CA2069726A1 - Aqueous dispersion of a cathode-deposited binder, and a method of manufacture and use thereof - Google Patents
Aqueous dispersion of a cathode-deposited binder, and a method of manufacture and use thereofInfo
- Publication number
- CA2069726A1 CA2069726A1 CA 2069726 CA2069726A CA2069726A1 CA 2069726 A1 CA2069726 A1 CA 2069726A1 CA 2069726 CA2069726 CA 2069726 CA 2069726 A CA2069726 A CA 2069726A CA 2069726 A1 CA2069726 A1 CA 2069726A1
- Authority
- CA
- Canada
- Prior art keywords
- binder
- powder
- weight
- additives
- dispersion
- 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.)
- Abandoned
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 79
- 239000006185 dispersion Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 27
- 239000000843 powder Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 125000002091 cationic group Chemical group 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 239000000049 pigment Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 2
- 125000004437 phosphorous atom Chemical group 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 claims 2
- 230000037452 priming Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 10
- 239000004922 lacquer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 125000003010 ionic group Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 amino epoxy resins Chemical compound 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 241000905957 Channa melasoma Species 0.000 description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 2
- 241001024304 Mino Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101150050192 PIGM gene Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- WLWIMKWZMGJRBS-UHFFFAOYSA-N primin Chemical compound CCCCCC1=CC(=O)C=C(OC)C1=O WLWIMKWZMGJRBS-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 1
- JLBXCKSMESLGTJ-UHFFFAOYSA-N 1-ethoxypropan-1-ol Chemical compound CCOC(O)CC JLBXCKSMESLGTJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZUXNHFFVQWADJL-UHFFFAOYSA-N 3,4,5-trimethoxy-n-(2-methoxyethyl)-n-(4-phenyl-1,3-thiazol-2-yl)benzamide Chemical compound N=1C(C=2C=CC=CC=2)=CSC=1N(CCOC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 ZUXNHFFVQWADJL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- 241001261858 Alsodes Species 0.000 description 1
- 241001578851 Anticrates Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- 241001207849 Canis anthus Species 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 241000784713 Cupido Species 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- 239000004243 E-number Substances 0.000 description 1
- 235000019227 E-number Nutrition 0.000 description 1
- 241000448280 Elates Species 0.000 description 1
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241001527806 Iti Species 0.000 description 1
- POSKOXIJDWDKPH-UHFFFAOYSA-N Kelevan Chemical compound ClC1(Cl)C2(Cl)C3(Cl)C4(Cl)C(CC(=O)CCC(=O)OCC)(O)C5(Cl)C3(Cl)C1(Cl)C5(Cl)C42Cl POSKOXIJDWDKPH-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 241000282339 Mustela Species 0.000 description 1
- 241000282337 Nasua nasua Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 241001307210 Pene Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 235000011483 Ribes Nutrition 0.000 description 1
- 241000220483 Ribes Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 102100036378 T-cell immunomodulatory protein Human genes 0.000 description 1
- 101710194900 T-cell immunomodulatory protein Proteins 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 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 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 229940075911 depen Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 210000000614 rib Anatomy 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
Herberts Gesellschaft mit beschrankter Haftung A b s t r a c t An aqueous dispersion of a cathode-deposited thermosetting cationic film-forming binder, manufactured by heating a slurry of the binder, used in the form of powder having a particle size of 0.1 to 1000 µm and a glass transition temperature of 35 to 130°C
a) in water, if the binder contains cationic groups, or b) in water and acid, if the binder contains cationic and/or basic groups, to a temperature of 40 to 90°C, for 5 minutes to 5 hours, a method of manufacturing the dispersion, and use thereof for cathodic deposition coating.
a) in water, if the binder contains cationic groups, or b) in water and acid, if the binder contains cationic and/or basic groups, to a temperature of 40 to 90°C, for 5 minutes to 5 hours, a method of manufacturing the dispersion, and use thereof for cathodic deposition coating.
Description
~ ) ~
2~972~
Hexberts Ge~ellschaf~ mit b~chr~nk~r Ha~tung An aqueou~ ~3pcr~ion ~ a ~thoa~-~epo~ited bin~er, an~ a ~et~ of m~nu~ ur~ a~ U3~ t~er~o~' The invention rel~te~ to aqUeous dispersions o~ càthode-depo~ited, ther~nosetting film-forming binderEi fc;~ ooatin~
an electri~ally conductiv~ s~bstratR conne~ted as cathode.
thodic elec~rodeposit~on coating is a known method of læ.cq~e:ring electrically condu~ ive surfaces, e.~. surfaces o~ metal or electrically corlductive pla:tics or electrica~ly ~onductive lacqu~r layers. In t~e method, the ~acquer con~ituent~ ar~ pracipitat~ad ~rom an elea~rodepo~:ition bath on to the s~rfa¢e of a workpi~ce connected a~: c~h4d~, usin~ direct current~ The coagula~ed lacquer con3~ikuents ~re ~en liquef ied and c:~osslinXed by hea$1ng to ele~ated temperatures. The re~ul~ homo~en~ous smooth film wi~h high meahanical and ¢hemical stability. The p~po~e of the ~ilm is to prote~t the su~strate ~rom mec~anical damage and cor~osion.
The usua~ method of producin~ e~ectrodepositioh baths is to tran~p~r~ liquid or pa~ty water-containin~ or ~o~vent-containin~ mat~rial~, e.g. binder disp~rsions r pi~ment pa~tes or sol~ent-containing pigm~nt and bind~r mixtures, to the co~ing installation, whe~e these pre~pr~ducts ~re diluted wi~h water ~o obtain the electrodeposition ~ath ready ~or use. After ho~o~enisation, the e~eatro-depositio~ bath ~an be used for coating.
In this method, it is necessary to transport large guantities ~$ water and liquid ~inders, si~e bind~r disp~rsions must have onl~ a relativ~ly low cont~n~ of - 2~69726 ~olids i~ they are to have the l~w viscosi~y required for proce~slng~ If an accident occurs during transport ~f ~e~ thinly viscous material~, there is a ri~k that the s~rroundin~ earth will ~e contaminated~ If ~olvent-containing system~ ~e txansporte~, the volu~e tr~nsported i5 smaller and th~ viscos~ty somewhat hiyh~r, but~owing to tbe ~ig~ content of ~olvent the environmental poliution i~
even worse in the event of an accident during txan'spo~t~
It is al~o uneaonomic to ~ransport large guan~ities o~
water, which are needed only fc)r the sa}ce c~f sta~ility and ~iSGo~ity .
,~
Other Xnown electrod~po~ition baths contain powder ¢onc~ituents. All these çlectr~depo~$~i~n bath~, howeve~, ~h~ist largely of free-flowin~ th~nly ~iscous electro-depositio~ co~ti.ng ~inders. The start~ng materials are mixed wi~h water by th8 manufacturer and deli~er~d in the ~orm of ~ dispersion or frcely 10wing paste to thc u~er, where they are ~dditionally diluted with water. These ~ystems also are uh~conomio and ri~ky during transport~
DE la$d-~pen spe~i~ication 15 71 083 desçribe~ ~yste~s consisting ~f ~no~cally deposited liquid binders and t~e~moplastic powder~. The mixture of liquid anodic binders, ~round pla~tic~ powder J pigmentC and additional solvents is addi~ionally diluted with wate~ to p~od~ce ~h~
coating agent. EP laid-open speci~ication 0 05~ B31 describes cathode-depo~ited electrodeposition coa~ihg agents consisting o~ a~thode-deposited liguid ~inder~ and p~lver~lent i~nic pla~tics h~ing ~ glass tr~nsi~ion temperature ~ 300~, ~he plastics are solid and ~elt ~t elevated tempe~atures, but a free-flowing XTL binder is f ~L' ~l~p~aitio~ ~d to o~t~ a atablo b~th.
~E laid-open speci~ication 2Z 48 836 likewise describes ~athode-deposited electrodeposition coating age~ts ~ 2~S9726 ~prising one or more Cationic reBinS and a hon-ionic pla~tic~; pow~er. The catic:~nic resin is liçluid and optiohally c:ontain~; or~anic ~olvents. The el~:t~o-depoxition ba~h ~ ~ u~ed for ooating at temperature~ of e. g. 30~:.
DE laid-open speçifi~t~on 26 S0 hll ~escri~es electro-phoretiaally deposited coating agents c:on6~i~3tin~ ~f non-ionic plastics powders, optional pigments and a liguid polyme~ which is soluble or disper~ible in water or di~xol~ed in solYents. ~he resulting ele~trophoreti~ally qepos~table lacquers are deposited by k~own method~
temperatures be~ween 30 and 35~.
A common f ea~ure o~ these universally-known compo~itions of ele~tr~phoretically d~posita~le ~inde~ i8 th~t they need ~o ~ntain l~quid binder~ or binder ~olution~ in addi~i~n to the plastics powders, which are ~ d ~nde~
the deposition condit~on~.
~he composition~ a~e tran~ported either in on~ componen~
or in two di~fsrent component~ t~ the u~er. Thes~
components, o~ing tv the necessary e~se of ~ixing with wate~, are in a thinly-liqui~ or pasty state. The mixture~ can either be in solvent form, i.e. w~th a hi~h c~nten~ of organic solvents, or in aqueou~ for~. Even the aqueo~s f~rm, however, con~ain~ proportions o~ organic ~ lv~3nt3. The~e free- flowing substances tnUB~ be handled particularly carefully during t~ansport or refilling, sillce they will cause ~evere damage and danger to the environm~nt if they escape.
Another d~sad~antaqe of the hitherto-known methods is that in order to obtain a suita~le pumpable, ~h~nly-flowing consistency, considerable qUantities o~ organic ~o~vents (up t~ 50%) or up ~o 70~ water i~ needed. These ~. ~
~.
r~ ~
2~g~726 unnece~s~rily incr~a~e the volu~e ~or t~ansport. Al~o, some of th~ con~ention~lly used organic ~olvents adv~rsely affec~ th~ c~rod~po~it~on ha~h. The~e constituents may need ~o be remo~ed ~rom the ba~h and subsequently dumped in a safe manner.
The aim of the ~n~ention is to provide a method of cathodic electrodepocition which c~n be carrie~ oUt w~h b~nders which are safe and cause l~tle pollution and enable the ~e~uired v~lume tran~ported to ~e reduced to a mlnimum~
~his pr~blem i 5 s~lve~ ~y ~ ~a~hode-deposited electrodeposition material which i~ manuf~c~ured a~d delivered to t~e consumer in p4wde~ ~orm~ It has ~een ~ound tha~ a pulYerulent material o~ this kihd, after di&persing in water, optionally with additional known la~uer a~lt~Ves, op~lonally u6ln~ di~per~iny equip~ent, and h~ting ~f the aqu~ous dispersions, can be u~ed to obtain clcctrod~position baths ~ich are free from liquid ~ilm- ~o~mlng ~inders or binder solutions and are suita~le for ele~trodeposition ~oating.
The in~ention t~erefore ~elate~ to aqueous di~persions o~
one or mor~ cathod~-deposited thermosetting cati~nic fil~-~ormin~ binder~, characterise~ in that they are ~anuf~otured ~y heating a ~lurry ~f the binder or binders, u~ed in the form o~ powder haYing a particle size o~ 0.1 to 1000 ~m and a glass transition tempeXature of 35 to 130~
a) in wa~er, ~ t~e binder~ cont~in c~tionic ~roups, or b) in water and acid, if the binders contain cationi~
and/or basic ~roup~, to a tempexatu~e of 40 to gO~, for 5 minutes to 5 hours~
- 2~72~
q~he dispersions accordin~ to the lnvention a~
~ub~tantially ~ree ~rom l~quid or dissolved binder re~ins can }~e used to Goat an electrically conduc~iv~
substrat~ con~eated a~ ca~hode. ~oatings from the di~pex~ion~; u~ed as ele~::trod~o~ition ~aths can be obtained at tempe~atu~es o~ 20 to 80C.
According to the invention, pulverulen~ binder~ cc~nt~ining cationic g3~oups can be used in c~rd~3r to avoid ~ran po~t of liquid or pasty materials ~rom the binder manufacturer to ~h~ user, and t~u~ avoid the r~sulting econom~c di~advant~ges and pollution o~ thc ~3nviroP~en~.
Th~ pulv~rul~n~c binder~ u3ed in the dispe~sion~ acco~dinq t~ the invention a~e resins in powde~ ~orm which are solid und~r the condltions of ~anu~acture and transport ~ut melt at higher tempe~tures and ~ox~ a sm~oth f ilm . They are not cro~61inked whe~ in powder for~. They contain cationic ~roups or basi~: group~ convertible into cation~c:
group~, an~, are therefore dispcrsible ~nd remain ~table in the aqueous p~as~ ~t tempe~atu~es of 40 to gOC. T~e r~sins are usually not ~is~;olved in a true solution in the a~[ueous phase.
