appropriately selected in consideration of adhesion and corrosion resistance to the target metal material. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-(meth)acrylate
Propyl, (meth)isopropyl acrylate, (meth)
n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate (Meth)acrylic acid esters such as stearyl acid, aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene, vinyl carboxylic acid esters such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl stearate, butadiene. , vinyl chloride, vinylidene chloride, (meth)acrylonitrile, (meth)acrylic glycidyl ether, etc. are used.
本発明の親水性重合体部分と疎水性重合体部分からなる
ブロック共重合体及びグラフト共重合体は、従来公知の
方法で合成できるが、特に工業的な生産性の容易さ、多
義にわたる性能的な面より、１分子中に２個以上のペル
オキシ結合を有するポリメリックペルオキシド、１分子
中に２＋ｌ！ｉｔ以上のアブ結合を有するポリアゾ化合
物、ラジカル共重合性基含有ペルオキシドを使用してラ
ジカル重合法により製造するのが好ましい。重合方法は
、通常の塊状重合法、懸濁重合法、溶液重合法、乳化重
合法等があげられる。The block copolymers and graft copolymers composed of a hydrophilic polymer part and a hydrophobic polymer part of the present invention can be synthesized by conventionally known methods, but they are especially easy to industrially produce, have a wide range of performance characteristics, From the viewpoint, a polymeric peroxide having two or more peroxy bonds in one molecule, 2+l! in one molecule! It is preferable to produce it by a radical polymerization method using a polyazo compound having an ab bond of more than it or a radical copolymerizable group-containing peroxide. Examples of polymerization methods include conventional bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.
次に、本発明のブロック共重合体の代表的な製造例とし
て、ポリメリックペルオキシドを重合開始剤とする重合
法について以下に説明する。まず、ポリメリックペルオ
キシドを用いて親水性の重合体を形成するビニル型単量
体の重合を行うと、連鎖中にペルオキシ結合が導入され
たペルオキシ結合含有親水性ビニル重合体が得られ、こ
れに疎水性重合体を形成するビニル型単量体を加えて重
合を行うと、ペルオキシ結合がその含有するペルオキシ
結合において開裂し、効率よくブロック共重合体が得ら
れる。Next, as a typical production example of the block copolymer of the present invention, a polymerization method using polymeric peroxide as a polymerization initiator will be described below. First, when a vinyl monomer that forms a hydrophilic polymer is polymerized using polymeric peroxide, a peroxy bond-containing hydrophilic vinyl polymer in which peroxy bonds are introduced into the chain is obtained, which has hydrophobic properties. When a vinyl type monomer that forms a polymer is added and polymerized, the peroxy bonds are cleaved at the peroxy bonds contained therein, and a block copolymer can be efficiently obtained.
また、本発明のグラフト共重合体の代表的な製造例とし
て、ラジカル共重合性基含有ペルオキシドを重合開始剤
とする重合法について以下に説明する。まず、ラジカル
共重合性基含有ペルオキシドのペルオキシ結合が開裂し
ない条件で通常の遊離基重合開始剤により親水性の重合
体を形成するビニル型単量体を共重合することにより、
ペルオキシ結合を含有する親水性共重合体が得られ、次
にこのペルオキシ結合が開裂する条件でこれに疎水性の
重合体を形成するビニル型単量体を加えて重合を行うと
、ペルオキシ結合がその含有するペルオキシ結合におい
て開裂し、効率よくグラフト共重合体が得られる。Further, as a typical production example of the graft copolymer of the present invention, a polymerization method using a radical copolymerizable group-containing peroxide as a polymerization initiator will be described below. First, by copolymerizing a vinyl monomer that forms a hydrophilic polymer with a common free radical polymerization initiator under conditions that do not cleave the peroxy bond of the radical copolymerizable group-containing peroxide,
A hydrophilic copolymer containing peroxy bonds is obtained, and when polymerization is carried out by adding a vinyl monomer that forms a hydrophobic polymer under conditions that cleave the peroxy bonds, the peroxy bonds are cleaved. The peroxy bonds contained therein are cleaved, and a graft copolymer can be efficiently obtained.
