CN100383174C - Polyaddition product and cationic electrodeposition coating comprising said polyaddition product - Google Patents
Polyaddition product and cationic electrodeposition coating comprising said polyaddition product Download PDFInfo
- Publication number
- CN100383174C CN100383174C CNB2004800096333A CN200480009633A CN100383174C CN 100383174 C CN100383174 C CN 100383174C CN B2004800096333 A CNB2004800096333 A CN B2004800096333A CN 200480009633 A CN200480009633 A CN 200480009633A CN 100383174 C CN100383174 C CN 100383174C
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- Prior art keywords
- electrodeposition coating
- weight
- affixture
- compound
- cation electrodeposition
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- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 240000000528 Ricinus communis Species 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PGEAEAYLSCKCCO-UHFFFAOYSA-N benzene;n-methylmethanamine Chemical compound CNC.C1=CC=CC=C1 PGEAEAYLSCKCCO-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical class [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229950003365 carbifene Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NHWHNTDVBXKGLW-UHFFFAOYSA-N methane;phenol Chemical compound C.OC1=CC=CC=C1.OC1=CC=CC=C1 NHWHNTDVBXKGLW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QSKPEAWKJSSIIG-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;2-methyloxirane Chemical compound CC1CO1.NCCNCCN QSKPEAWKJSSIIG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical class NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NMWCVZCSJHJYFW-UHFFFAOYSA-M sodium;3,5-dichloro-2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=C(Cl)C=C(Cl)C=C1S([O-])(=O)=O NMWCVZCSJHJYFW-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Abstract
This invention provides a polyaddition product formed from amine compound having polyoxyalkylene chain(s) and monoepoxysilane, which has a weight-average molecular weight within a range of 250-10,000, as an additive of favorable paint stability. The polyaddition product gives, when used in cationic electropaints, coating film which is excellent in coating operability such as finished appearance, oil-cissing resistance, water mark insensibility; sealer adherability; and corrosion resistance.
Description
Technical field
The present invention relates to have the novel poly-affixture of polyoxyalkylene chain and can form covering with paint operability such as finishability, spouting out property of oil resistant, water-fast mark and the cation electrodeposition electrodeposition coating that contains this poly-affixture of filming of the adhesivity excellence of filming with finish coat.
Background technology
The cation electrodeposition electrodeposition coating mainly is widely used in the purposes that comprises car body and auto parts, has up to the present developed the cation electrodeposition electrodeposition coating with various characteristics.
As the desired performance of cation electrodeposition electrodeposition coating, the adhesivity that can enumerate covering with paint operability such as finishability, spouting out property of oil resistant, water-fast mark, stain resistance and film with finish coat etc., when production line was covered with paint, lacquer, colour wash, etc. the car body of complicated shape, these performances were big events especially.
In order to improve above-mentioned performance, proposed in the cation electrodeposition electrodeposition coating to add the method for surface conditioner etc. in the past, for example adopt the method (1), (2) of the following stated etc.
Method (1): in coating, sneak into the method that surface conditioner is made emulsion.For example, be dispersed in the aqueous medium together at solidifying agent, other additives such as making matrix resins such as surface conditioner and amine addition Resins, epoxy, end-blocking (Block ロ Star Network) polyisocyanate compound, after making emulsion, use this emulsion and colo(u)rant dispersion thickener, make the method for cation electrodeposition electrodeposition coating.
Method (2): use emulsion and colo(u)rant dispersion thickener to make the cation electrodeposition electrodeposition coating in advance and bathe, the method for in this is bathed, adding surface conditioner.
Aforesaid method (1) since with surface conditioner with matrix resin and solidifying agent emulsification, so the dispersiveness of emulsion reduces, emulsion particle diameter increases, and probably can cause paint stability impaired, perhaps finishability, erosion resistance reduce.
In addition; in aforesaid method (2); immiscible the closing of filming of the bath of surface conditioner and cation electrodeposition electrodeposition coating or formation, can produce probably that equipment such as filter filter or the obstruction of UF filter are bad, the disengaging of sealer, in go up that finish coat films peel off, spout and hold etc.
As the means of improving these problems, for example having proposed to contain the cation electrodeposition precipitability gelation particulate that the epoxy amine affixture of water-disintegrable alkoxysilane group obtains with water-dispersion in the fair 6-76568 communique of spy is coupled in the cation electrodeposition electrodeposition coating, by its surface modulation effect, give filming of formation the anti-effect of spouting out.But, when adding in the cation electrodeposition electrodeposition coating behind these cation electrodeposition precipitability microgel particles, though have the anti-effect (going for aforesaid method (2)) of spouting out, if but the cation electrodeposition electrodeposition coating for a long time with pump circulation or stir when continuing to give mechanical shearing, problem such as the finishability that will produce the face of being coated with reduces and paint stability is impaired.
In addition, open in the 2001-3005 communique the spy, put down in writing alkylidene group class polyether glycols such as containing polymethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, perhaps separately bis-phenol or bis-phenol and glycol react obtain contain polyether glycol such as aromatic ring polyether glycol as surface conditioner, the cation electrodeposition electrodeposition coating that finishability and erosion resistance can not reduce.But opening the surface conditioner of putting down in writing in the 2001-3005 communique above-mentioned spy does not have water dispersible, can not after add in the bath of cation electrodeposition electrodeposition coating, therefore, existence can not fine adjustment improve the problems such as the anti-effect of spouting out of filming.In addition, if heavy addition, often the electro-deposition of Xing Chenging film and sealer between adhesivity reduce, perhaps with in go up the adhesivity that finish coat films and reduce.
In addition, open in the 2001-288407 communique the spy, proposed in the cation electrodeposition electrodeposition coating to add hydrophobic acrylic resin and had that specified molecular weight distributes and the oxyethane and/or the propylene oxide adduct of the higher alcohols of HLB, prevented that the oil of filming from spouting out, the generation of dry spot and water mark.But, open the method for putting down in writing in the 2001-288407 communique according to above-mentioned spy, must add hydrophobic acrylic resin and have that specified molecular weight distributes and these 2 kinds of the oxyethane of the higher alcohols of HLB and/or propylene oxide adducts as the emulsion composition, and according to the mixture ratio of 2 kinds of materials tend to produce that oil spouts out, dry spot etc., cover with paint, lacquer, colour wash, etc. operability and reduce.
And, open in the 2002-294165 communique the spy, proposed in electro-deposition coating, to contain number-average molecular weight that the reaction of di-epoxide and amino-polyether obtains and be 20000～100000 amino ethers modified epoxy as surface conditioner with polyether chain.Though this surface conditioner can be shown in aforesaid method (2) after add in the electro-deposition coating, relax coating stir under (for example, breadboard jar or small-sized groove) have good stability, but in covering with paint, lacquer, colour wash, etc. production line, when being subjected to the shearing of filter filter or UF filter etc. for a long time, often produce a part of aggegation of surface conditioner and stop up filter filter or UF filter, adhere to unfavorable conditions such as pit at the face of being coated with.