Optionally other conventional lacqu~r additives an~
constituents can be dispe~sed in the p~wders, e.~.
pigments, fillers, catalysts and other convention~
adjuvantc. The quantity o~ ~id necessary for neutr~lisation can als~ ~e distributed in the powders The~3e acid~3 ~re usually or~anic acids such ~s a~etic acid t formic acid, ~ulphamic a.cid, beh~oi~ acid or 1 actic acid.
q`he small ~uantities reguired can be àispersed without di~ficulty in the solid organi~ phase, so that even when the ac~ liquid the pvwder ~orm does~ not change.
Alternatively the resins conta.in~.ng p~ erulent CatiQr~iC
- ~ 206~726 or basic ~roups c~n be p~epared without additives, and pigmehts and optionally acid~ an~ othe~ additive~ and ~djuv~n~s can be added if nece~sary in the form of a conventional agueous pigment paste t~ the electro-deposition bath.
The disper~ion or the eleatxodepo~ition coa~iny agent i5 prepared ~rom the pulverulen~ starting material, op~lonally wl~n a pl~ment paste, a~ter ~llutlon Wlt~
water, optionally wi~h a~di~ion of aci~. To this end an aqueous s~urry i~ prepar~d ~n~ is prefer~bly ~oht~nuo~sly homogeni~ed, e.g. ~y vigorous ~gi~ation or pumping, and heated to a temperature of 40 to 90~, p~eferably over 60~. The ele~trodeposition ~ath i~ then ~eady for Goating~ at a temperature between 20 and 80C. A~ter dispersion, the ~ubstance can be ~ooled and re-he~ted fo~
d~p~sition~ The eleotrodepo~i~ion ~aths can be adjusted by the conventiona- adjusting agents.
The pulverulen~ resin~ used are powders having a particle size of 0.1 ~m to 100 ~m, preferably 2 to 40 ~m. CoarR~
poWder with a particle size o~ 100 to 1000 ~m may al~o be used. The par~i~le siZe of ~he powder will ~epend on the production facilities. Fine~y d~v$ded powder tends to produ~e more dust when poured. If equipment iS ava$1able for preventing ~he spread of du~t, the powder can have a par~icle siz~ of Q.l to 100 ~m. In oth~r cases, it i5 recommended to have a particle size of 100 ~o 1000 ~m.
Ano~hex possibility of avoiding dus~, which is ~npleasan~
and ~n explo~ion risk, i~ to produce powder slurri~s, e.g ~y a~itating 20 to ~0% by weight o~ powder, particle size 0.2 to 15 ~m, in 80 ~o 40~ by weight ~f deminerali~ed e~r~ p~slBnthiJ~n~n~u~yt~ f~
thixotropic, i~e. not liquid, and the~efore cannot pene~ate into the surroundin~ earth to any extent in the 8 2 ~72 6 event of ~n accident during tran~port. The pul~erulent resins have c~tion~ groups o~ basic group~ convertible into ~tiOhi~ grDUp~, so as to make the pulverulent re~ins di~per~ible in w~ter. The ~asic group~ are e.g. primary, secondary or ter~iary amino groups, ~hereas the cationic qroups ar~ ~g. quaternary nitrogon or qua~ernary~
phosphorus or tertiary sulphur atoms. These groups are firmly b~nded to the resin. rhe ~esins also cont~in reactive groups capable o~ arosslinking reactions, e.~. OH
groups, blocked N~ groups, p~mary ~d/or second~ry amino ~roups, SH groups, group~ o~pable of transesterification and~or gr~ups crosslinkable by Michael addition. The crosslinka~e groups can occur individually or in mixtures~
To give the pulverulent ~u~stance5 suffi~eht ~ta~ility in storage, the powdçrs mUst not coagulate. This i~ helped by the high gla~s transi~ion ~empe~a~Ure of the pow~er~, which is measured by the Differential S~nning Method, DSC, and is ovex 350C, pref~rably over 45~C. The uppe~
limit of the gla5s transi~ion temperature ghould be 130C, prefe~ably 100~, to ensure that the powders lique~y an~
~orm a smoo~h sur~aae ~ur ~ ng stoving.
~oagula~ion of the powders can be redu~e~ or prevente~
e~. by incorporating pi~ents by dispersion.
Alternatively the ~round binder powders can be surf~ce-treated with non- sticking organic or inorganic addit~ves. For example ~he powdex~ can be sur~ace-trea~ed with highly di~persed ~ilicic a~id. The resulting powdexs ~emain free-flowin~ and storable for a p~ticularly long time~
T~e p~lverulent cationi~ qroups or resins convertible into cationic groups can be ca~hode-depositea ~inders or mixtu~es thereof. These bind~rs ~an b~ self cro~slinXing , 20~9726 or extern~lly c~o~linked. In the case of ext~rnally cro~slinked binderq, cros~lin~ing agents c~n be added to the bin~er~ or ~inder mixture~ to obtain a chemi cally c~rosslinkable filr~. The c~ntent of cro~slinking agent in th~ powder can contain ionic groups. Alternatively it may be free from ionic groups, pr~vided it is us~d in~small proportions of less than 40% ~y weight r~lative to ~he total weight of binder. ~he binder components ne~ "ot individually h~Ye the ~tated gla~ transi tion ~empe~atures, par~i~le ~i~e~ and ionic g~oUp5. :s~t iS
sufficient if the mix~ure of film-forming r2sins or the mixtllre thereof with oro~link~ng agen~s meet~ the aiorementioned specif ications overall .
The pow~ers are e.g. amino epoxy resins obtained from poly~l~cidyl ethers with more than 1, preferably at le~st ~.S, epoxy ~roup~ per molecule, a~ter reaction with ami~e~
or compound~ o~ntaining ~ino g~oups. Polymex.
containing cationic or ~a~io gro~ps dnd ~ormed from ole~inical~y uns~turated polymerisabl~ monomers may also be used, AminP epox~ re~in~ are pre~erred. As mentioned, the bind~rs contain crosslinkable ~u~ctional gro~ps sueh as OH groups, blo~ked N~O groups, primary and~or s~condary amino groups, S~ groups, group~ ~apable of tran~-estexification and~or groups crosslinka~le ~y M~ahael addition, pre~ent individuall~ or in mix~ures.
The ~esin.~ used in th~ powders are preferably ~ho~e conYentionally provided for ~athodic el~ctrodeposition coatin~, such as tho~e h~therto use~ in liquid systems, e.g. a~ solutions ~ dispersions. The powders ~d~ ~e ~roduced from the liquid systems by removal of the ~olvents, o.~. by distillation and op~ional subsequen~
grinding. They can also be prepared in the melt and grouhd ~fter cooling. The b~5ic resins used in the powde~s can e.g. be amino epoxy re~ins or resin~
206~726 containing ami~o y~oup~ and obtaine~ by polymerisat~on o~
un~aturated monomers. The resins pre$e~ab1y have an amine nu~ber of 45 to 120 mglg KOH and a hydroxyl number o~ 50 to 400 mg/g KOH~
Examples of basic resins used in the powders are ~escribed in ~he l~id-open specifications EP O 08Z 291, EP O 234 395 ox EP ~ ~09 587. The resins prepared ~herei~ by ~
dissol~in~ in org~ic solvents can be ~onverte~ into powder ~y removing the solvent, e.g. by di~illation ~e.g.
i~ a thin-laye~ evapor~tor) and subsequent grinding. The s~bstances are amino epoxy resins b~sed on glycidyl ethers with more thah 1 epoxy group per molecule, preferably ~a~ed on ~i~phenol A or novGl~k and containing conventional primary, ~econdary and/or tertia~y ~mino ~roups. The amine number i~ usually between 45 and 120.
The amine nu~er oan be used to in~luence the di~persi~ility of the resin powder, and also t~ influence the quality of the. surface of ~he crosslink~d film o~
la~uex. If the ami"e number is too sm~ll, the resins canno~ disperse sufficient~y and do not form a ~t~ble di~persion. If the amine num~e~ is too high, the re~ult i~ a poor surface with inadequate prote~tion a~ainst cor~osion. These r~ins have OH group~ ~ additio~ to amino ~roup~. The hydroxyl number is preferably about 50 to 50V. ~l~ne acclve nyaroxyl ~oups~ ~y~ Pr wl~
reactive amino group~, are responsible f~r ~rosslinki~g.
Their num~er is preferably at ~ea~t 2, and particularly preferably ~t least 4 per molecule. ~r ~he de~ree of crosslinking of the ~ilms forme~ from the powders is too low, the films have poor mecha~ical p~operties after cro~slinkin~ the degree of crosslinking is ~oo high, the cros~linked ~ilms are brittle.
Other functional ~roup~ can be introduced e~ by reac~in~
OH or NH ~roups in the ~e~in mol~cules w~th isocyAnate~
- 2~72~
c~ntaininy the required fun~tional groups. If conventional semi-capped diisocyanate~ are used as the reaction component, ~el~ osslinking bin~ers are p~oduced via capped isocyana~e group~. O~her functional group~ can ~e introdu~ed, e.g. via ~meth)acrylic acld derivatives.
~h~ resulting ~inder~ will then con~ain ~, ~-unsat~u~ated carb~yl ~roup~. The binders can opt~onally b~ modified w~th other ~unctional groups. Anoth~r method o~ ~ynthesis i5 descri~ed e.g~ in EP-o OS~ ~31, where functionalised amino epoxy resin~ are produced in s~lid ~ol~ent~free form. ~or ~xample, epcxy resins i~ ~he melt are reacted ~ with ~mino ~lcohols and further processed in the mel~, optio~ally after solidifying to powder.
Other example~ of ~ros~linkable binders usable in the powders ~re de~cri~ed e.g. in EP-O ~61 385. These substance~ also ar~ resins dissolved ~n org~ni~ sol~en~s and conYertlble in~o powder as previously described~ ~hey ar~ polymers obtainable by polymerisation of radiaally polymerisable un~a~urated ~onomer~, at least part of which have ~unctional groups ~uitable for dissolvin~ or cros~linkin~ For exa~ple u~e can be made o~ saturated ~trai~h~-c~aih or branche~ a~ryli~ or ~et~c~ylic ~id esters, glycidyl ~m~th~ acrylates, allyl glyci~yl ethers, ; vinyl ether~, styrene, hydroxy ~meth) acryl~t~s or oth~r ~unctionali6ed aarylic acid an~/ox methacxyl~c a~c~d derivative~. Amino groups necessary for ~olubility can ~e ~ntroduced e.g~ by reactin~ epoxy yroups with secondary amine~ or amino alco~ols, o~ can be incorparate~ ~y p~lymerisation via compounds containing am~ no g~oup~ .
~he glass t~ansition temperature can be influenced via the nature of the monomers. The ~onomers can also be used to adjust the ~umber o~ crosslinkable group-~.
A~ mentioned, the.pulverulent res~ hS can be self-20~72~
crossli~king or externally crosslinXed. ~he follo~i~g resins are ex~mples of ~uita~le cro~xlinkiny agents:
~iazine resi~s, alkoxy methyl (~QthJ ac~ylic ami~e copolymers, blocked isocyanates, res~ns capable of trans-ssterification or tran~amidation, resin~ with ~ermin~l d~u~le ~onds or cros61inking agents capabl~ of Mic.hael reac~ion. Cxosslinking agentS of thi~ ki~d are curre~t in the literature and aescribed e.g. in EP l~id-open -~pecification 0 245 7~6, DE 34 36 345 or DE 37 1~ ~05 These ~ub~tance~ also ~re resins di~olved in organic solven~s ahd converti~le into powder ~ previousl~
described. In s~e c~ses they can also be produced in ~he substance and pulverised. The powders can ~ uni~o~m or in the form of mixture~ The individual powder parti~les can be homogeneous or he~erogeneou~ ~ixtures ~an ~e prep~red ~y ~ixing pr~fabri~ated powder p~rticles to~ether ana opllonally grlnu~ IU~ ~lL~lla~lV4'y ~lJ~y ~
manu~actured by processing mixed solutions until they are free from solvent and grinding them. Pre~erably the work is car~ied out so that al~ the powder particles have ~onic groups. If for example a non-ionic resin is used, it can bo proc4~0Qd with ~n lnni~ r~Rin tn nhtA;n he~.Rrn~P.nP.nu powder particles having ionic char~es.
Resin~ prod~ced in organia solvents are converted into ~
~orm containin~ little or no ~olvent. A low-solvent ~orm has a solven~ content which can be used to obtain a non~
sti~ky powder with a glas~ transition te~peratUXe of 35 to 130~. Alte~natively the Pinders can be p~oduced solvent-free, e.g. in the melt, ~nd th~n converted $nto powder.