このようにして得られるブロック共重合体、グラフト共
重合体は、親水性重合体部分、疎水性重合体部分の分子
量を自由に調節することが可能である。また、グラフト
共重合体においては、親水性重合体部分を幹とし、疎水
性重合体部分を枝とするグラフト共重合体又は疎水性重
合体部分を幹とし、親水性重合体部分を枝とするグラフ
ト共重合体のいずれであってもよい。本発明におけるブ
ロック共重合体及びグラフト共重合体の親水性重合体部
分／疎水性重合体部分の好ましい重量百分比は１０／９
０ないし９０／１０である。In the block copolymer and graft copolymer thus obtained, the molecular weights of the hydrophilic polymer portion and the hydrophobic polymer portion can be freely adjusted. In addition, in a graft copolymer, a graft copolymer has a hydrophilic polymer portion as a trunk and a hydrophobic polymer portion as branches, or a hydrophobic polymer portion as a trunk and a hydrophilic polymer portion as branches. It may be any graft copolymer. The preferred weight percentage of the hydrophilic polymer portion/hydrophobic polymer portion of the block copolymer and graft copolymer in the present invention is 10/9.
0 to 90/10.
本発明の界面活性剤としては、一般に使用されるもので
、非イオン系界面活性剤、陰イオン系界面活性剤、陽イ
オン系界面活性剤、両性イオン系界面活性剤から選ばれ
る１種以上の界面活性剤である。The surfactant of the present invention is one or more commonly used surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. It is a surfactant.
非イオン系界面活性剤としては、例えばポリオキシエチ
レンラウリルアルコール、ポリオキシエチレンラウリル
エーテル、ポリオキシエチレンオレイルエーテル等のポ
リオキシエチレン高級アルコールエーテル類、ポリオキ
シエチレンオクチルフェノール、ポリオキシエチレンノ
ニルフェノール等のポリオキシエチレンアルキルアリー
ルエーテル類、ポリオキシエチレングリコールモノステ
アレート等のポリオキシエチレンアシルエステル類、ポ
リプロピレングリコールエチレンオキサイド付加物、ポ
リオキシエチレンソルビタンモノラウレート、ポリオキ
シエチレンソルビタンモノステアレート等のポリオキシ
エチレンソルビタン脂肪酸エステル類、アルキルリン酸
エステル、ポリオキシエチレンアルキルエーテルリン酸
エステル等のリン酸エステル類、シュゴーエステル類、
セルロースエーテル類等が使用される。Examples of nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether, and polyoxyethylene such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol. Ethylene alkylaryl ethers, polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate, polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, etc. Fatty acid esters, alkyl phosphate esters, phosphate esters such as polyoxyethylene alkyl ether phosphate esters, sugar esters,
Cellulose ethers and the like are used.
陰イオン系界面活性剤としては、例えばオレイン酸ナト
リウム、オレイン酸カリウム等の脂肪酸塩、ラウリル硫
酸ナトリウム、ラウリル硫酸アンモニウム等の高級アル
コール硫酸エステル類、ドデシルベンゼンスルホン酸ナ
トリウム、アルキルナフタレンスルホン酸ナトリウム等
のアルキルベンゼンスルホン酸塩及びアルキルナフタレ
ンスルホン酸塩、ナフタレンスルホン酸ホルマリン縮合
物、ジアルキルスルホコハク酸塩、ジアルキルホスフェ
ート塩、ポリオキシエチレンアルキルエーテル硫酸ナト
リウム、ポリオキシエチレンアルキルフェニルエーテル
硫酸ナトリウム等のポリオキシエチレンサルフェート塩
等が使用される。Examples of anionic surfactants include fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylbenzenes such as sodium dodecylbenzene sulfonate and sodium alkylnaphthalene sulfonate. Sulfonates and alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, polyoxyethylene sulfate salts such as sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, etc. is used.
陽イオン系界面活性剤としては、例えばエタノールアミ
ン類、ラウリルアミンアセテート、トリエタノールアミ
ンモノステアレート蟻酸塩、ステアラミドエチルジエチ
ルアミン酢酸塩等のアミン塩、ラウリルトリメチルアン
モニウムクロライド、ジラウリルジメチルアンモニウム
クロライド、ラウリルジメチルベンジルアンモニウムク
ロライド、ステアリルジメチルベンジルアンモニウムク
ロライド等の第４級アンモニウム塩等が使用される。Examples of cationic surfactants include ethanolamines, amine salts such as laurylamine acetate, triethanolamine monostearate formate, stearamide ethyl diethylamine acetate, lauryl trimethylammonium chloride, dilauryl dimethylammonium chloride, and lauryl. Quaternary ammonium salts such as dimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride are used.