Therefore, the addition manner that need develop aforesaid method (1) and (2) is all applicable, and the good surface conditioners that keep equilibrated cation electrodeposition electrodeposition coating to use such as covering with paint operability such as finishability, spouting out property of oil resistant, water-fast mark, stain resistance, the adhesivity of filming with finish coat, the paint stability in coating line, solidified nature, erosion resistance.
Summary of the invention
The inventor etc. are in order to respond above-mentioned needs, constantly concentrated research, the result this time finds to make polyethers polyamine and monocycle oxosilane to react the poly-affixture of weight-average molecular weight in 250～10000 scopes that obtains, can be used in advance surface conditioner being sneaked into coating emulsive method, and the bath of making the cation electrodeposition electrodeposition coating, add any addition means in the method for surface conditioner then, and the cation electrodeposition electrodeposition coating that contains this poly-affixture can form finishability, spouting out property of oil resistant, water-fast mark, stain resistances etc. are covered with paint, lacquer, colour wash, etc. operability, the adhesivity of filming with finish coat, paint stability in covering with paint, lacquer, colour wash, etc. production line, solidified nature, filming of excellences such as erosion resistance, thus the present invention finished.
Therefore, the invention provides amine compound (a with polyoxyalkylene chain
1) and monocycle oxosilane (a
2) the poly-affixture (A) of weight-average molecular weight in 250～10000 scopes that form.
The present invention also is provided to contain and makes Resins, epoxy and contain amine addition Resins, epoxy that amino compound addition reaction obtains as matrix resin, and contain in the cation electrodeposition electrodeposition coating of blocked polyisocyanates compound as solidifying agent, the solid substance of matrix resin and solidifying agent adds up to per 100 weight parts, cooperates or adds the cation electrodeposition electrodeposition coating that the above-mentioned poly-affixture (A) in 0.1～20 weight part scope obtains.
Below, poly-affixture of the present invention and cation electrodeposition electrodeposition coating are described in further detail.
Poly-affixture (A):
Poly-affixture of the present invention (A) is by the amine compound (a with polyoxyalkylene chain
1) and monocycle oxosilane (a
2) react the material that obtains, have the weight-average molecular weight in 250～10000 scopes.
Amine compound (a with polyoxyalkylene chain
1) be included in and have the polyoxyalkylene chain in 1 molecule (this polyoxyalkylene chain both can be made of a kind of oxyalkylene units, also can constitute by oxyalkylene units more than 2 kinds or 2 kinds) and at least 1, the compound of preferred 1～3 amino, specifically, can enumerate the compound of following formula (1), (2), (3) and (4) expression.
(in the formula, R
0Expression NH
2Or OH, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a, b and n are respectively the integers more than 1, m is the integer more than 0)
Specific examples as the compound of above-mentioned formula (1) expression, can enumerate Sang Amilu TAP-10 (サ Application ア ミ-Le TAP-10) (weight-average molecular weight about 600), Sang Amilu TAP-40 (サ Application ア ミ-Le TAP-40) (weight-average molecular weight about 2300) (more than be Sanyo change into corporate system, trade(brand)name) etc.
H
2N(CH
2)
aO(R
1O)
n-(R
2O)
mR
3(2)
(in the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a and n are respectively the integers more than 1, m is the integer more than 0)
Specific examples as the compound of above-mentioned formula (2) expression, can enumerate Sang Amilu MAP-10 (サ Application ア ミ-Le MAP-10) (weight-average molecular weight about 600), Sang Amilu MAP-20 (サ Application ア ミ-Le MAP-20) (weight-average molecular weight about 1,300) (more than be Sanyo change into corporate system, trade(brand)name) etc.
(in the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, n is the integer more than 1, m is the integer more than 0)
Specific examples as the compound of above-mentioned formula (3) expression, can enumerate Jeff A Ming D400 (ジ エ Off ア-ミ Application D400) (weight-average molecular weight about 400), Jeff A Ming D2000 (ジ エ Off ア-ミ Application D2000) (weight-average molecular weight about 2000) (more than be Ha Application Star マ Application corporate system, trade(brand)name) etc.
(in the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a, b and n are respectively the integers more than 1, m is the integer more than 0)
Monocycle oxosilane (a
2) be included in the compound that has group shown in 1 epoxy group(ing) and 1 following formula in 1 molecule,
(wherein, Q
1, Q
2And Q
3Represent alkyl, alkoxyl group and alkyl carbonyl oxy respectively, but Q
1, Q
2And Q
3In at least 1 be group beyond the alkyl)
Specifically can enumerate the compound of following formula (5)～(11) expression.
Poly-affixture of the present invention (A) can be by above-mentioned amine compound (a with polyoxyalkylene chain
1) amino and monocycle oxosilane (a
2) epoxy group(ing) between opening preparation.This opening usually can be in suitable inert solvent, and at about 50～about 130 ℃, under the temperature in preferred about 70～about 110 ℃ of scopes, stir about 30 minutes～6 hours was implemented in preferred about 1～3 hour.Monocycle oxosilane (a
2) to amine compound (a
1) usage ratio do not have strict restriction, general amine compound (a
1) amino per 1 mole, preferably at 0.5～2 mole, particularly preferably in using monocycle oxosilane (a in 0.5～1.5 mole the scope
2).In addition, as operable solvent, can enumerate hydro carbons such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester classes such as methyl acetate, ethyl acetate, butylacetate; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; The perhaps mixture of these solvents.
So that be example with the compound of the compound of above-mentioned formula (1) and above-mentioned formula (5) as the situation of starting raw material, above-mentioned amine compound (a
1) and monocycle oxosilane (a
2) reaction shown in following reaction formula.
Thus, can prepare weight-average molecular weight 250～10000, preferred 500～6000, the more preferably poly-affixture (A) in 1000～3000 scopes.The weight-average molecular weight that gained gathers affixture (A) surpasses 10000, and in covering with paint, lacquer, colour wash, etc. production line, the stability when this poly-affixture is subjected to shearing for a long time reduces, on the contrary, if weight-average molecular weight is lower than 250, be coated with the surface modulation effect deficiency of face, be easy on the face spout out being coated with.In addition, the weight-average molecular weight of poly-affixture (A) is in above-mentioned scope the time, in coating line, even should gather the shearing that affixture is subjected to filter filter or UF filter etc. for a long time, poly-affixture (A) is also stable, can not produce the obstruction of filter or UF film and be coated with unfavorable conditions such as adhering to pit on the face.