Additive~ and pi~men~s can be contained in the powder~
~hey can be added at any time before y~inding. For example they can ~e added to solid re~ins Xor grinding or to a resin already in solution before the sol~e~t has ~een remo~ed. After removal of ~he ~olven~, the res~n~, 13 20~9726 optionally containing additive~; and pigmsnts, are ground to ~he necessary f ineness in a suita~le apparatus. T~e conte~t o~ solvents c)r licr4id constit:uent~ mus~ be so low ~h~t the resulting pow~ers do not co~gulate and can ~till flow freely afte~ ~ prolonged period. Suitable grinding appar~tU~ and ~ethods o~ grinding powder~ are known and freguently described in the ~iteratur~.
..
Small quantities of organic or inorganic acid~, e.g.
~or~i~ acid, ~cetic acid, l~atic acid or ~lkyl phosphoria acid, are ne~essary to neutralise the binder or to ~orm cationic groups. The acids used aan be li~uid or ~olid, e.g. ben80ic acid, sulphamic ac~d or ~lycolic acid.
~ptionally, polybasic ~cids ~uch as c~tric acid or ox~lic acid can al~o be usedO A~id anhydrides or ea~ily h~dr~lysed este~ oan ~lso be ad~ed. The follo~in~ are exampl~ thereof: acetic acid anhy~ride or maleic a~i~
anhyd~i~e or p-toluene~ulphoni~ acid meth~l e~ter. If the ne~tralising ~gents are added via the po}ymer powder, solid neutralising a~ent~ are pre~erred~
Suitable pigTnents can al60 ~e incorpora~ed in the polymer powders containing ionic groups. The pigments can e . ~. ~e titanium dioxide, carbon bl~k, organia or inor~anic po~dered dyes, fine~y-divi~ed filler~ such as highly-dispersed silicic acid, p~lverulent catal~sts or anti-corrosion pigments such as lead ~ilicatès.
The fillers can also be polyme~ micropart~¢le~ which do not melt under the sto~ing conditions. Cros~lin~ed polymer micropa~tiGles are preferred. The poly~er microparticles sho~ld preferably not ~ontain any ionic g~oup6 on the surface. Cationic groups, however, may be present on the surfa~e. They must be sufficlently crosslinked not to li~uef~ with the bind~r when stoved.
~L ~ h~ld b2 ~ 20 ~m, prn~ar~ly ~ m.
:
2~6~72~
~hey can b~ inc~rpora~ed like normal pigments ~n the binde~ or the pigment pa~e~. The pDlymsr particle~ may op~ion~lly carry surface unctional group~ such as OH, SH
or ~ster group~. These can react wi~h the b~nder during stoving. ~he po~ymer m~¢roparticles can ~e manu~actured e:.y. Vll ~ 1~ v ' ~ ~GL~ ~r r~~
or p~enol ~ormaldehyde resins.
The pi~m~nts a~e ~inely dist~ibuted in the binders in known manner, e.g. ~y ho~ageneously mixing ~he binder with the pigments in a sultable ~ixer, e.~. an extruder. The mixin~ process ~n also ~e assi~ted by elevated temp~rature. The mixt~e o~ binder and pigment is then commin~ted ln known apparatu~ ~nd ground to the necessary~
fineness in a mill . ~he pigmen~ particles are then ~o~ted with ~he polymer po~der and have a sultable particl~ size distribution.
Th~ pulverulent resins ~ontain~n~ ionic groups and ~ed a~cordinq to the lnvention can al~o be pro~uced without a~ding a pigment. In that aase a clear l~cquer ~oating is .
o~tained after deposition and ~toving. In another method, the binders are added in the ~'orm of pu~verulent pigment-free resins to the electrod~position ba~h and the pigmentsare a~ded to the b~t~ after ~eing prepared sepaxately~
The piqment preparat~ons can be obtained from ~onventional pi~ment paætes, produced by grindin~ pigments with wetting ~gents qr "paste resins" (binders used in ~rinding). For example EP laid-open specifi~ation O 183 025 describes pa~te resins based on epoxy resins with par~i~lly reacted oxazoli~in~ rings. The ~itation also des~ribes how pi~meht pastes are produ~ed ~rom ~he aforementioned binders ~oget~er with conventional pigment~. ~he pigmeht ~ C~ ~c~ h~ Llon elh~llld profr~hl ~
be aq~eous. They can be p~epared by the user and added to 2 ~ 2 6 th~ di~persion~
The pigment pa~tes are added in a proport$on of 0 to 20, preferabl~ O.5 to 20 partQ per 100 part~ o~ bind~r powder, preferably 2 to 10 parts. Owing to t~e s~all quantity, they cannot form films by themselves. They C:~n ~e ~o3.u~le or dispersible in Wate~. They can contain ionic groups or ~Q present without ionic ~roup~. Preferably they~ontain functional groups which can ~eact with the film-f~xming resin~ rhe paste binders should be p~e~ent in aqueoug disp~rsion and ~ontain only ~mall propo~tion~ of solvent.
Th~ paste resin~ are e.g. ~inders based on epoxy resin~, al~yd ~e~ln~, polyurethane resins or polyether~.
Non-~onic paste binder~ ~an also be prepared, e.g. base~
on a s~ralgn~-Gna1n or ~r~ u ~y~ y~ yly~v polypropylene glycol wi~h or ~ithout terminal gr~fted ethylehe ~xide compon~nts.
~xamples of pa~e re~ins are de~ri~ed e . g . in EP
pen specification 0 108 088~ EP O ~83 0~5 or EP 0 ~?0 877. They ar~ wettin~ agents or binders having a high capacity to wet pigment~ and ~iller~. ~hey should be easily co~npatible with the binder in the a~ueous coating agent ~nd should not al~er the properties of the binder mixture. They can optionally become crossli~ked with the binder ~ia functional group5. These pa~te xesins h~ve basic ~unction~l groups which, when neu~ralise~l with ac$d, make the paste.re~in~ disp~rsible in waterO
Alternati~ely, partly-re~cted catio~i~ functional groups m~y be present ~n the paste re~ins. Example~ o~ ~uch fun~tional ~roup~ are quaternary nitro~en atoms, quaternary phosphorus ~toms or ~ertiary sulphur 9TOUpB.
The sol~bility of the paste binders ~ 5 influenced via the number of these neutralised or ionic group~7 20~972~
T~e numb~r of cationic group~ can ~e so high that the pa~te re~ins c~nnot be ~epo~ited on the catho~e ~y themselves, i.e. do not produc~ a homogeneous uni~Drm fil~.
Preferably the paste resins have functiona~ groups for crosslinking to th~ ~ilm-formin~ resins, e.g. prim~ry or ~econd~ry OH ~OUp~, ~ea~t~ve amino gr~up-~, e~tet~qrollp~
capabl~ of tran~e~te~ification or c~pped l~o~yanate~, met~ylol groups or alkoxym~thyl groups, pr~ferably methox~me~hyl groups~
Piym~nt paste resins based on ~odified epoXy resins can be used e.g~ i they contain at least one, preferably at lea~t two epoxy group , where 50 to ~00 mol % of ~he free epoxy ~XOUp5 are rea~t~d with ~ prim~ry-ter~iary diamine, the ~x~ess epoXy groups are optionally previously reacted with sQconda~ or primary amine, and 80 to 100 ~ol % of the secondary amino groUps present have been re~cted with a car~onyl compound to form oxazo~idine structures. The~e binding agents can be converted into a~ a~ueou~ dispersio~
~y adding an acid. The molec~lar weight o~ ~he modif ied epoxy r~sin~ ~hould be 400 to 10000. The hydroxyl num~e~
:~nOUla De ~ l~U my r~ullt~ ~L'I~ ~' a~y ~ lVU IU~ n/y~
content of ~rga~ic solvents sh4uld be below 30~.
Example~ of u~ble non~ionia pa~te re~in~ ~r wetting ~gents ~e descri~ed in DE laid-open spec~iaations 30 18 715, 36 ~1 6~g and 26 0~ 831. They are no~-ionic re in aomponents which should have a good capacity to wet pigments an~ fillers~ They ~ust be eas~ly compatible with th~ binder system of the aqueous ooating agent and must not alter the proper~ies of the binder o~ binder mixture.
It is adv~ntageous i~ these pa~te binders can rea~t via ~unctional ~roups with the binder in the aqUeQUs coating agent. These non-ionic paste resins have good solu~ility 17 2 ~72 in w~te~. They ~annot be deposited at the ~hode by ~hemse}v~s, but only togPther with the ~inder system.
Samples of such substances are polyalXylene glycols.
Alternatively, non-ionic pa~te resins c~n be derived from epoxy re~ins, preferably from aro~ati~ epoxy resi~s which have been made more soluble in water vi~ polyethyiene oxide or polypropylene oxide component3, or alter~atively .
the non- ionic pa~te resins can be non-ionic wetting agents based on melamine or phenolic resin.
Pigment pastes can ~e made from the known paste xe~in~.
For exa~ple demiheralised water ca~ be added to the paste resin, opt~onally after it has been ne~tr~li6ed wi~h an a~id and thus made ~ispersible in water. Pi~ent~, fil~ers, ~atalys~s, anti-corrosion pigments, inorganic or organic colour pigments and othe~ additives a~e added to the thin-~lowing mixture. The additi~es are, for example, anti-foaming agent~, wetting ~gents, le~ellin~ agents or anti-crate~in~ a~ents. After th~ mixture has been thoroughly hom~genised, the viscosity o~ the pigment pa~te is ad3usted with c4mple~el~ dem~heral~Sed water, foilowed by grin~in~ ~o the necessary finene~s ~n ~ con~entional grinder~ e g. ~ pear~ mill. Th~ resulting pi~m~nt p~stes are aqueou~, p~pa~le and have good stability in storage.
The ele~trodeposition coating agents used ac~ordin~ to the inVention can be ~anufactured as follows: the polymer powder, thoroughly agita~ed and ho~ogenised, i~ slow~y added ~o the amount of completely demineralise~ wa~er necessary for the electrodeposition ~oatin~ ~ath.
ca~e mus~ be taken ~hat the polymer powders do not coagulate but ~e~in ~inely dispersed. If the a~ueoug powder slurry does not ~low freely, i~ ~an be ~etered through a pump for thick matter. Op~onally a pigment .~ ~
18 2~63726 paste ~an be added, with tho~ough mixing, to the ~in~er dispersion. Alternatively the pi~ment~ c~n already be pre5ent in the pol~er powde~, or ~ pigment-free K~L
system can be used. Preferably the pigments ar~ dispersea in the polymer po~der when used~
Aft~r thoroug~ ~omogeni~tion, the ele~trodepositi4n coating bath is hea~ed for S minu~ex ~o 5 hour~.
Alternatively, homogeni3ation can ~e bro~ght a~out directly at t~e ~eposition temperature nf the ~ath. The heating t~mp~rature is about 40 to 90~, pre~erably 50 to 80DC, particularly prefer~bly 60 to 75OC. In the proce~
the bath is continuously homo~nis~d. Preferably the h~ating temperature is chosen from the prcviously-mentioned ~ange to mat~h the glass tranSition ~e~pe~ture of the binder powde~ u~ed, i~e. a moderate heAting te~perature ior a low glaas transition t~mperature and a hRn~,in~ t,Rm~r~tl~r~, frnm tlh~, uD~,r ~f~r~,~Rntinn~ r~nu nt. hi~h~ ~aa~ t~an~ n temue~atl~e~, ~he h~tinu temperat~re ~hould be chosen so ~hat it is not ab~ve ~he melting-point of the polymer used.
I~ the electrodeposition bath is used to top up an exis~ins ~ath, t~e pulverulent electrod~position lacguer and binder ~ompo~ition and optional}y the pigment paste ~ay also be dispersed in the exis~ing e~ectxodeposition bath. After h~ogeni~ation and heatin~ to elevat~d tompor~tura, ~h~ thnrli~ Q~ trnrl~l~n~;t inn hn1-h ~ rP~ly ~or coating.