両性イオン系界面活性剤としては、ジメチルアルキルラ
ウリルベタイン、ジメチルアルキルラウリルベタインン
等の脂肪酸型両性界面活性剤、ジメチルアルキルスルホ
ベタインのようなスルホン酸型両性界面活性剤、アルキ
ルグリシン等が使用される。As the amphoteric surfactant, fatty acid type amphoteric surfactants such as dimethylalkyl lauryl betaine and dimethylalkyl lauryl betaine, sulfonic acid type amphoteric surfactants such as dimethylalkyl sulfobetaine, alkyl glycine, etc. are used. .
上記のような界面活性剤を添加することによって、十分
な親水性を得ることができるが、特に親水持続性に効果
がある界面活性剤は非イオン系界面活性剤と陰イオン系
界面活性剤とを併用したものである。Sufficient hydrophilicity can be obtained by adding the above-mentioned surfactants, but surfactants that are particularly effective in maintaining hydrophilicity include nonionic surfactants and anionic surfactants. This is a combination of
前記ブロック又はグラフト共重合体と界面活性剤の配合
割合は、共重合体の固形分１００重量部に対し、界面活
性剤１〜４０重量部が好ましい。The blending ratio of the block or graft copolymer and the surfactant is preferably 1 to 40 parts by weight of the surfactant per 100 parts by weight of the solid content of the copolymer.
界面活性剤の配合割合が１重量部未満では、親水性の高
い金属表面用被覆組成物を得にくくなり、４０重量部を
超えると塗膜強度が低下する傾向を示す。If the proportion of the surfactant is less than 1 part by weight, it becomes difficult to obtain a highly hydrophilic coating composition for metal surfaces, and if it exceeds 40 parts by weight, the coating film strength tends to decrease.
本発明で使用する金属キレート型架橋剤は、前記した一
般式で表される化合物であり、そのうち樹脂の安定性、
耐蝕性の面からアルミニウムモノアセチルアセトネート
ビス（エチルアセトアセテート）、アルミニウムトリス
（アセチルアセトネート）、ジイソプロポキシビス（ア
セチルアセトネート）チタン、テトラ−ｎ−ブトキシチ
タンの単独又は組み合わせたものが好適である。なお、
金属キレート型架橋剤の一般式中の各範囲は、通常金属
キレート型架橋剤として使用されている化合物を包含す
る範囲を表すものである。The metal chelate type crosslinking agent used in the present invention is a compound represented by the above-mentioned general formula, and among them, the stability of the resin,
From the viewpoint of corrosion resistance, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(acetylacetonate), diisopropoxybis(acetylacetonate) titanium, and tetra-n-butoxytitanium are preferably used alone or in combination. It is. In addition,
Each range in the general formula of the metal chelate crosslinking agent represents a range that includes compounds commonly used as metal chelate crosslinking agents.
この金属キレート型架橋剤（固形分）の配合割合は、ブ
ロック又はグラフト共重合体の固形分１００重量部に対
して５〜３０重量部が好ましい。The mixing ratio of the metal chelate type crosslinking agent (solid content) is preferably 5 to 30 parts by weight based on 100 parts by weight of the solid content of the block or graft copolymer.
この配合割合が５重量部未満では耐蝕性を向上させにく
く、３０重量部を超えると親水性能が低下する傾向があ
る。If this blending ratio is less than 5 parts by weight, it is difficult to improve corrosion resistance, and if it exceeds 30 parts by weight, hydrophilic performance tends to decrease.
次に、本発明の金属表面用被覆組成物を金属表面に被覆
する方法について説明する。−船釣には金属表面用被覆
組成物を金属材料表面に塗布し加熱硬化させる方法が採
用される。塗布方法は、通常の塗料における塗布手段、
つまりロールコート法、スプレー法、浸漬法、へヶ塗り
法、スピンコード法等が適用される。Next, a method for coating a metal surface with the metal surface coating composition of the present invention will be explained. - For boat fishing, a method is adopted in which a coating composition for metal surfaces is applied to the surface of a metal material and cured by heating. The application method is the application means of ordinary paint,
That is, a roll coating method, a spray method, a dipping method, a dipping method, a spin cord method, etc. are applied.