The cation electrodeposition electrodeposition coating:
Poly-affixture of the present invention (A) can be as described below after matrix resin and solidifying agent, other coating disperse to make emulsion with additive, makes the cation electrodeposition electrodeposition coating.
In addition, for example in acetate, formic acid or their mixture and poly-affixture (A), further add water-dispersion, can make water dispersion (A with organic acid
1).This water dispersion (A
1) can add to later in the bath of synthetic in advance cation electrodeposition electrodeposition coating, for example, can be when coating line be stopped work, interpolation such as off-day.Above-mentioned organic acid converts with the mgKOH of every 1g resin solid substance of poly-affixture (A), can be 10～100, and preferred 20～70, more preferably use in 30～50 the scope.The organic acid usage quantity converts with the mgKOH of every 1g resin solid substance, when being lower than 10mgKOH/g, be difficult to make poly-affixture (A) to become water dispersion, on the contrary, if surpass 100, the acid concentration (MEQ) of the cation electrodeposition electrodeposition coating of interpolation will rise, and therefore coulomb (Network-ロ Application) efficient reduces, can not make unfavorable conditions such as film even be easy to produce energising, and problem such as pin hole in GA material (hot dip alloyed zinc electroplating steel plate) is covered with paint, lacquer, colour wash, etc., occur.
According to the present invention, the cation electrodeposition electrodeposition coating that can cooperate or add poly-affixture (A) preferably contain as the cationic resin of matrix resin and as the blocked polyisocyanates compound of solidifying agent as basal component.
Resin cation (R.C.) as matrix resin is the resin that has the group of cationicallyizatioies such as amino, ammonium salt base, sulfonium salt Ji, phosphonium salt base in molecule, as the resin kind, can be usually as those of the matrix resin of electro-deposition coating, the resin of any one types such as epoxies, acrylic acid or the like, polybutadiene, Synolac class, polyester for example.Make particularly that to contain the amine addition Resins, epoxy that amino compound and polyepoxide addition reaction obtain proper.
As above-mentioned amine addition Resins, epoxy, can enumerate (1) polyepoxide and uncle single-and polyamine, Zhong Dan-and polyamine or primary, the secondary affixture (for example, referring to No. 3984299 specification sheets of United States Patent (USP)) that mixes polyamine; (2) polyepoxide and have the Zhong Dan of the primary amino of ketoimineization-and the affixture (for example, referring to No. 4017438 specification sheets of United States Patent (USP)) of polyamine; (3) polyepoxide and have reactant (for example, opening clear 59-43013 communique) that the oxy-compound etherificate of the primary amino of ketoimineization obtains etc. referring to the spy.
The polyepoxide that uses in the preparation of above-mentioned amine addition Resins, epoxy is to have 1 above epoxy group(ing) in 1 molecule, the compound of preferred 2 above epoxy group(ing), in general, have at least 200, preferred 400～4000, the more preferably number-average molecular weight and at least 160 in 800～2500 scopes, preferred 180～2500, more preferably the compound of the epoxy equivalent (weight) in 400～1500 scopes is proper, the compound that preferred especially polyphenol compound and epichlorohydrin reaction obtain.
As can be used in the polyphenol compound that forms this polyepoxide, can enumerate two (4-hydroxy phenyls)-2,2-propane, 4,4 '-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl-2 or the 3-tertiary butyl-phenyl)-2,2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyl)-1,1,2,2-ethane, 4,4 '-dihydroxy-diphenyl sulfone, phenolic varnish (Off エ ノ-Le ノ ボ ラ Star Network), cresols phenolic varnish (Network レ ゾ-Le ノ ボ ラ Star Network) etc.
This polyepoxide can be the material that obtains with partial reactions such as polyvalent alcohol, polyether glycol, polyester polyol, daiamid, poly carboxylic acid, polyisocyanate compounds, also can be the material that graft polymerizations such as caprolactone, Acrylic Acid Monomer such as 6-caprolactone are obtained.
As the uncle who in the preparation of the amine addition Resins, epoxy of above-mentioned (1), uses single-and polyamine, Zhong Dan-and polyamine or primary, the secondary polyamine that mixes, can enumerate list or dialkylamines such as single methylamine, dimethylamine, mono aminoethane, diethylamine, single Isopropylamine, Diisopropylamine, dibutyl amine, dibutylamine; Monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, monomethyl monoethanolamine etc. alkanolamine; Alkylidene group polyamine such as quadrol, propylene diamine, butanediamine, hexanediamine, diethylenetriamine, Triethylenetetramine (TETA) etc.
As the Zhong Dan of the primary amino that in the preparation of the amine addition Resins, epoxy of above-mentioned (2), uses-and polyamine with ketoimineization, can enumerate make ketone compound single with the uncle who in the preparation of the amine addition Resins, epoxy of above-mentioned (1), uses-and polyamine, Zhong Dan-and polyamine or primary, the secondary ketoimine thing that mixes compound (for example, single methylamine, monoethanolamine, quadrol, diethylenetriamine etc.) the reaction formation that has primary amino in the polyamine.
Oxy-compound as the primary amino that in the preparation of the amine addition Resins, epoxy of above-mentioned (3), uses with ketoimineization, can enumerate make ketone compound single with the uncle who in the preparation of the amine addition Resins, epoxy of above-mentioned (1), uses-and polyamine, Zhong Dan-and polyamine or primary, secondaryly mixes the ketoimine thing that contains hydroxyl that the compound (for example, monoethanolamine, list (2-hydroxypropyl) amine etc.) that has primary amino and hydroxyl in the polyamine reacts formation.
Above-mentioned amine addition Resins, epoxy also comprises making to have the polyol compound that the compound addition that contains active hydrogen group more than 2 obtains in above-mentioned polyepoxide, caprolactone and 1 molecule and contain the polyalcohol modified amine addition Resins, epoxy that amino compound reaction forms, and can preferably use.
Have the compound that contains active hydrogen group more than 2 in above-mentioned 1 molecule and have 62～5000 usually, the number-average molecular weight in 62～1500 scopes particularly, preferred per 1 molecule contains 2～30,2～10 groups that contain reactive hydrogen particularly, contain the group of reactive hydrogen as this, can enumerate hydroxyl, primary amino, secondary amino group etc.
As having the specific examples that contains the compound of active hydrogen group more than 2 in above-mentioned 1 molecule, can enumerate ethylene glycol, propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1, low molecular weight polyols such as 6-hexylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane; A wire or a chain polyether glycol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polymer with bis phenol A glycol ether; Organic dicarboxylic acid such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, toxilic acid, cyclohexane cyclohexanedimethanodibasic, phthalic acid, m-phthalic acid, terephthalic acid or organic diols such as its acid anhydrides and the above-mentioned low molecular weight polyols polyester polyol that polycondensation forms under the excessive condition of organic diol; Butanediamine, hexanediamine, tetren, penten, monoethanolamine, diethanolamine, trolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, 1, amine compound such as 3-diamino methylcyclohexanone, isophorone diamine, benzene dimethylamine, m-xylene diamine, diaminodiphenyl-methane, phenylenediamine, quadrol, propylene diamine, diethylenetriamine, Triethylenetetramine (TETA); Piperazine or with by the amine adduct of these amine compound deutero-polymeric amide, daiamid, epoxy compounds, ketoimine, aldimine etc.