~he cathodic electrodeposition bath is used fo~ coating at ~0 to 80DC, pre~erably 30 to 60~C. The ele~rodeposition coating agent is st~ble at these temperaturl3~ and does no~
~ecompose . The method according to the invent ion is o~
particular use e.g. for c:oating industrial products made . of ~netal, t:onductive plastic:s or electricall~r conduct~ng 7 ~ ~
lac~uer layers. T~e guality of the coatin-3s ~ill depen~l Oh the h2~ture of the products. Produots not expos~d to the weather, e . g . sl~elves, coated ~y the method can be given a di~ier~nt grade of powder from t~at U~;e~ f or car bodies, The powdexs used for washing-machines no~m~lly h~ve good resistanc~ to alkalis after stoving, in~ad~tion ~o ot~er import~nt prope~ties. ~he ranqe of indu~trial products wh~ch can be coated ac~ording ~o the invcntion is the same as for exi~ting elect~odeposition baths. Af~er deposition, the coatings have ~ood propertie~, i.e. good ~r~ rmlnn ~n~l ~rlh~inn ~.n t.h~ ~r~ace un~neath, coated parts are Purther treate~ in conv~n~ional manner, e.g. they are washed clean ~nd cro ~linked at ~levated te~perature. Wet-in-wet f~rthe~ co~ting is also possible.
Conventional ad~usting agents can be added to the electrodeposition coating agent~ according to the inventionn If necessary, for example, acid can sub~e~uently ~e add~d to the ~ath, i.e. the aforementioned acids conventionally used in elec~rodepo~ition coating.
Also, substances can be added to prevent the ~ath from foaming, or levelling agents s~ch a~ fatty alcohols containing 12 - zo car~on atoms, or ~u~tances for adjusting the l~yer thickne~s or anti- ora~ering additives if neces~ary, e.g. as described in D~-OS ~0 18 87fi. The resulting cathode-deposited electrodepo~ition coating baths give smooth level film~ a~ter crosslinXing. The edge~ have good properties as regards re~istanae to co~rosion or weatherinq. ~he coatin~ have good resis~ance to gravel.
The resultin~ C:o~tings on condu~tive metal substrates can b~ single layers, o~ alternativcly additional laye~ ~uch as fillers or cDvering la~quer~ can be applied to ~h~
primin~ layers. The resulting single-~ayer or multilayer coatihgs have a gDDd appearance.
2~72~
~he in~entio~ wi~l now be explained in detail with reference ~o v~riou~ exam~le~. All percentage6 are by weight~
~e~in a~mpl~
A. As per EP-B-0 012 463, 3~1 g diethanol~mine, 189 g of 3-(N,N-dimethylamino)-propylamine and 1147 g of an ad~uct fr~ 2 mol hexane diamine-1,6 and 4 mol gly~idyl ester of ver~ati~ ~c~d (cardur~ E10) wexe added to S~73 g bisphenol ~-epoxy resin ~poxide e~uivalent weight approx. 47~) in 3000 g of ethoxy propanol. The reaction mixtur~ w~s heated with agitation at 85 to 90~C for 4 hours and then ~ep~ at 120C for 1 hour. The solven~ was then distille~
off in vacuo in a thin-layer evaporator and ~he resulting ~in tg1A~ Ln~ n t!~:mpc~u~ ~ 40n) u~a a~minu~cd to a si~e of ab~t 5 m~ in ~ suitable apparatus.
B. 160 g of ~prolactam was ~lowly added with agitation at 70C to 453 g o~ a ~olu~ion of a ~e~ction product ~rom 3 mol isophorone diisocyana~e and 1 m~l trimethylol propane ~7~ in ethyl acetate). The reaction ~ix~ure was then kept at 70C until the NC0 content had fallen to zer4. ~he solvent was ~he dist~lled o~ in vacuo in a thin-layer evaporator and the resultin~ re~in ~glass transit~on temperature ~ 40~C) was ~o~nuted to a size of a~out 5 mm in a ~uitable apparatus.
~e resulting resins a~ per A and ~ were mixed in ~he ratio 8 : 2 (solids).
Pi~nt paste example 2:
A. g50 g o~ an epoxy ~esin based on bispheno~ A (2 epoxy equivalents) was d~ssolved in 633 ~ xylene ~nd added at 60 21 2~7~
~ ~OnQ t~ ~ ~ni~tsur-- ~t 100 y Q ~th~l h~x~l~ils~ ~
diethyl aminopro~yl ~mine. The t~mperature wa~ pt ~elow 75~. A~ter all t~e epoxy groups had ~e~an compl~ely us~d up, 59 g paraform~ldehyde (91%) wa~ added. The mix~ure wa~ heat~d until the ~eaction water had heen azsotropically ~o~d.
The xylene was then distilled off in a ~atch and the binder, af~er ~dding 780 mmol acetic acid per loO g solid resin, was dilu~ed with deionised ~ater to a solid ~ontent Qf 30%~
B~ 143 ~ of a commercial aluminium ~ilic~ta powder, 10 g carbon bla~k, 16 g pyrogenic silicic a~id and 8 g dibutyl tin oxide powder was added t~ 53 ~ o~ pa~ta resin A ~30%
in water) in a high~peed agitator. ~he solids wer~
ad~ust~d to a~out 44% -with 115 g completely demin~ralis~d wal,~ VUII~ y ~ y <,~
pigment paste~
Pigmont paste example 3:
125 ~ ~f a commercial N-butanol etherifi~d ~la~ine/
~ormaldehyde resin t75% sol ids in butanol, vi~co~ty 6500-6800 mPas) w~re ~i~ed with 24 g di~tyl tin oxide, 5 g carbon ~lack~ 160 g titanium dioxide and 35 g bu~oxyet~anol and gxound in A suita~le mill to a fineness ~elow 5 ~m.
Lacquer ex~mpl~ 4:
Po~dered resin as per example 1 was mixed ~ith 0.3%
dibutyl tin dilaura~e ~nd ground in a suitable mill to finenes~ below 25 ~m.
1.0 g of a co~mercial ~etti~ ag~n~ ~50%) and 5.5 g for~ic 2~9726 acid ~50~) wer~ add~d to 1000 g completely demineralised water. 150 ~ of the previously-descxi~ed binder powder was ad~ed with agitat~on. ~he ~a~h was ~ade up to 2000 g with ~o~pletely ~eminer~lised w~er. ~h~ ba~h wa~ he~ted to about ~o~c for 15 m1n~tes and agitatedA It remained stable and did not pr~cipi~at~.
L~e~W~ a~ a~tAw~olcw~r7no~ nu~ Q~ ~nll m~terial a~here~ firmly. The films o~ained after stoving had a ~od s~fac~ and a layer thickness of about 25 ~m and 20 ~m.
~acguer example 5:
A. lO g di~lltyl ~in ~xide, 3 g oxalic a~d, 7 g carbon bla~ and 30 g titaniu~ dioxide we~ added ~o S00 g o~ the bind~r mixture in exampl~ 1 and wer~ homogen~ou~ly mix~d in suitable apparatu~ and ~hen ground to a siz~ of les~
th~n 40 ~.
B. 7.~ ~ wettin~ agent (50S) was added to lOoO g completely dem~ne~alised water, ~ollowed by 120 g of the powder in A, with vigorous agitation. The bath was heated to 70C for 30 ~inuteæ and was then ready ~or coati~g.
T~e metal sheets wexe coated at 30~ and at 55C, wa~hed clean and then sto~ed a~ 180~C for ~0 minutes. The film~
had a thick~ess between 20 and 30 ~m and a good su~dce.
Laagu~r e~ample ~:-A clear la~quer was made from 5 g we~tin~ agen~, 7~5 gformic acid, 1000 ~ water and 150 g resin powder as per example 1 ~round to about 30 ~m). The lacquer was made up ~o ~uu~ g wlth w~t~r. ~ ~r ~idl l~v~ll;~y agent/butyl glycol ~l ~ l) waæ a~de~ and 132 g of a 2~972~
pigm~nt paste as per example 2. ThQ lacquer w~s h~ated to 600C and applied a~ter co~liny.
Lacouer examnla 7:
A clear lacquer wa~ made from S q wetting agent, 7.5 g ~ormic acid, 1000 g water and 150 g resin powdRr as per examplc 1 ~ground to a~ut lo ~m~. 4~ g of a pi~m~nt pa~te as per exa~pl~ 3 was ~dded to the mixt~re With ~igo~ agitation and th~ lacquer ~a~ heated to ~0C.
~he lacquer was diluted with ~000 g complRtQly de~ineralised water and ~ould be applied after cooling.
.
~cguer exa~ple 8:
A, 10 g dibutyl tin oxide, ~1 g ~ulphamic a~id, 7 ~ carbon blaa~ ~nd 30 g tltanium dioxide were added ~O
500 g of the binder mixture as per example 1, uniformly mixed in ~uitable apparatus ~d then ground to ~ 40 ~m.
R~ 7. 5 ~ wettin~ agent ~SO%) wa~ added to 1000 g c~pletely deminerali~ed water, ~ollowe~ ~y 120 g o~ the powder in A, with vigorous agitation. The bath wa~ heated t~ 7~c for 30 ~inute~ and w~s then ready for coating.
The metal sheets were coated at 30DC and It 55C~ washed clean and then ~toved at 180~ for 30 minute6. The film~
had a thickness betweeh ~0 ah~ 30 ~m ~nd a good surface.
.
Hexberts Ge~ellschaf~ mit b~chr~nk~r Ha~tung An aqueou~ ~3pcr~ion ~ a ~thoa~-~epo~ited bin~er, an~ a ~et~ of m~nu~ ur~ a~ U3~ t~er~o~' The invention rel~te~ to aqUeous dispersions o~ càthode-depo~ited, ther~nosetting film-forming binderEi fc;~ ooatin~
an electri~ally conductiv~ s~bstratR conne~ted as cathode.
thodic elec~rodeposit~on coating is a known method of læ.cq~e:ring electrically condu~ ive surfaces, e.~. surfaces o~ metal or electrically corlductive pla:tics or electrica~ly ~onductive lacqu~r layers. In t~e method, the ~acquer con~ituent~ ar~ pracipitat~ad ~rom an elea~rodepo~:ition bath on to the s~rfa¢e of a workpi~ce connected a~: c~h4d~, usin~ direct current~ The coagula~ed lacquer con3~ikuents ~re ~en liquef ied and c:~osslinXed by hea$1ng to ele~ated temperatures. The re~ul~ homo~en~ous smooth film wi~h high meahanical and ¢hemical stability. The p~po~e of the ~ilm is to prote~t the su~strate ~rom mec~anical damage and cor~osion.
The usua~ method of producin~ e~ectrodepositioh baths is to tran~p~r~ liquid or pa~ty water-containin~ or ~o~vent-containin~ mat~rial~, e.g. binder disp~rsions r pi~ment pa~tes or sol~ent-containing pigm~nt and bind~r mixtures, to the co~ing installation, whe~e these pre~pr~ducts ~re diluted wi~h water ~o obtain the electrodeposition ~ath ready ~or use. After ho~o~enisation, the e~eatro-depositio~ bath ~an be used for coating.
In this method, it is necessary to transport large guantities ~$ water and liquid ~inders, si~e bind~r disp~rsions must have onl~ a relativ~ly low cont~n~ of - 2~69726 ~olids i~ they are to have the l~w viscosi~y required for proce~slng~ If an accident occurs during transport ~f ~e~ thinly viscous material~, there is a ri~k that the s~rroundin~ earth will ~e contaminated~ If ~olvent-containing system~ ~e txansporte~, the volu~e tr~nsported i5 smaller and th~ viscos~ty somewhat hiyh~r, but~owing to tbe ~ig~ content of ~olvent the environmental poliution i~
even worse in the event of an accident during txan'spo~t~
It is al~o uneaonomic to ~ransport large guan~ities o~
water, which are needed only fc)r the sa}ce c~f sta~ility and ~iSGo~ity .
,~
Other Xnown electrod~po~ition baths contain powder ¢onc~ituents. All these çlectr~depo~$~i~n bath~, howeve~, ~h~ist largely of free-flowin~ th~nly ~iscous electro-depositio~ co~ti.ng ~inders. The start~ng materials are mixed wi~h water by th8 manufacturer and deli~er~d in the ~orm of ~ dispersion or frcely 10wing paste to thc u~er, where they are ~dditionally diluted with water. These ~ystems also are uh~conomio and ri~ky during transport~
DE la$d-~pen spe~i~ication 15 71 083 desçribe~ ~yste~s consisting ~f ~no~cally deposited liquid binders and t~e~moplastic powder~. The mixture of liquid anodic binders, ~round pla~tic~ powder J pigmentC and additional solvents is addi~ionally diluted with wate~ to p~od~ce ~h~
coating agent. EP laid-open speci~ication 0 05~ B31 describes cathode-depo~ited electrodeposition coa~ihg agents consisting o~ a~thode-deposited liguid ~inder~ and p~lver~lent i~nic pla~tics h~ing ~ glass tr~nsi~ion temperature ~ 300~, ~he plastics are solid and ~elt ~t elevated tempe~atures, but a free-flowing XTL binder is f ~L' ~l~p~aitio~ ~d to o~t~ a atablo b~th.