この場合に用いる溶剤としては、水、メタノール・エタ
ノール、ｎ−プロパツール、イソプロパツール、ｎ−ブ
タノール、ジアセトンアルコール等のアルコール系溶剤
、メチルセロソルブ、エチルセロソルブ、ブチルセロソ
ルブ、メチルカルピトール、エチルカルピトール、ブチ
ルカルピトール等のアルコール系溶剤、メチルエチルケ
トン、メチルイソブチルケトン等のケトン系溶剤、酢酸
メチル、酢酸エチル、酢酸ブチル等のエステル系ＮＬベ
ンゼン、トルエン、キシレン等の芳香族炭化水素系溶剤
、ホルムアミド、ジメチルポルムアミド等のアミド系溶
剤、アセトニトリル、アセチルニトリル等のニトリル系
溶剤があげられる。Solvents used in this case include water, alcoholic solvents such as methanol/ethanol, n-propanol, isopropanol, n-butanol, and diacetone alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, and ethyl carpitol. Alcohol solvents such as toll and butyl carpitol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester series such as methyl acetate, ethyl acetate and butyl acetate, NL benzene, aromatic hydrocarbon solvents such as toluene and xylene, formamide , amide solvents such as dimethylpolamide, and nitrile solvents such as acetonitrile and acetylnitrile.
［作用］
前記手段を採用したことにより、ブロック共重合体又は
グラフト共重合体の親水性重合体部分と界面活性剤が親
和して、そのブロック又はグラフト共重合体が均一に界
面活性剤を分散するとともに、金属キレート型架橋剤は
自己架橋や共重合体の官能基との架橋作用により被膜内
部への水の浸透を防いで耐蝕性を発揮する。この組成物
から形成される被膜は、ブロック又はグラフト共重合体
の親水性重合体部分が界面活性剤のアンカーとして作用
し、しっかりと界面活性剤を被膜中に固着する。そして
、被膜上に水分が付着したとき、被膜内部から徐々に界
面活性剤がブリードしてブロック又はグラフト共重合体
の親水性重合体部分の機能とブリードしてきた界面活性
剤の機能の相乗効果で親水性能と親水持続性が飛曜的に
向上する。[Function] By employing the above means, the hydrophilic polymer portion of the block copolymer or graft copolymer and the surfactant become compatible, and the block or graft copolymer uniformly disperses the surfactant. At the same time, the metal chelate type crosslinking agent exhibits corrosion resistance by preventing water from penetrating into the coating through self-crosslinking or crosslinking with the functional groups of the copolymer. In the coating formed from this composition, the hydrophilic polymer portion of the block or graft copolymer acts as an anchor for the surfactant, firmly fixing the surfactant in the coating. When moisture adheres to the film, the surfactant gradually bleeds from inside the film, resulting in a synergistic effect between the function of the hydrophilic polymer portion of the block or graft copolymer and the function of the bleeding surfactant. Hydrophilic performance and hydrophilic sustainability are dramatically improved.
一方、ブロック又はグラフト共重合体の疎水性重合体部
分は金属表面と密着し、被膜は優れた耐水性、耐蝕性及
び強度を発揮する。On the other hand, the hydrophobic polymer portion of the block or graft copolymer adheres closely to the metal surface, and the coating exhibits excellent water resistance, corrosion resistance, and strength.
［実施例］
以下、実施例及び比較例をあげて本発明を具体的に説明
する。単量体の仕込み部数は表−１及び２にまとめて示
した。なお部数表示はいずれも重量基準である。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The number of monomers charged is summarized in Tables 1 and 2. All copies shown are based on weight.
（参考例１〜６及び１０〜１２）（ブロック共重合体の
製造）
温度計、攪拌器及び還流冷却器を備えた反応器に、メチ
ルセロソルブ２３０部を仕込み、窒素ガスを吹き込みな
がら７２℃に加熱し、それに、メチルセロソルブ
１００部親水性単量体
Ａ 部架橋官能基を持つビニル型単量体 Ｂ 部−
（Ｃｏ （ＣＨ２）４ ＣＯＯ（Ｃ２Ｈ４０）３Ｃｏ
（ＣＨ２）４ Ｃ００Ｏ） ｌ。(Reference Examples 1 to 6 and 10 to 12) (Production of block copolymer) 230 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 72°C while blowing nitrogen gas. Heat and add methyl cellosolve to it
100 parts hydrophilic monomer
Part A Vinyl type monomer with a crosslinking functional group Part B -
(Co (CH2)4 COO(C2H40)3Co
(CH2)4C00O) l.
２０部
からなる混合液を２時間かけて仕込み、さらに２時間、
重合反応を行った。その後、
メチルセロソルブ ２８５部疎水性単量
体 Ｃ部架橋官能基を持つビニル
型単量体 Ｄ 部からなる混合液を３０分かけて仕込
み７５℃で５時間重合反応を行った。なお、上記Ａ−Ｄ
の部数は表−１及び２に示した通りである。重合結果も
表−１及び２に併せて示す。A mixture consisting of 20 parts was prepared over 2 hours, and then for another 2 hours.