As with above-mentioned 1 molecule in have the caprolactone of the compound addition reaction that contains active hydrogen group more than 2, can enumerate γ-Ji Neizhi, 6-caprolactone, δ-caprolactone etc., preferred especially 6-caprolactone.
Having the compound that contains active hydrogen group more than 2 and the addition reaction of caprolactone in above-mentioned 1 molecule can carry out according to itself known method, obtains polyol compound by this addition reaction.
The aminocompound that contains that uses in the preparation of above-mentioned polyalcohol modified amine addition Resins, epoxy is to import amino in resin, be used to make the cationic of this resin cationization to give composition, for example can use to have at least 1 compound with the reactive hydrogen of epoxy reaction.That its specific examples can be enumerated the uncle who uses in can the preparation as the amine addition Resins, epoxy of above-mentioned (1) is single-and polyamine, Zhong Dan-and polyamine or primary, the secondary polyamine that mixes; The Zhong Dan of the primary amino that in the preparation of the amine addition Resins, epoxy of above-mentioned (2), uses with ketoimineization-and polyamine; The material that the oxy-compound of the primary amino with ketoimineization that uses in the preparation of the amine addition Resins, epoxy of above-mentioned (3) uses.
The common number-average molecular weight of cationic resin is 700～6000, preferably 850～5000, further preferred in 1000～4000 scope, every 1kg resin, preferably at 0.5～3 equivalent, particularly preferably in 0.6～2.5 equivalent, further contain the cationic group particularly preferably in 0.7～2 normal scope.
In addition, the cationic resin is having the occasion of amino as the group of cationicallyization, with organic carboxyl acids such as formic acid, acetate, propionic acid, lactic acid; Acid neutralization such as mineral acid such as hydrochloric acid, sulfuric acid can water-solubleization or water-dispersionization, in addition, has the occasion of alkali such as ammonium salt base, sulfonium salt Ji Huo phosphonium salt base as the group of cationicallyization, can direct water-solubleization or water-dispersionization, and need not neutralize.
The cationic resin can water-solubleization or water-dispersion use, also can make organic solvent solution and use.The cationic resin dissolves in aqueous medium or dispersion with the acid neutralization, and the cation electrodeposition deposit is covered with paint, lacquer, colour wash, etc. becomes possibility.
And, also can use the xylene formaldehyde resin modification to contain aminoepoxy resin as matrix resin.The xylene formaldehyde resin modification contains aminoepoxy resin and comprises that xylene formaldehyde resin and the Resins, epoxy that contains aminocompound and epoxy equivalent (weight) 180～3000 react the aminoepoxy resin that contains that obtains.
As the preparation the above-mentioned Resins, epoxy that contains the parent material of aminoepoxy resin, preferably with regard to the same Resins, epoxy of the described material of above-mentioned cationic resin.
Xylene formaldehyde resin works to the inside plasticized (modification) of Resins, epoxy, for example can be in the presence of an acidic catalyst, make dimethylbenzene and formaldehyde and the phenols that further according to circumstances uses carries out condensation reaction and prepares.
As above-mentioned formaldehyde, the formalin, paraformaldehyde, trioxymethylene etc. that can enumerate industrial easy acquisition produce the compound of formaldehyde etc.
And, above-mentioned phenols comprises 1 yuan or 2 yuan of phenoloids with 2 or 3 reaction site, specifically can enumerate phenol, cresols, paraoctyl phenol, nonylphenol, bisphenol A, bis-phenol methane, Resorcinol, pyrocatechol, quinhydrones, p-tert-butylphenol, bisphenol sulphone, bis-phenol ether, p-phenyl phenol etc., these materials can be distinguished use separately, perhaps are used in combination more than 2 kinds.Wherein, preferred especially phenol, cresols.
As an acidic catalyst that in the condensation reaction of above-mentioned dimethylbenzene and formaldehyde and the phenols that further according to circumstances uses, uses, can enumerate sulfuric acid, hydrochloric acid, tosic acid, oxalic acid etc., sulfuric acid is suitable especially usually.
Condensation reaction for example can be by being heated to the temperature that the dimethylbenzene that is present in the reactive system, phenols, water, formalin etc. reflux, and about 80 ℃～about 100 ℃ temperature is carried out usually, and about 2～6 hours finish usually.
Under these conditions, in the presence of an acidic catalyst, make dimethylbenzene and formaldehyde and the phenols that further according to circumstances uses carries out reacting by heating, can obtain xylene formaldehyde resin.
The xylene formaldehyde resin that obtains like this can have 20～50000 centipoises (25 ℃) usually, preferred 25～35000 centipoises (25 ℃), the more preferably viscosity in 30～15000 centipoises (25 ℃) scope, usually preferably have 100～50000 in addition, preferred especially 150～30000, the hydroxyl equivalent in further preferred especially 200～10000 scopes.
Contain aminocompound and be and in Resins, epoxy, import aminoly, be used to make the cationic of this cationic epoxy resinization to give composition, the same aminocompound that contains that uses in the time of can using with above-mentioned cationic resin manufacture.
Above-mentioned xylene formaldehyde resin and contain aminocompound and can carry out according to order arbitrarily the reaction of above-mentioned Resins, epoxy preferably makes xylene formaldehyde resin usually and contains aminocompound and reacts with Resins, epoxy simultaneously.
Above-mentioned addition reaction usually can be in appropriate solvent, at about 80～about 170 ℃, carries out preferred about 1～5 hour about 1～6 hour under preferred about 90～about 150 ℃ temperature.As above-mentioned solvent, can enumerate hydro carbons such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester classes such as methyl acetate, ethyl acetate, butylacetate; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Perhaps mixture of these solvents etc.
The usage ratio of each reacted constituent does not have strict restriction in the above-mentioned addition reaction, can appropriate change, and be benchmark with Resins, epoxy, xylene formaldehyde resin and the total solid weight that contains these 3 kinds of compositions of aminocompound, more suitable in following scope.That is, Resins, epoxy uses in the scope of preferred 50～85 weight % usually at 50～90 weight %; Xylene formaldehyde resin uses in the scope of preferred 6～43 weight % usually at 5～45 weight %; Contain aminocompound usually 5～25%, use in the scope of preferred 6～20 weight %.