~E laid-open speci~ication 2Z 48 836 likewise describes ~athode-deposited electrodeposition coating age~ts ~ 2~S9726 ~prising one or more Cationic reBinS and a hon-ionic pla~tic~; pow~er. The catic:~nic resin is liçluid and optiohally c:ontain~; or~anic ~olvents. The el~:t~o-depoxition ba~h ~ ~ u~ed for ooating at temperature~ of e. g. 30~:.
DE laid-open speçifi~t~on 26 S0 hll ~escri~es electro-phoretiaally deposited coating agents c:on6~i~3tin~ ~f non-ionic plastics powders, optional pigments and a liguid polyme~ which is soluble or disper~ible in water or di~xol~ed in solYents. ~he resulting ele~trophoreti~ally qepos~table lacquers are deposited by k~own method~
temperatures be~ween 30 and 35~.
A common f ea~ure o~ these universally-known compo~itions of ele~tr~phoretically d~posita~le ~inde~ i8 th~t they need ~o ~ntain l~quid binder~ or binder ~olution~ in addi~i~n to the plastics powders, which are ~ d ~nde~
the deposition condit~on~.
~he composition~ a~e tran~ported either in on~ componen~
or in two di~fsrent component~ t~ the u~er. Thes~
components, o~ing tv the necessary e~se of ~ixing with wate~, are in a thinly-liqui~ or pasty state. The mixture~ can either be in solvent form, i.e. w~th a hi~h c~nten~ of organic solvents, or in aqueou~ for~. Even the aqueo~s f~rm, however, con~ain~ proportions o~ organic ~ lv~3nt3. The~e free- flowing substances tnUB~ be handled particularly carefully during t~ansport or refilling, sillce they will cause ~evere damage and danger to the environm~nt if they escape.
Another d~sad~antaqe of the hitherto-known methods is that in order to obtain a suita~le pumpable, ~h~nly-flowing consistency, considerable qUantities o~ organic ~o~vents (up t~ 50%) or up ~o 70~ water i~ needed. These ~. ~
~.
r~ ~
2~g~726 unnece~s~rily incr~a~e the volu~e ~or t~ansport. Al~o, some of th~ con~ention~lly used organic ~olvents adv~rsely affec~ th~ c~rod~po~it~on ha~h. The~e constituents may need ~o be remo~ed ~rom the ba~h and subsequently dumped in a safe manner.
The aim of the ~n~ention is to provide a method of cathodic electrodepocition which c~n be carrie~ oUt w~h b~nders which are safe and cause l~tle pollution and enable the ~e~uired v~lume tran~ported to ~e reduced to a mlnimum~
~his pr~blem i 5 s~lve~ ~y ~ ~a~hode-deposited electrodeposition material which i~ manuf~c~ured a~d delivered to t~e consumer in p4wde~ ~orm~ It has ~een ~ound tha~ a pulYerulent material o~ this kihd, after di&persing in water, optionally with additional known la~uer a~lt~Ves, op~lonally u6ln~ di~per~iny equip~ent, and h~ting ~f the aqu~ous dispersions, can be u~ed to obtain clcctrod~position baths ~ich are free from liquid ~ilm- ~o~mlng ~inders or binder solutions and are suita~le for ele~trodeposition ~oating.
The in~ention t~erefore ~elate~ to aqueous di~persions o~
one or mor~ cathod~-deposited thermosetting cati~nic fil~-~ormin~ binder~, characterise~ in that they are ~anuf~otured ~y heating a ~lurry ~f the binder or binders, u~ed in the form o~ powder haYing a particle size o~ 0.1 to 1000 ~m and a glass transition tempeXature of 35 to 130~
a) in wa~er, ~ t~e binder~ cont~in c~tionic ~roups, or b) in water and acid, if the binders contain cationi~
and/or basic ~roup~, to a tempexatu~e of 40 to gO~, for 5 minutes to 5 hours~
- 2~72~
q~he dispersions accordin~ to the lnvention a~
~ub~tantially ~ree ~rom l~quid or dissolved binder re~ins can }~e used to Goat an electrically conduc~iv~
substrat~ con~eated a~ ca~hode. ~oatings from the di~pex~ion~; u~ed as ele~::trod~o~ition ~aths can be obtained at tempe~atu~es o~ 20 to 80C.
According to the invention, pulverulen~ binder~ cc~nt~ining cationic g3~oups can be used in c~rd~3r to avoid ~ran po~t of liquid or pasty materials ~rom the binder manufacturer to ~h~ user, and t~u~ avoid the r~sulting econom~c di~advant~ges and pollution o~ thc ~3nviroP~en~.
Th~ pulv~rul~n~c binder~ u3ed in the dispe~sion~ acco~dinq t~ the invention a~e resins in powde~ ~orm which are solid und~r the condltions of ~anu~acture and transport ~ut melt at higher tempe~tures and ~ox~ a sm~oth f ilm . They are not cro~61inked whe~ in powder for~. They contain cationic ~roups or basi~: group~ convertible into cation~c:
group~, an~, are therefore dispcrsible ~nd remain ~table in the aqueous p~as~ ~t tempe~atu~es of 40 to gOC. T~e r~sins are usually not ~is~;olved in a true solution in the a~[ueous phase.
Optionally other conventional lacqu~r additives an~
constituents can be dispe~sed in the p~wders, e.~.
pigments, fillers, catalysts and other convention~
adjuvantc. The quantity o~ ~id necessary for neutr~lisation can als~ ~e distributed in the powders The~3e acid~3 ~re usually or~anic acids such ~s a~etic acid t formic acid, ~ulphamic a.cid, beh~oi~ acid or 1 actic acid.
q`he small ~uantities reguired can be àispersed without di~ficulty in the solid organi~ phase, so that even when the ac~ liquid the pvwder ~orm does~ not change.
Alternatively the resins conta.in~.ng p~ erulent CatiQr~iC
- ~ 206~726 or basic ~roups c~n be p~epared without additives, and pigmehts and optionally acid~ an~ othe~ additive~ and ~djuv~n~s can be added if nece~sary in the form of a conventional agueous pigment paste t~ the electro-deposition bath.
The disper~ion or the eleatxodepo~ition coa~iny agent i5 prepared ~rom the pulverulen~ starting material, op~lonally wl~n a pl~ment paste, a~ter ~llutlon Wlt~
water, optionally wi~h a~di~ion of aci~. To this end an aqueous s~urry i~ prepar~d ~n~ is prefer~bly ~oht~nuo~sly homogeni~ed, e.g. ~y vigorous ~gi~ation or pumping, and heated to a temperature of 40 to 90~, p~eferably over 60~. The ele~trodeposition ~ath i~ then ~eady for Goating~ at a temperature between 20 and 80C. A~ter dispersion, the ~ubstance can be ~ooled and re-he~ted fo~
d~p~sition~ The eleotrodepo~i~ion ~aths can be adjusted by the conventiona- adjusting agents.
The pulverulen~ resin~ used are powders having a particle size of 0.1 ~m to 100 ~m, preferably 2 to 40 ~m. CoarR~
poWder with a particle size o~ 100 to 1000 ~m may al~o be used. The par~i~le siZe of ~he powder will ~epend on the production facilities. Fine~y d~v$ded powder tends to produ~e more dust when poured. If equipment iS ava$1able for preventing ~he spread of du~t, the powder can have a par~icle siz~ of Q.l to 100 ~m. In oth~r cases, it i5 recommended to have a particle size of 100 ~o 1000 ~m.
Ano~hex possibility of avoiding dus~, which is ~npleasan~
and ~n explo~ion risk, i~ to produce powder slurri~s, e.g ~y a~itating 20 to ~0% by weight o~ powder, particle size 0.2 to 15 ~m, in 80 ~o 40~ by weight ~f deminerali~ed e~r~ p~slBnthiJ~n~n~u~yt~ f~
thixotropic, i~e. not liquid, and the~efore cannot pene~ate into the surroundin~ earth to any extent in the 8 2 ~72 6 event of ~n accident during tran~port. The pul~erulent resins have c~tion~ groups o~ basic group~ convertible into ~tiOhi~ grDUp~, so as to make the pulverulent re~ins di~per~ible in w~ter. The ~asic group~ are e.g. primary, secondary or ter~iary amino groups, ~hereas the cationic qroups ar~ ~g. quaternary nitrogon or qua~ernary~
phosphorus or tertiary sulphur atoms. These groups are firmly b~nded to the resin. rhe ~esins also cont~in reactive groups capable o~ arosslinking reactions, e.~. OH
groups, blocked N~ groups, p~mary ~d/or second~ry amino ~roups, SH groups, group~ o~pable of transesterification and~or gr~ups crosslinkable by Michael addition. The crosslinka~e groups can occur individually or in mixtures~
To give the pulverulent ~u~stance5 suffi~eht ~ta~ility in storage, the powdçrs mUst not coagulate. This i~ helped by the high gla~s transi~ion ~empe~a~Ure of the pow~er~, which is measured by the Differential S~nning Method, DSC, and is ovex 350C, pref~rably over 45~C. The uppe~
limit of the gla5s transi~ion temperature ghould be 130C, prefe~ably 100~, to ensure that the powders lique~y an~
~orm a smoo~h sur~aae ~ur ~ ng stoving.
~oagula~ion of the powders can be redu~e~ or prevente~
e~. by incorporating pi~ents by dispersion.
Alternatively the ~round binder powders can be surf~ce-treated with non- sticking organic or inorganic addit~ves. For example ~he powdex~ can be sur~ace-trea~ed with highly di~persed ~ilicic a~id. The resulting powdexs ~emain free-flowin~ and storable for a p~ticularly long time~
T~e p~lverulent cationi~ qroups or resins convertible into cationic groups can be ca~hode-depositea ~inders or mixtu~es thereof. These bind~rs ~an b~ self cro~slinXing , 20~9726 or extern~lly c~o~linked. In the case of ext~rnally cro~slinked binderq, cros~lin~ing agents c~n be added to the bin~er~ or ~inder mixture~ to obtain a chemi cally c~rosslinkable filr~. The c~ntent of cro~slinking agent in th~ powder can contain ionic groups. Alternatively it may be free from ionic groups, pr~vided it is us~d in~small proportions of less than 40% ~y weight r~lative to ~he total weight of binder. ~he binder components ne~ "ot individually h~Ye the ~tated gla~ transi tion ~empe~atures, par~i~le ~i~e~ and ionic g~oUp5. :s~t iS
sufficient if the mix~ure of film-forming r2sins or the mixtllre thereof with oro~link~ng agen~s meet~ the aiorementioned specif ications overall .
The pow~ers are e.g. amino epoxy resins obtained from poly~l~cidyl ethers with more than 1, preferably at le~st ~.S, epoxy ~roup~ per molecule, a~ter reaction with ami~e~
or compound~ o~ntaining ~ino g~oups. Polymex.
containing cationic or ~a~io gro~ps dnd ~ormed from ole~inical~y uns~turated polymerisabl~ monomers may also be used, AminP epox~ re~in~ are pre~erred. As mentioned, the bind~rs contain crosslinkable ~u~ctional gro~ps sueh as OH groups, blo~ked N~O groups, primary and~or s~condary amino groups, S~ groups, group~ ~apable of tran~-estexification and~or groups crosslinka~le ~y M~ahael addition, pre~ent individuall~ or in mix~ures.
The ~esin.~ used in th~ powders are preferably ~ho~e conYentionally provided for ~athodic el~ctrodeposition coatin~, such as tho~e h~therto use~ in liquid systems, e.g. a~ solutions ~ dispersions. The powders ~d~ ~e ~roduced from the liquid systems by removal of the ~olvents, o.~. by distillation and op~ional subsequen~
grinding. They can also be prepared in the melt and grouhd ~fter cooling. The b~5ic resins used in the powde~s can e.g. be amino epoxy re~ins or resin~
206~726 containing ami~o y~oup~ and obtaine~ by polymerisat~on o~
un~aturated monomers. The resins pre$e~ab1y have an amine nu~ber of 45 to 120 mglg KOH and a hydroxyl number o~ 50 to 400 mg/g KOH~
Examples of basic resins used in the powders are ~escribed in ~he l~id-open specifications EP O 08Z 291, EP O 234 395 ox EP ~ ~09 587. The resins prepared ~herei~ by ~
dissol~in~ in org~ic solvents can be ~onverte~ into powder ~y removing the solvent, e.g. by di~illation ~e.g.
i~ a thin-laye~ evapor~tor) and subsequent grinding. The s~bstances are amino epoxy resins b~sed on glycidyl ethers with more thah 1 epoxy group per molecule, preferably ~a~ed on ~i~phenol A or novGl~k and containing conventional primary, ~econdary and/or tertia~y ~mino ~roups. The amine number i~ usually between 45 and 120.