A polymerization reaction was performed. Thereafter, a mixed solution consisting of 285 parts of methyl cellosolve, a hydrophobic monomer, a part C, a vinyl monomer having a crosslinking functional group, and a part D was charged over 30 minutes and a polymerization reaction was carried out at 75° C. for 5 hours. In addition, the above A-D
The number of copies is as shown in Tables 1 and 2. The polymerization results are also shown in Tables 1 and 2.
（参考例７〜９）（グラフト共重合体の製造）温度針、
攪拌器及び還流冷却器を備えた反応器にメチルセロソル
ブ２３０部を仕込み、窒素ガスを吹き込みながら８５℃
に加熱し、それにｔ−ブチルペルオキシオクタノエート
（日本油脂株式会社製商品名［パーブチル０Ｊ）１．０
部、ラジカル共重合性有機過酸化物としてｔ−プチルペ
ルオキシメタシクロイロキシエチルカーボネート３．８
部に
親水性単量体 Ａ 部架橋官能基
を持つビニル型単量体 Ｂ 部メチルセロソルブ
１００部を混合し、この混合液を２時間か
けて仕込み、さらに７時間重合反応を行った。その後１
１０℃に加熱し、
疎水性単量体 Ｃ部架橋官能基を
持つビニル型単量体 Ｄ 部メチルセロソルブ
２８５部からなる混合液を２時間かけて仕込
み、さらに７時間グラフト重合反応を行いグラフト共重
合体を製造した。前記Ａ−Ｄの部数、及び重合結果を表
２に示す。(Reference Examples 7 to 9) (Production of graft copolymer) Temperature needle,
230 parts of methyl cellosolve was charged into a reactor equipped with a stirrer and a reflux condenser, and heated to 85°C while blowing nitrogen gas.
1.0% of t-butyl peroxyoctanoate (product name: Perbutyl 0J, manufactured by Nippon Oil & Fats Co., Ltd.)
3.8 parts, t-butylperoxymetacycloyloxyethyl carbonate as the radical copolymerizable organic peroxide
Part: hydrophilic monomer; Part A: vinyl monomer with crosslinking functional group; Part B: methyl cellosolve.
100 parts were mixed, this mixed solution was charged over 2 hours, and the polymerization reaction was further carried out for 7 hours. then 1
Hydrophobic monomer C part Vinyl monomer with crosslinking functional group D part Methyl cellosolve
A mixed solution consisting of 285 parts was charged over 2 hours, and the graft polymerization reaction was further carried out for 7 hours to produce a graft copolymer. Table 2 shows the number of parts of A-D and the polymerization results.
（参考例１３〜１５）（ランダム共重合体の製造）温度
針、攪拌器及び環流冷却器を備えた反応器にメチルセロ
ソルブ２３０部を仕込み、窒素ガスを吹き込みながら７
０℃に加熱し、それにメチルセロソルブ
１００部親水性単量体 Ａ 部
架橋官能基を持つビニル型単量体 Ｂ 部疎水性単量
体 Ｃ部架橋官能基を持つビニル
型単量体 Ｄ 部ＣＨ３Ｃ（ＣＨ３）２０ＯＣＯＣ（
ＣＨ３）３４．３部
からなる混合液を２時間かけて仕込み、さらに５時間か
けて共重合反応を行った。前記Ａ−Ｄの部表−１
表−２
上記表−１及び表−２における略号は次の意味を表す。(Reference Examples 13 to 15) (Production of random copolymer) 230 parts of methyl cellosolve was charged into a reactor equipped with a temperature needle, a stirrer, and a reflux condenser, and while blowing nitrogen gas,
Heat to 0℃ and add methyl cellosolve to it.
100 parts Hydrophilic monomer A part Vinyl type monomer with a crosslinking functional group B part Hydrophobic monomer C part Vinyl type monomer having a crosslinking functional group D part CH3C(CH3)20OCOC(
A mixed solution consisting of 34.3 parts of CH3) was charged over a period of 2 hours, and a copolymerization reaction was carried out over a further 5 hours. Section A-D Table-1 Table-2 The abbreviations in Table-1 and Table-2 above have the following meanings.