As with the solidifying agent of above-mentioned matrix resin and usefulness, consider that from aspects such as solidified nature, non-corrosibilities preferred polyisocyanate compound and encapsulant are shown the product that the addition reaction of chemical theory amount obtains greatly, promptly end capped polyisocyanate compound.
Polyisocyanate compound used herein can use known in the past material, can enumerate tolylene diisocyanate, xylylene vulcabond, phenylene vulcabond, ditan-2,4 '-vulcabond, ditan-4, aromatic series, aliphatics or alicyclic polyisocyanates compounds such as 4 '-vulcabond (being commonly referred to " MDI "), rough MDI, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; The cyclized polymer of these polyisocyanate compounds, isocyanic ester biuret body; Make the low molecule active hydrogen compounds of ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol, castor-oil plant wet goods and excessive these polyisocyanate compounds react the compound etc. that the end that obtains contains isocyanic ester.These compounds can use separately respectively or be used in combination more than 2 kinds.
On the other hand, encapsulant is the material that the isocyanate group addition of polyisocyanate compound is sealed, the blocked polyisocyanates compound of addition generation is stable at normal temperatures in addition, be preferably in when being heated to the sintering temperature (about 100～about 200 ℃ usually) of filming, encapsulant dissociates, and the free isocyanate group can be regenerated.
Satisfy the encapsulant of this important document and can enumerate lactone compounds such as 6-caprolactone, γ-Ji Neizhi; Oxime compounds such as methyl ethyl ketoxime, cyclohexanone-oxime; Phenolic compounds such as phenol, p-tert-butylphenol, cresols; Aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; Aromatic series such as phenylcarbinol, methylbenzyl alcohol alkyl alcohols; Ether alcohol such as ethylene glycol monobutyl ether, carbiphene compounds etc.
Except that these encapsulants, using the molecular weight with 2 hydroxyls reactive inequality is that 76～150 glycol or molecular weight are 106～500 contain carboxylic diol and also can be used as solidifying agent as the end capped polyisocyanates of encapsulant.
Above-mentioned glycol can have 2 reactive different hydroxyls, for example primary hydroxyl and secondary hydroxyl, primary hydroxyl and tert-hydroxyl, 2 hydroxyls of the combination of secondary hydroxyl and tert-hydroxyl, and has 76～150 molecular weight, can enumerate propylene glycol, dipropylene glycol, 1, the 3-butyleneglycol, 1, the 2-butyleneglycol, the 3-methyl isophthalic acid, the 2-butyleneglycol, 1, the 2-pentanediol, 1, the 4-pentanediol, 3-methyl-4, the 3-pentanediol, 3-methyl-4, the 5-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 5-hexylene glycol, 1,4-hexylene glycol etc. has the glycols of 2 reactive different hydroxyls.
Wherein, from the reactivity of end capped polyisocyanates, the reduction of weight loss on heating, the viewpoints such as storage stability of coating, preferred propylene glycol.These glycol are usually by reactivity high hydroxyl and isocyanic ester radical reaction, blocked isocyanate base.
Above-mentioned carboxylic glycol comprises the carboxylic diol that contains of molecular weight 106～500, owing to have carboxyl in the molecule, can improve dissociating property of low temperature, and can improve solidified nature under the low temperature, as curing catalysts, when using organo-tin compound, can greatly improve the solidified nature under the low temperature especially.
As containing carboxylic diol, can enumerate 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, dihydroxymethyl valeric acid, R-Glyceric acid etc.
Above-mentioned matrix resin and solidifying agent are benchmark with both total solids usually, matrix resin can be at 50～95 weight %, especially at 60～90 weight %, further in the scope of 65～85 weight %, use especially, solidifying agent can be at 5～50 weight %, at 10～40 weight %, further in the scope of 15～35 weight %, use especially especially.
In addition, the cation electrodeposition electrodeposition coating is a total solid with matrix resin and solidifying agent, can especially at 10～30 weight %, contain under the further special concentration in the scope of 15～25 weight % at 10～40 weight %.
The cation electrodeposition electrodeposition coating is except matrix resin and these 2 kinds of basal component of solidifying agent, as required, can also contain other coating additive, for example tinting pigment, filler pigment, rust-stabilising pigment, organic solvent, pigment dispersing agent, surface conditioner, tensio-active agent, acid, catalyzer etc. can contain with normally used amount.
The poly-affixture (A) of the invention described above can be in any stage of preparation cation electrodeposition electrodeposition coating, be coupled to (hereinafter referred to as " preceding additive process ") in the cation electrodeposition electrodeposition coating composition, perhaps also can add to (hereinafter referred to as " back additive process ") in the synthetic in advance cation electrodeposition electrodeposition coating.
In preceding additive process, for example can be dispersed in the aqueous medium with additive gathering affixture (A) other coating with matrix resin, solidifying agent and use according to circumstances, after forming emulsion, use this emulsion and colo(u)rant dispersion thickener, modulation cation electrodeposition electrodeposition coating.
When making above-mentioned emulsion, can be with other coating of gathering affixture (A), matrix resin, solidifying agent and according to circumstances using with additive thorough mixing together, make dissolving varnish, in aqueous medium, to the neutralizing agent that wherein adds the mixture more than 2 kinds or 2 kinds be selected from formic acid, acetate, lactic acid, propionic acid, citric acid, oxysuccinic acid, thionamic acid, these acid etc., water-dispersionization is made cation electrodeposition electrodeposition coating emulsion.
The use level of poly-affixture (A) is considered from aspects such as paint stabilities, as solid substance, per 100 weight parts of the total solid of matrix resin and solidifying agent, preferably,, further special in the scope of 1～10 weight part especially at 0.5～15 weight part at 0.1～20 weight part.
In addition, in the additive process of back, at first, add organic acids such as acetate, formic acid, lactic acid in poly-affixture (A), the mgKOH that makes it to reach with every its solid substance of 1g converts, 10～100, preferred 20～70, more preferably in 30～50 the scope, will gather affixture (A) water-dispersionization, modulate the water dispersion of poly-affixture (A).
In addition, according to usual method, add neutralizing agent in additive at above-mentioned matrix resin, solidifying agent and other coating of according to circumstances using, carry out water-dispersionization, make emulsion, to wherein adding the colo(u)rant dispersion thickener, as required, use medium, modulation cation electrodeposition electrodeposition coating.
In synthetic cation electrodeposition electrodeposition coating so in advance, add the water dispersion of above-mentioned poly-affixture (A), as solid substance, per 100 weight parts of the total solid of matrix resin and solidifying agent, with 0.1～20 weight part, 0.5～15 weight part particularly, further particularly add in the scope of 1～10 weight part, can obtain cation electrodeposition electrodeposition coating of the present invention.The interpolation of poly-affixture (A) can be carried out in the stage that the cation electrodeposition deposit is covered with paint, lacquer, colour wash, etc.