The amine nu~er oan be used to in~luence the di~persi~ility of the resin powder, and also t~ influence the quality of the. surface of ~he crosslink~d film o~
la~uex. If the ami"e number is too sm~ll, the resins canno~ disperse sufficient~y and do not form a ~t~ble di~persion. If the amine num~e~ is too high, the re~ult i~ a poor surface with inadequate prote~tion a~ainst cor~osion. These r~ins have OH group~ ~ additio~ to amino ~roup~. The hydroxyl number is preferably about 50 to 50V. ~l~ne acclve nyaroxyl ~oups~ ~y~ Pr wl~
reactive amino group~, are responsible f~r ~rosslinki~g.
Their num~er is preferably at ~ea~t 2, and particularly preferably ~t least 4 per molecule. ~r ~he de~ree of crosslinking of the ~ilms forme~ from the powders is too low, the films have poor mecha~ical p~operties after cro~slinkin~ the degree of crosslinking is ~oo high, the cros~linked ~ilms are brittle.
Other functional ~roup~ can be introduced e~ by reac~in~
OH or NH ~roups in the ~e~in mol~cules w~th isocyAnate~
- 2~72~
c~ntaininy the required fun~tional groups. If conventional semi-capped diisocyanate~ are used as the reaction component, ~el~ osslinking bin~ers are p~oduced via capped isocyana~e group~. O~her functional group~ can ~e introdu~ed, e.g. via ~meth)acrylic acld derivatives.
~h~ resulting ~inder~ will then con~ain ~, ~-unsat~u~ated carb~yl ~roup~. The binders can opt~onally b~ modified w~th other ~unctional groups. Anoth~r method o~ ~ynthesis i5 descri~ed e.g~ in EP-o OS~ ~31, where functionalised amino epoxy resin~ are produced in s~lid ~ol~ent~free form. ~or ~xample, epcxy resins i~ ~he melt are reacted ~ with ~mino ~lcohols and further processed in the mel~, optio~ally after solidifying to powder.
Other example~ of ~ros~linkable binders usable in the powders ~re de~cri~ed e.g. in EP-O ~61 385. These substance~ also ar~ resins dissolved ~n org~ni~ sol~en~s and conYertlble in~o powder as previously described~ ~hey ar~ polymers obtainable by polymerisation of radiaally polymerisable un~a~urated ~onomer~, at least part of which have ~unctional groups ~uitable for dissolvin~ or cros~linkin~ For exa~ple u~e can be made o~ saturated ~trai~h~-c~aih or branche~ a~ryli~ or ~et~c~ylic ~id esters, glycidyl ~m~th~ acrylates, allyl glyci~yl ethers, ; vinyl ether~, styrene, hydroxy ~meth) acryl~t~s or oth~r ~unctionali6ed aarylic acid an~/ox methacxyl~c a~c~d derivative~. Amino groups necessary for ~olubility can ~e ~ntroduced e.g~ by reactin~ epoxy yroups with secondary amine~ or amino alco~ols, o~ can be incorparate~ ~y p~lymerisation via compounds containing am~ no g~oup~ .
~he glass t~ansition temperature can be influenced via the nature of the monomers. The ~onomers can also be used to adjust the ~umber o~ crosslinkable group-~.
A~ mentioned, the.pulverulent res~ hS can be self-20~72~
crossli~king or externally crosslinXed. ~he follo~i~g resins are ex~mples of ~uita~le cro~xlinkiny agents:
~iazine resi~s, alkoxy methyl (~QthJ ac~ylic ami~e copolymers, blocked isocyanates, res~ns capable of trans-ssterification or tran~amidation, resin~ with ~ermin~l d~u~le ~onds or cros61inking agents capabl~ of Mic.hael reac~ion. Cxosslinking agentS of thi~ ki~d are curre~t in the literature and aescribed e.g. in EP l~id-open -~pecification 0 245 7~6, DE 34 36 345 or DE 37 1~ ~05 These ~ub~tance~ also ~re resins di~olved in organic solven~s ahd converti~le into powder ~ previousl~
described. In s~e c~ses they can also be produced in ~he substance and pulverised. The powders can ~ uni~o~m or in the form of mixture~ The individual powder parti~les can be homogeneous or he~erogeneou~ ~ixtures ~an ~e prep~red ~y ~ixing pr~fabri~ated powder p~rticles to~ether ana opllonally grlnu~ IU~ ~lL~lla~lV4'y ~lJ~y ~
manu~actured by processing mixed solutions until they are free from solvent and grinding them. Pre~erably the work is car~ied out so that al~ the powder particles have ~onic groups. If for example a non-ionic resin is used, it can bo proc4~0Qd with ~n lnni~ r~Rin tn nhtA;n he~.Rrn~P.nP.nu powder particles having ionic char~es.
Resin~ prod~ced in organia solvents are converted into ~
~orm containin~ little or no ~olvent. A low-solvent ~orm has a solven~ content which can be used to obtain a non~
sti~ky powder with a glas~ transition te~peratUXe of 35 to 130~. Alte~natively the Pinders can be p~oduced solvent-free, e.g. in the melt, ~nd th~n converted $nto powder.
Additive~ and pi~men~s can be contained in the powder~
~hey can be added at any time before y~inding. For example they can ~e added to solid re~ins Xor grinding or to a resin already in solution before the sol~e~t has ~een remo~ed. After removal of ~he ~olven~, the res~n~, 13 20~9726 optionally containing additive~; and pigmsnts, are ground to ~he necessary f ineness in a suita~le apparatus. T~e conte~t o~ solvents c)r licr4id constit:uent~ mus~ be so low ~h~t the resulting pow~ers do not co~gulate and can ~till flow freely afte~ ~ prolonged period. Suitable grinding appar~tU~ and ~ethods o~ grinding powder~ are known and freguently described in the ~iteratur~.
..
Small quantities of organic or inorganic acid~, e.g.
~or~i~ acid, ~cetic acid, l~atic acid or ~lkyl phosphoria acid, are ne~essary to neutralise the binder or to ~orm cationic groups. The acids used aan be li~uid or ~olid, e.g. ben80ic acid, sulphamic ac~d or ~lycolic acid.
~ptionally, polybasic ~cids ~uch as c~tric acid or ox~lic acid can al~o be usedO A~id anhydrides or ea~ily h~dr~lysed este~ oan ~lso be ad~ed. The follo~in~ are exampl~ thereof: acetic acid anhy~ride or maleic a~i~
anhyd~i~e or p-toluene~ulphoni~ acid meth~l e~ter. If the ne~tralising ~gents are added via the po}ymer powder, solid neutralising a~ent~ are pre~erred~
Suitable pigTnents can al60 ~e incorpora~ed in the polymer powders containing ionic groups. The pigments can e . ~. ~e titanium dioxide, carbon bl~k, organia or inor~anic po~dered dyes, fine~y-divi~ed filler~ such as highly-dispersed silicic acid, p~lverulent catal~sts or anti-corrosion pigments such as lead ~ilicatès.
The fillers can also be polyme~ micropart~¢le~ which do not melt under the sto~ing conditions. Cros~lin~ed polymer micropa~tiGles are preferred. The poly~er microparticles sho~ld preferably not ~ontain any ionic g~oup6 on the surface. Cationic groups, however, may be present on the surfa~e. They must be sufficlently crosslinked not to li~uef~ with the bind~r when stoved.
~L ~ h~ld b2 ~ 20 ~m, prn~ar~ly ~ m.
:
2~6~72~
~hey can b~ inc~rpora~ed like normal pigments ~n the binde~ or the pigment pa~e~. The pDlymsr particle~ may op~ion~lly carry surface unctional group~ such as OH, SH
or ~ster group~. These can react wi~h the b~nder during stoving. ~he po~ymer m~¢roparticles can ~e manu~actured e:.y. Vll ~ 1~ v ' ~ ~GL~ ~r r~~
or p~enol ~ormaldehyde resins.
The pi~m~nts a~e ~inely dist~ibuted in the binders in known manner, e.g. ~y ho~ageneously mixing ~he binder with the pigments in a sultable ~ixer, e.~. an extruder. The mixin~ process ~n also ~e assi~ted by elevated temp~rature. The mixt~e o~ binder and pigment is then commin~ted ln known apparatu~ ~nd ground to the necessary~
fineness in a mill . ~he pigmen~ particles are then ~o~ted with ~he polymer po~der and have a sultable particl~ size distribution.
Th~ pulverulent resins ~ontain~n~ ionic groups and ~ed a~cordinq to the lnvention can al~o be pro~uced without a~ding a pigment. In that aase a clear l~cquer ~oating is .
o~tained after deposition and ~toving. In another method, the binders are added in the ~'orm of pu~verulent pigment-free resins to the electrod~position ba~h and the pigmentsare a~ded to the b~t~ after ~eing prepared sepaxately~
The piqment preparat~ons can be obtained from ~onventional pi~ment paætes, produced by grindin~ pigments with wetting ~gents qr "paste resins" (binders used in ~rinding). For example EP laid-open specifi~ation O 183 025 describes pa~te resins based on epoxy resins with par~i~lly reacted oxazoli~in~ rings. The ~itation also des~ribes how pi~meht pastes are produ~ed ~rom ~he aforementioned binders ~oget~er with conventional pigment~. ~he pigmeht ~ C~ ~c~ h~ Llon elh~llld profr~hl ~
be aq~eous. They can be p~epared by the user and added to 2 ~ 2 6 th~ di~persion~
The pigment pa~tes are added in a proport$on of 0 to 20, preferabl~ O.5 to 20 partQ per 100 part~ o~ bind~r powder, preferably 2 to 10 parts. Owing to t~e s~all quantity, they cannot form films by themselves. They C:~n ~e ~o3.u~le or dispersible in Wate~. They can contain ionic groups or ~Q present without ionic ~roup~. Preferably they~ontain functional groups which can ~eact with the film-f~xming resin~ rhe paste binders should be p~e~ent in aqueoug disp~rsion and ~ontain only ~mall propo~tion~ of solvent.
Th~ paste resin~ are e.g. ~inders based on epoxy resin~, al~yd ~e~ln~, polyurethane resins or polyether~.
Non-~onic paste binder~ ~an also be prepared, e.g. base~
on a s~ralgn~-Gna1n or ~r~ u ~y~ y~ yly~v polypropylene glycol wi~h or ~ithout terminal gr~fted ethylehe ~xide compon~nts.
~xamples of pa~e re~ins are de~ri~ed e . g . in EP
pen specification 0 108 088~ EP O ~83 0~5 or EP 0 ~?0 877. They ar~ wettin~ agents or binders having a high capacity to wet pigment~ and ~iller~. ~hey should be easily co~npatible with the binder in the a~ueous coating agent ~nd should not al~er the properties of the binder mixture. They can optionally become crossli~ked with the binder ~ia functional group5. These pa~te xesins h~ve basic ~unction~l groups which, when neu~ralise~l with ac$d, make the paste.re~in~ disp~rsible in waterO
Alternati~ely, partly-re~cted catio~i~ functional groups m~y be present ~n the paste re~ins. Example~ o~ ~uch fun~tional ~roup~ are quaternary nitro~en atoms, quaternary phosphorus ~toms or ~ertiary sulphur 9TOUpB.
The sol~bility of the paste binders ~ 5 influenced via the number of these neutralised or ionic group~7 20~972~
T~e numb~r of cationic group~ can ~e so high that the pa~te re~ins c~nnot be ~epo~ited on the catho~e ~y themselves, i.e. do not produc~ a homogeneous uni~Drm fil~.
Preferably the paste resins have functiona~ groups for crosslinking to th~ ~ilm-formin~ resins, e.g. prim~ry or ~econd~ry OH ~OUp~, ~ea~t~ve amino gr~up-~, e~tet~qrollp~
capabl~ of tran~e~te~ification or c~pped l~o~yanate~, met~ylol groups or alkoxym~thyl groups, pr~ferably methox~me~hyl groups~
Piym~nt paste resins based on ~odified epoXy resins can be used e.g~ i they contain at least one, preferably at lea~t two epoxy group , where 50 to ~00 mol % of ~he free epoxy ~XOUp5 are rea~t~d with ~ prim~ry-ter~iary diamine, the ~x~ess epoXy groups are optionally previously reacted with sQconda~ or primary amine, and 80 to 100 ~ol % of the secondary amino groUps present have been re~cted with a car~onyl compound to form oxazo~idine structures. The~e binding agents can be converted into a~ a~ueou~ dispersio~
~y adding an acid. The molec~lar weight o~ ~he modif ied epoxy r~sin~ ~hould be 400 to 10000. The hydroxyl num~e~
:~nOUla De ~ l~U my r~ullt~ ~L'I~ ~' a~y ~ lVU IU~ n/y~
content of ~rga~ic solvents sh4uld be below 30~.