■：２−ヒドロキシエチルメタクリレート■ニアクリロ
イルモルフォリン
■：ビニルピロリドン
■ニジメチルアクリルアミド
■：２−アクリルアミドー２−メチルプロパンスルホン
酸
■：グリシジルメタクリレート
■：Ｎ−メチロールアクリルアミド
■：メチルメタクリレート
■：エチルメタクリレート
■＝ニブチルメタクリレー
トニアクリル酸
＊；固形分（重量％）
※：２５℃における粘度（Ｐ）
（実施例１〜１１及び比較例１〜１０）参考例１〜１５
で製造した重合体１００重量部に対し、表−３及び５に
示した界面活性剤及び金属キレート型架橋剤を配合し、
その組成物を表−４及び６に示した金属に塗布し、乾燥
膜厚が約１μｍとなるよう２３０℃、３０秒の硬化条件
で焼き付けを行った。これらの被覆物について表−７〜
１０に示した各種試験を行った。その結果を同表−７〜
ＩＯに示した。■: 2-Hydroxyethyl methacrylate ■ Niacryloylmorpholine ■: Vinylpyrrolidone ■ Nidimethylacrylamide ■: 2-acrylamide 2-methylpropanesulfonic acid ■: Glycidyl methacrylate ■: N-methylol acrylamide ■: Methyl methacrylate ■: Ethyl methacrylate ■ = Nibutyl methacrylate diacrylic acid *; Solid content (wt%) *: Viscosity at 25°C (P) (Examples 1 to 11 and Comparative Examples 1 to 10) Reference Examples 1 to 15
The surfactant and metal chelate type crosslinking agent shown in Tables 3 and 5 were blended with 100 parts by weight of the polymer produced in
The composition was applied to the metals shown in Tables 4 and 6, and baked at 230° C. for 30 seconds to give a dry film thickness of about 1 μm. Table 7~ regarding these coatings
Various tests shown in 10 were conducted. The results are shown in Table 7.
Shown in IO.
表
上記表−３中の数字は重量部を示す。また、界面活性剤
及び金属キレート型架橋剤の略号は次の意味を表す。The numbers in Table 3 above indicate parts by weight. Furthermore, the abbreviations for surfactant and metal chelate crosslinking agent have the following meanings.
（ａ）：ポリオキシエチレンノニルフェニルエーテル、
日本油脂株式会社製商品名ノニオンＮＳ −２１２（ｂ
）ニジオクチルスルホコハク酸ナトリウム、日本油脂株
式会社製商品名ラピゾールＢ−８０（Ｃ）：オクタデシ
ルトリメチルアンモニウムクロライド、日本油脂株式会
社製商品名カヂオンＡＢ（ｄ）ニジメチルアルキル（ヤ
シ）ベタイン、日本油脂株式会社製商品名アノンＢＦ
（ｅ）ニジプロポキシビス（アセチルアセトナート）チ
タン、７５％溶液、日本曹達株式会社製商品名（ｆ）：
テトラーｎ−ブトキシチタン、７５％溶液、日本曹達株
式会社製商品名ＴＢＴ
（ｇ）ニアルミニウムモノアセチルアセトネートビス（
エチルアセトアセテ−１−）、７６％溶液、川研ファイ
ンケミカル株式会社製商品名アルミキレートＤ
（ｈ）ニアルミニウムトリス（アセチルアセトネート）
、７６％溶液、川研ファインケミカル株式会社製商品名
アルミキレートＡ
上記表
４の略号は次の意味を表す。(a): polyoxyethylene nonylphenyl ether,
Product name: Nonion NS-212 (b) manufactured by Nippon Oil & Fats Co., Ltd.
) Nidioctyl sodium sulfosuccinate, manufactured by NOF Corporation, trade name Rapizol B-80 (C): Octadecyltrimethylammonium chloride, manufactured by NOF Corporation, trade name Cadion AB (d) Nidimethylalkyl (coconut) betaine, NOF Corporation Company product name: Anon BF (e) Nidipropoxybis(acetylacetonate) titanium, 75% solution, Nippon Soda Co., Ltd. product name (f):
Tetra n-butoxytitanium, 75% solution, manufactured by Nippon Soda Co., Ltd., trade name TBT (g) Nialuminum monoacetylacetonate bis(
Ethylacetoacetate-1-), 76% solution, manufactured by Kawaken Fine Chemical Co., Ltd. Product name Aluminum Chelate D (h) Nialuminum tris (acetylacetonate)
, 76% solution, manufactured by Kawaken Fine Chemical Co., Ltd. Product name Aluminum Chelate A The abbreviations in Table 4 above have the following meanings.