As above synthetic cation electrodeposition electrodeposition coating of the present invention can be covered with paint, lacquer, colour wash, etc. by the cation electrodeposition deposit, covers with paint, lacquer, colour wash, etc. on desirable substrate surface.
Electro-deposition is covered with paint, lacquer, colour wash, etc. usually can be with dilutions such as deionized waters, so that the solid concentration of bathing is about 5～about 40 weight %, further use the cation electrodeposition electrodeposition coating in pH regulator to 5.5～9.0 scopes to bathe, under the condition of bathing 15～35 ℃ of temperature and load voltage 100～400V, carry out usually.
There is no particular limitation for the thickness that the cation electrodeposition deposit of using cation electrodeposition electrodeposition coating of the present invention to form is filmed, usually based on cured coating film, preferably at 10～40 μ m, in the scope particularly preferably in 10～25 μ m.In addition, about the sintering temperature of filming, general about 120～about 200 ℃ on the coated article surface, the temperature in preferred about 140～about 180 ℃ of scopes is more suitable, and sintering time is 5～60 minutes, preferred about 10～30 minutes.
The cation electrodeposition electrodeposition coating of the present invention that contains poly-affixture (A) be coated with the finishability of face, spouting out property of oil resistant, water-fast mark, stain resistance etc. cover with paint, lacquer, colour wash, etc. operability and with the aspect excellences such as adhesivity of finish coat coating, especially when production line is covered with paint, lacquer, colour wash, etc. complex-shaped car body, poly-affixture of the present invention (A) is as water dispersion, (the time of having a rest when coating line production stops, time of having a rest when relieving, off-day etc.), can directly add in coatings tank, therefore operability is covered with paint, lacquer, colour wash, etc. in improvement and adjusting extremely easily.
In addition, when the pigment composition in the cation electrodeposition electrodeposition coating is reduced to 5 weight %～18 weight %, though can improve the settleability and the redispersibility of coating, can see the tendency that the face of being coated with is easy to spout out usually, but poly-affixture (A) does not make the non-corrosibility of filming reduce, therefore can add in the cation electrodeposition electrodeposition coating with the amount of the wide region of 0.1～20 weight part, cover with paint, lacquer, colour wash, etc. operability and be able to very big improvement.
Embodiment
Enumerate embodiment below and be described more specifically the present invention, but the present invention is not limited in these embodiment.In addition, " part " and " % " is weight part and " weight % ".
The manufacturing of poly-affixture (A):
Production Example 1
In reaction vessel, add " Sang Amilu TAP-40 (サ Application ア ミ-Le TAP-40) " (trade(brand)name, Sanyo changes into society's system, polyetheramine, weight-average molecular weight about 2300) 1150 parts, " KBM-403 " (trade(brand)name, chemistry society of SHIN-ETSU HANTOTAI system, γ-glycidoxy (グ リ シ De キ シ) propyl trimethoxy silicane, molecular weight about 240) 240 parts and ethylene glycol monobutyl ether are 345 parts, are warming up to 90 ℃.Keep this temperature and stirred 3 hours, obtaining the resin solid substance is 80%, and weight-average molecular weight is 2800, the poly-affixture No.1 of amine value 40mgKOH/g.
Production Example 2
In reaction vessel, add " Jeff A Ming D2000 (ジ エ Off ア-ミ Application D-2000) " (trade(brand)name, Ha Application Star マ Application society system, polyetheramine, weight-average molecular weight about 2000) 220 parts of 1000 parts, " KBM-403 " 240 parts and ethylene glycol monobutyl ether are warming up to 90 ℃.Keep this temperature and stirred 3 hours, obtaining the resin solid substance is 80%, and weight-average molecular weight is 2500, the poly-affixture No.2 of amine value 45mgKOH/g.
The manufacturing of water dispersion:
Production Example 3
In 1735 parts of poly-affixture No.1 that Production Example 1 obtains, add 5170 parts in 45 parts of acetate (mgKOH that amounts to every 1g by the resin solid substance converts, and is equivalent to 30) and water, make it water-dispersionization, obtain solid substance and be 20% water dispersion No.1.
Production Example 4
In 1550 parts of poly-affixture No.2 that Production Example 2 obtains, add 4610 parts in 40 parts of acetate (mgKOH that amounts to every 1g by the resin solid substance converts, and is equivalent to 30) and water, make it water-dispersionization, obtain solid substance and be 20% water dispersion No.2.
Production Example 5
In reaction vessel, add 320 parts of Virahols, under agitation be warming up to reflux temperature (about 83 ℃).Under reflux temperature under (about 83～87 ℃), through about 2 hours, toward wherein dripping following monomer and polymerization starter: 272 parts of vinylbenzene, 224 parts of n-butyl acrylates, 80 parts of vinylformic acid 2-hydroxy methacrylates, 144 parts of dimethylaminoethyl methacrylates, KBM-503 (SHIN-ETSU HANTOTAI's chemical industry system, trade(brand)name, γ-methacryloxypropyl trimethoxy silane, molecular weight about 250) mixture that 80 parts, Diisopropyl azodicarboxylate are 24 parts.
Then, further stir 30 minutes after, through 1 hour, drip 8 parts of the two dihydroxymethyl valeronitriles of azo be dissolved in the solution that obtains in 120 parts of the Virahols, stir about dropped into 320 parts of Virahols and cooling after 1 hour.Obtain solid substance 51% like this, amine value 64, hydroxyl valency 48, the acrylic copolymer varnish of number-average molecular weight about 20000.
Then, in 780 parts in this acrylic copolymer varnish, add 6.4 parts of acetate, about 30 ℃ stir 5 minutes down after, under violent stirring, dripped 1156 parts of deionized waters through about 30 minutes.Like this, obtain the oyster white water dispersion No.3 of solid substance 20%.
Production Example 6 (according to the special embodiment 1 that opens the 2002-294165 communique)
(Sanyo changes into the polypropylene glycol diglycidyl ether of industrial society system to add triumphant rice Oulu EP-400P (ケ ミ オ-Le EP-400P) in the reaction vessel, epoxy equivalent (weight) 297) 129.7 parts, Wo Sadaimu 216 (バ-サ ダ イ the system 216) (dimeracid of ヘ Application ケ Le plain boiled water society system, acid value 192) 99.6 parts and phenmethyl dimethylamine are 0.6 part, 160 ℃ down reaction is below 0.5 until acid value, obtain epoxy equivalent (weight) and be 2300 di-epoxide.
Then, add 41.0 parts of the amino-polyethers (Sanyo changes into the diethylenetriamine propylene oxide adduct of society's system, trade(brand)name: AP-10, molecular weight 684) of amine value 255 in this compound,, obtain the compound of number-average molecular weight 27000 80 ℃ of insulations 4 hours down.