Example~ of u~ble non~ionia pa~te re~in~ ~r wetting ~gents ~e descri~ed in DE laid-open spec~iaations 30 18 715, 36 ~1 6~g and 26 0~ 831. They are no~-ionic re in aomponents which should have a good capacity to wet pigments an~ fillers~ They ~ust be eas~ly compatible with th~ binder system of the aqueous ooating agent and must not alter the proper~ies of the binder o~ binder mixture.
It is adv~ntageous i~ these pa~te binders can rea~t via ~unctional ~roups with the binder in the aqUeQUs coating agent. These non-ionic paste resins have good solu~ility 17 2 ~72 in w~te~. They ~annot be deposited at the ~hode by ~hemse}v~s, but only togPther with the ~inder system.
Samples of such substances are polyalXylene glycols.
Alternatively, non-ionic pa~te resins c~n be derived from epoxy re~ins, preferably from aro~ati~ epoxy resi~s which have been made more soluble in water vi~ polyethyiene oxide or polypropylene oxide component3, or alter~atively .
the non- ionic pa~te resins can be non-ionic wetting agents based on melamine or phenolic resin.
Pigment pastes can ~e made from the known paste xe~in~.
For exa~ple demiheralised water ca~ be added to the paste resin, opt~onally after it has been ne~tr~li6ed wi~h an a~id and thus made ~ispersible in water. Pi~ent~, fil~ers, ~atalys~s, anti-corrosion pigments, inorganic or organic colour pigments and othe~ additives a~e added to the thin-~lowing mixture. The additi~es are, for example, anti-foaming agent~, wetting ~gents, le~ellin~ agents or anti-crate~in~ a~ents. After th~ mixture has been thoroughly hom~genised, the viscosity o~ the pigment pa~te is ad3usted with c4mple~el~ dem~heral~Sed water, foilowed by grin~in~ ~o the necessary finene~s ~n ~ con~entional grinder~ e g. ~ pear~ mill. Th~ resulting pi~m~nt p~stes are aqueou~, p~pa~le and have good stability in storage.
The ele~trodeposition coating agents used ac~ordin~ to the inVention can be ~anufactured as follows: the polymer powder, thoroughly agita~ed and ho~ogenised, i~ slow~y added ~o the amount of completely demineralise~ wa~er necessary for the electrodeposition ~oatin~ ~ath.
ca~e mus~ be taken ~hat the polymer powders do not coagulate but ~e~in ~inely dispersed. If the a~ueoug powder slurry does not ~low freely, i~ ~an be ~etered through a pump for thick matter. Op~onally a pigment .~ ~
18 2~63726 paste ~an be added, with tho~ough mixing, to the ~in~er dispersion. Alternatively the pi~ment~ c~n already be pre5ent in the pol~er powde~, or ~ pigment-free K~L
system can be used. Preferably the pigments ar~ dispersea in the polymer po~der when used~
Aft~r thoroug~ ~omogeni~tion, the ele~trodepositi4n coating bath is hea~ed for S minu~ex ~o 5 hour~.
Alternatively, homogeni3ation can ~e bro~ght a~out directly at t~e ~eposition temperature nf the ~ath. The heating t~mp~rature is about 40 to 90~, pre~erably 50 to 80DC, particularly prefer~bly 60 to 75OC. In the proce~
the bath is continuously homo~nis~d. Preferably the h~ating temperature is chosen from the prcviously-mentioned ~ange to mat~h the glass tranSition ~e~pe~ture of the binder powde~ u~ed, i~e. a moderate heAting te~perature ior a low glaas transition t~mperature and a hRn~,in~ t,Rm~r~tl~r~, frnm tlh~, uD~,r ~f~r~,~Rntinn~ r~nu nt. hi~h~ ~aa~ t~an~ n temue~atl~e~, ~he h~tinu temperat~re ~hould be chosen so ~hat it is not ab~ve ~he melting-point of the polymer used.
I~ the electrodeposition bath is used to top up an exis~ins ~ath, t~e pulverulent electrod~position lacguer and binder ~ompo~ition and optional}y the pigment paste ~ay also be dispersed in the exis~ing e~ectxodeposition bath. After h~ogeni~ation and heatin~ to elevat~d tompor~tura, ~h~ thnrli~ Q~ trnrl~l~n~;t inn hn1-h ~ rP~ly ~or coating.
~he cathodic electrodeposition bath is used fo~ coating at ~0 to 80DC, pre~erably 30 to 60~C. The ele~rodeposition coating agent is st~ble at these temperaturl3~ and does no~
~ecompose . The method according to the invent ion is o~
particular use e.g. for c:oating industrial products made . of ~netal, t:onductive plastic:s or electricall~r conduct~ng 7 ~ ~
lac~uer layers. T~e guality of the coatin-3s ~ill depen~l Oh the h2~ture of the products. Produots not expos~d to the weather, e . g . sl~elves, coated ~y the method can be given a di~ier~nt grade of powder from t~at U~;e~ f or car bodies, The powdexs used for washing-machines no~m~lly h~ve good resistanc~ to alkalis after stoving, in~ad~tion ~o ot~er import~nt prope~ties. ~he ranqe of indu~trial products wh~ch can be coated ac~ording ~o the invcntion is the same as for exi~ting elect~odeposition baths. Af~er deposition, the coatings have ~ood propertie~, i.e. good ~r~ rmlnn ~n~l ~rlh~inn ~.n t.h~ ~r~ace un~neath, coated parts are Purther treate~ in conv~n~ional manner, e.g. they are washed clean ~nd cro ~linked at ~levated te~perature. Wet-in-wet f~rthe~ co~ting is also possible.
Conventional ad~usting agents can be added to the electrodeposition coating agent~ according to the inventionn If necessary, for example, acid can sub~e~uently ~e add~d to the ~ath, i.e. the aforementioned acids conventionally used in elec~rodepo~ition coating.
Also, substances can be added to prevent the ~ath from foaming, or levelling agents s~ch a~ fatty alcohols containing 12 - zo car~on atoms, or ~u~tances for adjusting the l~yer thickne~s or anti- ora~ering additives if neces~ary, e.g. as described in D~-OS ~0 18 87fi. The resulting cathode-deposited electrodepo~ition coating baths give smooth level film~ a~ter crosslinXing. The edge~ have good properties as regards re~istanae to co~rosion or weatherinq. ~he coatin~ have good resis~ance to gravel.
The resultin~ C:o~tings on condu~tive metal substrates can b~ single layers, o~ alternativcly additional laye~ ~uch as fillers or cDvering la~quer~ can be applied to ~h~
primin~ layers. The resulting single-~ayer or multilayer coatihgs have a gDDd appearance.
2~72~
~he in~entio~ wi~l now be explained in detail with reference ~o v~riou~ exam~le~. All percentage6 are by weight~
~e~in a~mpl~
A. As per EP-B-0 012 463, 3~1 g diethanol~mine, 189 g of 3-(N,N-dimethylamino)-propylamine and 1147 g of an ad~uct fr~ 2 mol hexane diamine-1,6 and 4 mol gly~idyl ester of ver~ati~ ~c~d (cardur~ E10) wexe added to S~73 g bisphenol ~-epoxy resin ~poxide e~uivalent weight approx. 47~) in 3000 g of ethoxy propanol. The reaction mixtur~ w~s heated with agitation at 85 to 90~C for 4 hours and then ~ep~ at 120C for 1 hour. The solven~ was then distille~
off in vacuo in a thin-layer evaporator and ~he resulting ~in tg1A~ Ln~ n t!~:mpc~u~ ~ 40n) u~a a~minu~cd to a si~e of ab~t 5 m~ in ~ suitable apparatus.
B. 160 g of ~prolactam was ~lowly added with agitation at 70C to 453 g o~ a ~olu~ion of a ~e~ction product ~rom 3 mol isophorone diisocyana~e and 1 m~l trimethylol propane ~7~ in ethyl acetate). The reaction ~ix~ure was then kept at 70C until the NC0 content had fallen to zer4. ~he solvent was ~he dist~lled o~ in vacuo in a thin-layer evaporator and the resultin~ re~in ~glass transit~on temperature ~ 40~C) was ~o~nuted to a size of a~out 5 mm in a ~uitable apparatus.
~e resulting resins a~ per A and ~ were mixed in ~he ratio 8 : 2 (solids).
Pi~nt paste example 2:
A. g50 g o~ an epoxy ~esin based on bispheno~ A (2 epoxy equivalents) was d~ssolved in 633 ~ xylene ~nd added at 60 21 2~7~
~ ~OnQ t~ ~ ~ni~tsur-- ~t 100 y Q ~th~l h~x~l~ils~ ~
diethyl aminopro~yl ~mine. The t~mperature wa~ pt ~elow 75~. A~ter all t~e epoxy groups had ~e~an compl~ely us~d up, 59 g paraform~ldehyde (91%) wa~ added. The mix~ure wa~ heat~d until the ~eaction water had heen azsotropically ~o~d.
The xylene was then distilled off in a ~atch and the binder, af~er ~dding 780 mmol acetic acid per loO g solid resin, was dilu~ed with deionised ~ater to a solid ~ontent Qf 30%~
B~ 143 ~ of a commercial aluminium ~ilic~ta powder, 10 g carbon bla~k, 16 g pyrogenic silicic a~id and 8 g dibutyl tin oxide powder was added t~ 53 ~ o~ pa~ta resin A ~30%
in water) in a high~peed agitator. ~he solids wer~
ad~ust~d to a~out 44% -with 115 g completely demin~ralis~d wal,~ VUII~ y ~ y <,~
pigment paste~
Pigmont paste example 3:
125 ~ ~f a commercial N-butanol etherifi~d ~la~ine/
~ormaldehyde resin t75% sol ids in butanol, vi~co~ty 6500-6800 mPas) w~re ~i~ed with 24 g di~tyl tin oxide, 5 g carbon ~lack~ 160 g titanium dioxide and 35 g bu~oxyet~anol and gxound in A suita~le mill to a fineness ~elow 5 ~m.
Lacquer ex~mpl~ 4:
Po~dered resin as per example 1 was mixed ~ith 0.3%
dibutyl tin dilaura~e ~nd ground in a suitable mill to finenes~ below 25 ~m.
1.0 g of a co~mercial ~etti~ ag~n~ ~50%) and 5.5 g for~ic 2~9726 acid ~50~) wer~ add~d to 1000 g completely demineralised water. 150 ~ of the previously-descxi~ed binder powder was ad~ed with agitat~on. ~he ~a~h was ~ade up to 2000 g with ~o~pletely ~eminer~lised w~er. ~h~ ba~h wa~ he~ted to about ~o~c for 15 m1n~tes and agitatedA It remained stable and did not pr~cipi~at~.
L~e~W~ a~ a~tAw~olcw~r7no~ nu~ Q~ ~nll m~terial a~here~ firmly. The films o~ained after stoving had a ~od s~fac~ and a layer thickness of about 25 ~m and 20 ~m.
~acguer example 5:
A. lO g di~lltyl ~in ~xide, 3 g oxalic a~d, 7 g carbon bla~ and 30 g titaniu~ dioxide we~ added ~o S00 g o~ the bind~r mixture in exampl~ 1 and wer~ homogen~ou~ly mix~d in suitable apparatu~ and ~hen ground to a siz~ of les~
th~n 40 ~.
B. 7.~ ~ wettin~ agent (50S) was added to lOoO g completely dem~ne~alised water, ~ollowed by 120 g of the powder in A, with vigorous agitation. The bath was heated to 70C for 30 ~inuteæ and was then ready ~or coati~g.
T~e metal sheets wexe coated at 30~ and at 55C, wa~hed clean and then sto~ed a~ 180~C for ~0 minutes. The film~
had a thick~ess between 20 and 30 ~m and a good su~dce.
Laagu~r e~ample ~:-A clear la~quer was made from 5 g we~tin~ agen~, 7~5 gformic acid, 1000 ~ water and 150 g resin powder as per example 1 ~round to about 30 ~m). The lacquer was made up ~o ~uu~ g wlth w~t~r. ~ ~r ~idl l~v~ll;~y agent/butyl glycol ~l ~ l) waæ a~de~ and 132 g of a 2~972~
pigm~nt paste as per example 2. ThQ lacquer w~s h~ated to 600C and applied a~ter co~liny.