表−５ 表 上記表 ６中の略号の意味は前記表 ４と同じ である。Table-5 table Above table The meanings of the abbreviations in 6 are shown in the table above. Same as 4 It is.
表
上記表
５における数字は重量部を表し、
また
界面活性剤及び金属キレート型架橋剤の略号は前表−８
表
表−１０
上記表−７，８，９，１０の略号の意味は次の通りであ
る。The numbers in Table 5 above represent parts by weight, and the abbreviations for surfactants and metal chelate crosslinking agents are as follows: That's right.
＃：初期接触角（度）
＊：サイクルテスト後の接触角（度）
サイクルテストは流水浸漬７時間、５０ ’ｃ乾燥１７
時間を１サイクルとして、サイクル終了後、接触角を測
定した。#: Initial contact angle (degrees) *: Contact angle after cycle test (degrees) The cycle test was immersed in running water for 7 hours and dried at 50'C for 17 hours.
The time was defined as one cycle, and the contact angle was measured after the cycle was completed.
☆：塩水噴霧テスト、ＪＩＳＺ−２３７１に準じて行っ
た。☆: Salt spray test, conducted according to JISZ-2371.
Ｏ；変化なし △；やや錆あり ×；剥離又は全面錆あ
り
※：密着性テスト、ＪＩＳＤ−０２０２に準じて行った
（基盤目剥離テスト）。O: No change △: Slight rust ×: Peeling or full-scale rust *: Adhesion test, conducted according to JISD-0202 (substrate grain peeling test).
（ａｌ ； １００／１００ （ｂ） ； ９０／１
００ ｔｃ＋ ｉ ７０／１００（ｄｌ 、 ６０／
１００
上記表−７〜１０に示されるように、本発明の被覆組成
物は金属表面に施されて形成された被膜の親水持続性、
耐蝕性、密着性が良好にしかもバランスよく発揮される
ことがわかった。これに対してランダム共重合体を被覆
した場合、また界面活性剤等を配合しなかった場合これ
らの３特性のいづれかに欠点があり、被覆剤としては不
十分な性能であることがわかった。(al; 100/100 (b); 90/1
00 tc+i 70/100(dl, 60/
100 As shown in Tables 7 to 10 above, the coating composition of the present invention maintains hydrophilicity of the coating formed by applying it to a metal surface.
It was found that corrosion resistance and adhesion were exhibited well and in a well-balanced manner. On the other hand, it was found that when a random copolymer was coated or when a surfactant or the like was not mixed, there was a defect in any of these three properties, resulting in insufficient performance as a coating material.
［発明の効果］
本発明の金属表面用被覆組成物は、金属表面に形成され
た被膜表面の親水性に優れ、その効果を永続的に維持す
ることができるとともに、各種金属材料との密着性にも
優れ、被膜の耐水性や機械的物性も非常に良好であると
いう効果を奏する。[Effects of the Invention] The coating composition for metal surfaces of the present invention has excellent hydrophilicity on the surface of the coating formed on the metal surface, can permanently maintain this effect, and has excellent adhesion to various metal materials. The film also has excellent water resistance and mechanical properties.
従って、各種金属成形材料、エアコンの熱交換器、自動
車のラジェータ、建築材料等の親水化剤としての用途に
非常に有用である。Therefore, it is very useful as a hydrophilic agent for various metal forming materials, heat exchangers for air conditioners, radiators for automobiles, building materials, etc.