Use another container, 261.1 parts of this compounds are joined in the mixed solution of 379.1 parts of 12.2 parts of 50% lactic acid and deionized waters and stir, further regulate, obtain the water dispersion No.4 of solid substance 20% with deionized water.
Production Example 7 (manufacturing of matrix resin No.1)
In the internal volume that thermometer, reflux cooler and stirrer are housed was 2 liters branch neck flask, pack into 50% formalin 240g, phenol 55g, 98% commercial sulphuric acid 101g and m-xylene 212g were 84～88 ℃ of reactions 4 hours down.After reaction finishes, leave standstill, separation resin mutually and aqueous sulfuric acid phase washes resin with water 3 times mutually, and under the condition of 20～30mmHg/120～130 ℃, the unreacted m-xylene of stripping 20 minutes obtains the xylene formaldehyde resin 1 of viscosity 1050 centipoises (25 ℃).
In another flask, add Ai Pikaote 828EL (エ ピ コ-the ト 828EL) ((ジ of Co., Ltd. of japan epoxy resin company
ヤパ Application エ Port キ シ レ ジ Application (strain)) system, trade(brand)name, Resins, epoxy, epoxy equivalent (weight) 190, molecular weight 350) 1000g, dihydroxyphenyl propane 400g and dimethyl benzene methylamine 0.2g, reacting until epoxy equivalent (weight) down at 130 ℃ is 750.
Then, the ketoimine thing 65g that adds above-mentioned xylene formaldehyde resin 1 300g, diethanolamine 140g and diethylenetriamine, after reacting 4 hours under 120 ℃, add ethylene glycol butyl ether 420g, the xylene formaldehyde resin modification that obtains amine value 52, resin solid substance 80% contains aminoepoxy resin, i.e. matrix resin No.1.
Production Example 8 (manufacturing of matrix resin No.2)
In PP-400 (Sanyo changes into industrial society system, trade(brand)name, polypropylene glycol, molecular weight 400) 400g, add 6-caprolactone 300g, be warming up to 130 ℃.Afterwards, add four titanium butoxide 0.01g, be warming up to 170 ℃.When keeping this temperature, through the time sampling, by infrared absorption spectrometry, follow the trail of unreacted 6-caprolactone amount, reach 98% when above in reactivity, cool off, obtain properties-correcting agent 1.
In addition, at Ai Pikaote 828EL (エ ピ コ-the ト 828EL) ((ジ of Co., Ltd. of japan epoxy resin company
ヤパ Application エ Port キ シ レ ジ Application (strain) system, trade(brand)name, Resins, epoxy, epoxy equivalent (weight) 190, molecular weight 350) add dihydroxyphenyl propane 400g and dimethyl benzene methylamine 0.2g among the 1000g, 130 ℃ down reaction be 750 until epoxy equivalent (weight).
Add nonylphenol 120g therein, reacting until epoxy equivalent (weight) down at 130 ℃ is 1000.Then, the ketoimine thing 65g that adds properties-correcting agent 1 200g, diethanolamine 95g and diethylenetriamine, after reacting 4 hours under 120 ℃, add ethylene glycol butyl ether 414g, obtain the polyalcohol modified aminoepoxy resin that contains of the nonylphenol addition of amine value 40, resin solid substance 80%, i.e. matrix resin No.2.
Production Example 9 (manufacturing of solidifying agent)
In Cowes Mo Nate M-200 (コ ス モ ネ-ト M-200) (Mitsui Chemicals, Inc's system, trade(brand)name, rough MDI) 270g, add methyl iso-butyl ketone (MIBK) 46g, be warming up to 70 ℃.After slowly adding carbiphene 281g again, be warming up to 90 ℃.
When keeping this temperature, through the time sampling, by infrared absorption spectrometry, confirm not exist stopped reaction after the absorption of unreacted isocyanic ester, regulate quantity of solvent, obtain the blocked polyisocyanates solidifying agent of solid substance 90%.
Production Example 10 (manufacturing of emulsion No.1)
8.2 parts in solidifying agent 33.3 parts of (30 parts of solid substances), mulberry Knicks PP-1000 (サ Application ニ Star Network ス PP-1000) that matrix resin No.1 87.5 parts of (70 parts of solid substances), Production Examples 9 that poly-affixture No.1 6.25 parts of (5 parts of solid substances), the Production Examples 7 that cooperate Production Example 1 to obtain obtain obtain 5 parts (annotating 1) and 10% formic acid, and after stirring, under violent stirring, dripped 173.8 parts of deionized waters, obtain the cation electrodeposition electrodeposition coating emulsion No.1 of solid substance 34% through 15 minutes.
Production Example 11～13 (manufacturings of emulsion No.2～4)
According to the cooperation shown in the table 1, the same with Production Example 10, obtain cation electrodeposition electrodeposition coating emulsion No.2～4.
The cooperation content of table 1 emulsion
(solid substance)
(annotating 1) mulberry Knicks PP-1000 (サ Application ニ Star Network ス PP-1000): Sanyo changes into society's system, trade(brand)name, polypropylene glycol
Production Example 14 (manufacturing of colo(u)rant dispersion thickener)
Mix 20 parts of quaternary Resins, epoxy 5.83 parts of (3.5 parts of solid substances), 14.5 parts of titanium whites of 60%, 0.3 part of carbon black, 7.0 parts of filler pigments, 1.0 parts of bismuth hydroxides, 1 part of organotin and deionized waters, obtain the colo(u)rant dispersion thickener of solid substance 55.0 weight %.
Embodiment and comparative example
Embodiment 1 (manufacturing of cation electrodeposition electrodeposition coating No.1)
The cation electrodeposition electrodeposition coating with emulsion No.1 309 parts (105 parts of solid substances) in, add 173.8 parts of colo(u)rant dispersion thickener that Production Example 14 obtains 49.6 parts (27.3 parts of solid substances) and deionized waters, obtain the cation electrodeposition electrodeposition coating No.1 of solid substance 20%.
Embodiment 2～4 and comparative example 1～4
According to the cooperation shown in the table 2, the same with embodiment 1, obtain cation electrodeposition electrodeposition coating No.2～No.8
The coating of table 2 cation electrodeposition electrodeposition coating cooperates
The making of test board
Each the cation electrodeposition electrodeposition coating that uses the foregoing description and comparative example to obtain, making with handkerchief Shandong Bond #3020 (パ Le ボ Application De #3020) (Japanese metal rust preventing company (Japanese パ-カ ラ イ ジ Application グ society)), trade(brand)name, zinc phosphate treatment agent) having carried out implementing electro-deposition on the cold rolling dull-finish steel of 150mm * 70mm * 0.8mm that chemical transformation handles and the zinc electroplating steel plate covers with paint, lacquer, colour wash, etc.In electric hot air dryer, at 170 ℃, sintering is filmed, and obtains test board.