Lacouer examnla 7:
A clear lacquer wa~ made from S q wetting agent, 7.5 g ~ormic acid, 1000 g water and 150 g resin powdRr as per examplc 1 ~ground to a~ut lo ~m~. 4~ g of a pi~m~nt pa~te as per exa~pl~ 3 was ~dded to the mixt~re With ~igo~ agitation and th~ lacquer ~a~ heated to ~0C.
~he lacquer was diluted with ~000 g complRtQly de~ineralised water and ~ould be applied after cooling.
.
~cguer exa~ple 8:
A, 10 g dibutyl tin oxide, ~1 g ~ulphamic a~id, 7 ~ carbon blaa~ ~nd 30 g tltanium dioxide were added ~O
500 g of the binder mixture as per example 1, uniformly mixed in ~uitable apparatus ~d then ground to ~ 40 ~m.
R~ 7. 5 ~ wettin~ agent ~SO%) wa~ added to 1000 g c~pletely deminerali~ed water, ~ollowe~ ~y 120 g o~ the powder in A, with vigorous agitation. The bath wa~ heated t~ 7~c for 30 ~inute~ and w~s then ready for coating.
The metal sheets were coated at 30DC and It 55C~ washed clean and then ~toved at 180~ for 30 minute6. The film~
had a thickness betweeh ~0 ah~ 30 ~m ~nd a good surface.
.
Claims (28)
1. An aqueous dispersion of a cathode-deposited thermosetting cationic film-forming binder, characterised in the it is manufactured by heating a slurry of the binder, used in the form of powder having a particle size of 0.1 to 1000 µm and a glass transition temperature of 35 to 130°C
a) in water, if the binder contains cationic groups, of b) in water and acid, if the binder contains cationic and/or basic groups, to a temperature of 40 to 90°C, for 5 minutes to 5 hours.
a) in water, if the binder contains cationic groups, of b) in water and acid, if the binder contains cationic and/or basic groups, to a temperature of 40 to 90°C, for 5 minutes to 5 hours.
2. A dispersion according to claim 1, characterised in that the pulverulent binder used is surface-treated with non-sticking organic or inorganic additives.
3. A dispersion according to claim 1 or 2, characterised in that the binder consists of a mixture of binders, one or more self-crosslinking resins and/or a mixture of one or more externally crosslinking resins with one or more activators.
4. A dispersion according to claim 1, 2 or 3, characterised in that the pulverulent binder is made from solutions of conventional cathode-deposited binders in organic solvents by removing the solvent and subsequent pulverisation.
5. A dispersion according to claim 1, 2, 3 or 4, characterised in that the pulverulent binder has an OH number of 50 to 400 mg/g KOH and an amine number of 45 to 120 mg/g KOH, determined by primary, secondary tert. amino groups or quaternary nitrogen atoms, or instead of the amino groups has a quantity of quaternary phosphorus atoms and/or tert. sulphur atoms equivalent to the amine number, and a quantity of functional groups reactive with OH or NH and sufficient for crosslinking.
6. A dispersion according to any of claims 1 to 5, characterised in that the binder powder contains solid and/or liquid acid.
7. A dispersion according to any of claims 1 to 6, characterised in that the water used in manufacture contains conventional additives present in cathode-deposited baths and/or is mixed with the powder after it has been dispersed.
8. A dispersion according to claim 7, characterised in that the water used in manufacture contains the following additives and/or is mixed therewith after the powder has been dispersed:
fillers and/or pigments 0 to 60 parts by weight catalysts and/or acid 0 to 10 parts by weight paste resin for grinding fillers, pigments and/or catalysts 0 to 20 parts by weight additives and/or solvents 0 to 10 parts by weight in each case per 100 parts by weight of binder powder, the hinder powder and the additives being added or present in quantities such that the total solid content of the dispersion is about 5 to 30% by weight.
fillers and/or pigments 0 to 60 parts by weight catalysts and/or acid 0 to 10 parts by weight paste resin for grinding fillers, pigments and/or catalysts 0 to 20 parts by weight additives and/or solvents 0 to 10 parts by weight in each case per 100 parts by weight of binder powder, the hinder powder and the additives being added or present in quantities such that the total solid content of the dispersion is about 5 to 30% by weight.
9. A dispersion according to any of claims 1 to 8, characterised in that the water used for manufacture is a cathode-deposited bath used for regeneration with the binder powder.
10. A dispersion according to claim 9, characterised in that the original composition of the bath to be regenerated corresponds to the composition of the dispersion according to claim 8.
11. A dispersion according to any of claims 8 to 10, characterised in that the additives are wetting agents, levelling agents and/or anti-foam agents.
12. A method of producing an aqueous dispersion of a cathode-deposited cationic thermosetting fiim-forming binder, characterised in that a slurry is formed from a binder powder having a particle size of 0.1 to 1000 µm and with a glass transition temperature of 35 to 130°C
a) in water if the binder contains cationic groups, or b) in water and acid if the binder contains cationic and/or basic groups and the slurry is heated to a temperature of 40 to 90°C for 5 minutes to 5 hours.
a) in water if the binder contains cationic groups, or b) in water and acid if the binder contains cationic and/or basic groups and the slurry is heated to a temperature of 40 to 90°C for 5 minutes to 5 hours.
13. A method according to claim 12, characterised by use of a pulverulent binder surface-treated with non-sticking organic or inorganic additives.
14. A method according to claim 12 or 13, characterised in that the binder consists of a self crosslinking resin or a resin/activator mixture.
15. A method according to claim 12, 13 or 14, characterised in that the pulverulent binder is produced from solutions of conventional cathode-deposited binders in organic solvents by removing the solvent and subsequent pulverisation.
16. A method according to claim 12, 13, 14 or 15;
characterised in that the pulverulent binder has an OH number of 50 to 400 mg/g KOH and an amine number of 45 to 120 mg/g KOH determined by a primary, secondary, tert. amino groups or quaternary nitrogen atoms, or instead of the amino groups has a quantity of quaternary phosphorus atoms and/or tert. sulphur atoms equivalent to the amine number, and a quantity of functional groups reactive with OH or NH and sufficient for crosslinking.
characterised in that the pulverulent binder has an OH number of 50 to 400 mg/g KOH and an amine number of 45 to 120 mg/g KOH determined by a primary, secondary, tert. amino groups or quaternary nitrogen atoms, or instead of the amino groups has a quantity of quaternary phosphorus atoms and/or tert. sulphur atoms equivalent to the amine number, and a quantity of functional groups reactive with OH or NH and sufficient for crosslinking.
17. A method according to any of claims 12 to 16, characterised in that the binder powder contains solid and/or liquid acid.
18. A method according to any of claim 12 to 17, characterised in that the water used for manufacture contains conventional additives present in cathode-deposited baths and/or is mixed therewith after the powder has been dispersed.
19. A method according to claim 18, characterised in that the water used in manufacture contains the following additives and/or is mixed therewith after the powder has been dispersed.
fillers and/or pigments 0 to 60 parts by weight catalysts and/or acid 0 to 10 parts by weight paste resin for grinding fillers, pigments and/or catalysts 0 to 20 parts by weight additives and/or solvents 0 to 10 parts by weight in each case per 100 parts by weight of binder powder, the binder powder and the additives being added or present in quantities such that the total solid content of the dispersion is about 5 to 30% by weight.
fillers and/or pigments 0 to 60 parts by weight catalysts and/or acid 0 to 10 parts by weight paste resin for grinding fillers, pigments and/or catalysts 0 to 20 parts by weight additives and/or solvents 0 to 10 parts by weight in each case per 100 parts by weight of binder powder, the binder powder and the additives being added or present in quantities such that the total solid content of the dispersion is about 5 to 30% by weight.
20. A method according to any of claims 12 to 19, characterised in that the water used in manufacture is a used-up cathode-deposited bath which is regenerated by mixing with the binder powder.
21. A method according to claim 20, characterised in that the original composition of the used-up bath corresponds to the composition of the dispersion in claim 8.
22. A method according to any of claims 19 to 21, characterised in that the additives are wetting agents, levelling agents and/or anti-foam agents.
23. A method aacording to any of claims 12 to 17, characterised in that the binder powder contains dispersed fillers, pigments and/or catalysts.
24. A dispersion according to any of claims 1 to 6, characterised in that the binder powder contains dispersed fillers, pigments and/or catalysts.
25. Use of the aqueous dispersion according to any of claims 1 to 11 and 24 for cathodic electrodeposition coating.
26. Use according to claim 25 for priming electrically conducting parts of motor vehicles.
27. A substrate with a coating obtained by use according to claim 25 or 26.
28. A method of electrodeposition coating of substrates, characterised by use of an electrodeposition bath containing an aqueous dispersion according to any of claims 1 to 11 or 27, or an aqueous dispersion prepared according to any of claims 12 to 23, and electrodeposition coating is carried out at a temperature of 30 to 60°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19914117417 DE4117417A1 (en) | 1991-05-28 | 1991-05-28 | AQUEOUS DISPERSION OF A CATHODICALLY DEPOSITABLE BINDING AGENT, METHOD FOR THE PRODUCTION AND THE USE THEREOF |
DEP4117417.8 | 1991-05-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2069726A1 true CA2069726A1 (en) | 1992-11-29 |
Family
ID=6432613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2069726 Abandoned CA2069726A1 (en) | 1991-05-28 | 1992-05-27 | Aqueous dispersion of a cathode-deposited binder, and a method of manufacture and use thereof |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0516066A3 (en) |
JP (1) | JPH05171074A (en) |
CA (1) | CA2069726A1 (en) |
DE (1) | DE4117417A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4331780A1 (en) * | 1993-09-18 | 1995-03-23 | Herberts Gmbh | Low-solvent aqueous dispersions, their preparation and use in coating compositions for cathodic dip coating |
ES2140607T3 (en) * | 1994-11-28 | 2000-03-01 | Basf Corp | PROCEDURE FOR PRODUCING FLUID POWDER COATING COMPOSITIONS. |
US6150465A (en) | 1998-10-01 | 2000-11-21 | Basf Corporation | Powder slurry compositions with solid particulate carbamate resin component dispersed in liquid aminoplast resin carrier |
BR9914137A (en) * | 1998-12-14 | 2001-06-19 | Basf Corp | Powdery paste composition containing particulate carbamate functional compounds |
DE10353638A1 (en) * | 2003-11-17 | 2005-06-23 | Basf Coatings Ag | Pseudoplastic, aqueous dispersions, process for their preparation and their use |
US7790011B2 (en) * | 2006-05-03 | 2010-09-07 | Basf Coatings Gmbh | Solid resin-crosslinker mixture for use in aqueous coatings |
JP5555569B2 (en) * | 2010-07-27 | 2014-07-23 | 日本ペイント株式会社 | Cured electrodeposition coating film and method for forming multilayer coating film |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU509166B2 (en) * | 1975-11-04 | 1980-04-24 | Toyo Kohan Co. Ltd. | Composite coated steel sheet |
DE2939897A1 (en) * | 1979-10-02 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | Aq. polyester and vinyl(idene) polymer dispersion prepn. - by separately dispersing in water, mixing, after-stirring and use as lacquer binder |
US4460546A (en) * | 1980-08-11 | 1984-07-17 | Kapralis Imants P | Trigger to controllably initiate crystallization |
DE3044447C2 (en) * | 1980-11-26 | 1982-12-09 | Basf Farben + Fasern Ag, 2000 Hamburg | Process for coating an electrically conductive substrate connected as a cathode and aqueous dispersion therefor |
DE3123536A1 (en) * | 1981-06-13 | 1982-12-30 | Basf Farben + Fasern Ag, 2000 Hamburg | BINDERS FOR CATHODICALLY DEPOSITABLE COATING MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
JPS5975955A (en) * | 1982-10-22 | 1984-04-28 | Kansai Paint Co Ltd | Resin composition for self-heat-curing paint |
EP0351135B1 (en) * | 1988-07-08 | 1996-09-18 | Nippon Paint Co., Ltd. | Aqueous dispersion of cationic crosslinked resin particles and its usage |
TR200003884T2 (en) * | 1998-06-30 | 2001-05-21 | Zeria Pharmaceutical Co., Ltd. | N-Phenyl-N'-Phenylpropylpiperazine derivatives and their preparation process |
-
1991
- 1991-05-28 DE DE19914117417 patent/DE4117417A1/en not_active Withdrawn
-
1992
- 1992-05-27 CA CA 2069726 patent/CA2069726A1/en not_active Abandoned
- 1992-05-27 JP JP4134595A patent/JPH05171074A/en active Pending
- 1992-05-27 EP EP19920108901 patent/EP0516066A3/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
JPH05171074A (en) | 1993-07-09 |
EP0516066A2 (en) | 1992-12-02 |
DE4117417A1 (en) | 1992-12-03 |
EP0516066A3 (en) | 1993-05-12 |
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