Claims (1)
重合体、界面活性剤及び下記の金属キレート型架橋剤を
含有することを特徴とする金属表面用被覆組成物。 ブロック又はグラフト共重合体：グリシジル基、Ｎ−メ
チロール基、Ｎ−ブトキシメチロール基、アミノ基、カ
ルボン酸基、スルホン酸基のいずれかの官能基を有する
ラジカル重合性の単量体からなる群（以下Ａ群という）
から選ばれる単量体の１種又は２種以上に基づく構造単
位５〜３５重量％及び上記Ａ群の単量体と共重合性を有
する親水性単量体の１種又は２種以上に基づく構造単位
６５〜９５重量％よりなる親水性重合体部分と、上記Ａ
群の単量体から選ばれる単量体の１種又は２種以上に基
づく構造単位５〜３０重量％及び上記Ａ群の単量体と共
重合性を有する疎水性単量体の１種又は２種以上に基づ
く構造単位７０〜９５重量％よりなる疎水性重合体部分
からなるブロック又はグラフト共重合体。 金属キレート型架橋剤：一般式ＡｌＸ＿ｎＹ＿３＿−＿
ｎ〔式中Ｘは炭素原子数１〜５のアルコキシ基、ＹはＲ
＾１ＣＯＣＨ＿２ＣＯＲ＾２又はＲ＾３ＣＯＣＨ＿２Ｃ
ＯＯＲ＾４を示し、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４は
炭素原子数１〜１０のアルキル基であり、ｎは０、１又
は２である〕又は一般式ＴｉＸ＿ｎＹ＿４＿−＿ｎ〔式
中Ｘは炭素原子数１〜５のアルコキシ基又は水酸基、Ｙ
はＯＣ（ＣＨ＿３）ＣＨＣＯＣＨ＿３、ＯＣ＿２Ｈ＿４
Ｎ（Ｃ＿２Ｈ＿４ＯＨ）、ＯＣＨ（ＣＨ＿３）ＣＯＯＨ
であり、ｎは０又は１〜４までの整数である〕で表され
る化合物。[Scope of Claims] 1. A coating composition for metal surfaces, characterized by containing the following block or graft copolymer having self-crosslinking properties, a surfactant, and the following metal chelate type crosslinking agent. Block or graft copolymer: a group consisting of radically polymerizable monomers having a functional group of glycidyl group, N-methylol group, N-butoxymethylol group, amino group, carboxylic acid group, or sulfonic acid group ( (hereinafter referred to as group A)
5 to 35% by weight of structural units based on one or more monomers selected from and one or more hydrophilic monomers copolymerizable with the monomers of Group A above. A hydrophilic polymer portion consisting of 65 to 95% by weight of structural units, and the above A
5 to 30% by weight of structural units based on one or more monomers selected from the monomers of Group A and one or more hydrophobic monomers copolymerizable with the monomers of Group A above. A block or graft copolymer consisting of a hydrophobic polymer portion consisting of 70 to 95% by weight of structural units based on two or more types. Metal chelate type crosslinking agent: General formula AlX_nY_3_-_
n [In the formula, X is an alkoxy group having 1 to 5 carbon atoms, Y is R
^1COCH_2COR^2 or R^3COCH_2C
OOR^4, R^1, R^2, R^3, R^4 are alkyl groups having 1 to 10 carbon atoms, and n is 0, 1 or 2] or the general formula TiX_nY_4_-_n [In the formula, X is an alkoxy group or a hydroxyl group having 1 to 5 carbon atoms, Y
is OC(CH_3) CHCOCH_3, OC_2H_4
N(C_2H_4OH), OCH(CH_3)COOH
and n is 0 or an integer from 1 to 4].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25522888A JPH02102278A (en) | 1988-10-11 | 1988-10-11 | Coating composition for metal surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25522888A JPH02102278A (en) | 1988-10-11 | 1988-10-11 | Coating composition for metal surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02102278A true JPH02102278A (en) | 1990-04-13 |
Family
ID=17275812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25522888A Pending JPH02102278A (en) | 1988-10-11 | 1988-10-11 | Coating composition for metal surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02102278A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02219876A (en) * | 1989-02-21 | 1990-09-03 | Sumitomo Light Metal Ind Ltd | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger |
| JP2002188076A (en) * | 2000-12-21 | 2002-07-05 | Nippon Shokubai Co Ltd | Composition for hydrophilizing treatment and member by using the same |
| JP2012072336A (en) * | 2010-09-30 | 2012-04-12 | Kobe Steel Ltd | Coating composition and aluminum fin material using the same |
| JP2019172598A (en) * | 2018-03-27 | 2019-10-10 | 株式会社コーセー | Oily eyeliner cosmetics |
-
1988
- 1988-10-11 JP JP25522888A patent/JPH02102278A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02219876A (en) * | 1989-02-21 | 1990-09-03 | Sumitomo Light Metal Ind Ltd | Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger |
| JP2002188076A (en) * | 2000-12-21 | 2002-07-05 | Nippon Shokubai Co Ltd | Composition for hydrophilizing treatment and member by using the same |
| JP2012072336A (en) * | 2010-09-30 | 2012-04-12 | Kobe Steel Ltd | Coating composition and aluminum fin material using the same |
| JP2019172598A (en) * | 2018-03-27 | 2019-10-10 | 株式会社コーセー | Oily eyeliner cosmetics |
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