According to following test conditions the gained test board is tested.Its result is as shown in table 3.
Table 3 test-results
(annotating 6) finishability: the surface roughness Ra value of the outer plate surface that usefulness Sa Futaisite 301 (サ-Off テ ス ト 301) (MITSUTOYO society system, trade(brand)name, surface roughness meter) mensuration electro-deposition is filmed.
Zero expression Ra value is lower than 0.25 μ m
△ represents that the Ra value is 0.25～0.35 μ m
* expression Ra value surpasses 0.35 μ m.
(annotating 7) spouting out property of oil resistant: the machine oil of 1ml is put into bottle cap, place it on the wet plate after electro-deposition is covered with paint, lacquer, colour wash, etc.Afterwards, 170 ℃ of sintering 20 minutes, observe the state of the face that is coated with.
Zero expression is not caved in, spouted out, and is good
The part that △ is illustrated in the face of the being coated with depression that sporadically appears
* be illustrated in whole being coated with and can see on the face and reach spouting out of substrate deeply
(annotating 8) water mark: drip 1ml deionized water, sintering afterwards on the wet plate after electro-deposition is covered with paint, lacquer, colour wash, etc.
The water mark is almost can't see in zero expression, and precision work is no problem
△ represents to confirm the water mark, can see that finishability reduces.
The water mark can be obviously confirmed in * expression, and finishability significantly reduces.
(annotating 9) sealer adhesivity: on each test board; with 10mm * 6mm * 6mm (vertical * horizontal * thick) coating Sang Sida 1065T (サ Application ス 1 065T) (day star company (サ Application ス -society) system; trade(brand)name; sealer); coated plate is vertically sling, measured the adhesion of sealer after 12 hours.
Not skew of zero expression, no problem
Below the △ presentation surface protective layer skew 5mm
* presentation surface protective layer is from the coated plate landing
(annotate 10) non-corrosibility: on the electro-deposition of each electro-deposition coated plate (the zinc electroplating steel plate that uses chemical transformation to handle) that 170 ℃ of sintering temperatures obtain under-20 minutes is filmed, scratch after substrate with the knife crosscut, according to JISZ-2371, carry out salt water resistance spray testing in 840 hours, become rusty, heave the length of amplitude (one-sided) from the evaluation of cutter cut.
Zero expression rust, the amplitude of heaving are lower than 3mm (one-sided)
△ represents rust, heaves amplitude 3～4mm (one-sided)
* expression rust, the amplitude of heaving surpass 4mm (one-sided)
(annotating 11) coating stability: use laboratory pump, under 30 ℃ the coating circulation after 12 hours, is being used 400 order filtering nets, measure and filter residual volume.
Below the zero expression 10mg/L
△ represents 11～20mg/L
* expression surpasses 20mg/L.
Claims (7)
1. cation electrodeposition coating, it is to contain aminocompound and Resins, epoxy and carry out amine addition Resins, epoxy or xylene formaldehyde resin modification that addition reaction obtains and close aminoepoxy resin as matrix resin containing to make, and contain the cation electrodeposition electrodeposition coating of blocked polyisocyanates compound as solidifying agent, in any stage of modulating it, cooperate by amine compound (a with polyoxyalkylene chain
1) and monocycle oxosilane (a
2) the poly-affixture of weight-average molecular weight in 250～10000 scopes that form, wherein, with respect to total solid 100 weight parts of matrix resin and solidifying agent, the poly-affixture amount of cooperation is 0.1～20 weight part.
2. the described cation electrodeposition coating of claim 1 wherein, has the amine compound (a of polyoxyalkylene chain
1) be selected from the compound of following formula (1), (2), (3) and (4) expression,
In the formula, R
0Expression NH
2Or OH, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a, b and n are respectively the integers more than 1, m is the integer more than 0,
H
2N(CH
2)
aO(R
1O)
n-(R
2O)
mR
3(2)
In the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a and n are respectively the integers more than 1, m is the integer more than 0,
In the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, n is the integer more than 1, m is the integer more than 0,
In the formula, R
1And R
2Represent C respectively
2H
4Perhaps C
3H
6, R
3Expression H, C
2H
5Perhaps C
3H
7, a, b and n are respectively the integers more than 1, m is the integer more than 0.
3. the described cation electrodeposition coating of claim 1, wherein, monocycle oxosilane (a
2) be selected from the compound of following formula (5)～(11) expressions,
4. the described cation electrodeposition coating of claim 1, wherein, poly-affixture is the amine compound (a with polyoxyalkylene chain
1) amino per 1 mole, with the monocycle oxosilane (a in 0.5～2 molar range
2) carry out that opening obtains.
5. the described cation electrodeposition coating of claim 1, wherein, poly-affixture has the weight-average molecular weight in 1000～3000 scopes.
6. each described cation electrodeposition electrodeposition coating in the claim 1～5, its following formation: in poly-affixture, add organic acid, mgKOH with every 1g solid substance converts, make it to reach 10～100, water-dispersion formation water dispersion is adding the water dispersion that forms in the synthetic cation electrodeposition electrodeposition coating in advance, per 100 weight parts of the total solid of matrix resin and solidifying agent add water dispersion 0.1～20 weight part.
7. each described cation electrodeposition electrodeposition coating carries out the coated article that the electro-deposition covering with paint obtains in the use claim 1～6.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2003106047 | 2003-04-10 | ||
| JP106047/2003 | 2003-04-10 | ||
| JP349810/2003 | 2003-10-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1771305A CN1771305A (en) | 2006-05-10 |
| CN100383174C true CN100383174C (en) | 2008-04-23 |
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ID=36751924
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| CNB2004800096333A Expired - Fee Related CN100383174C (en) | 2003-04-10 | 2004-03-30 | Polyaddition product and cationic electrodeposition coating comprising said polyaddition product |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433046A (en) * | 2010-09-29 | 2012-05-02 | 关西涂料株式会社 | Pigment dispersion pulp for electrophoretic coating and cationic electrophoretic coating composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5110962B2 (en) * | 2006-10-31 | 2012-12-26 | 関西ペイント株式会社 | Cationic electrodeposition coating composition and articles coated with the electrodeposition coating |
| CN110028763B (en) * | 2019-04-12 | 2021-08-06 | 西北工业大学 | Preparation method of low-density high-rate epoxy resin microporous material |
| KR20220011944A (en) * | 2020-07-22 | 2022-02-03 | 주식회사 케이씨씨 | Composition for electro-deposition coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5209871A (en) * | 1990-11-28 | 1993-05-11 | Ford Motor Company | Self-sealing liquid electrolyte useful in electrochromic device |
| US5789468A (en) * | 1997-03-27 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Internal anticratering agent for cathodic electrocoating compositions |
| CN1374991A (en) * | 1999-09-23 | 2002-10-16 | 纳幕尔杜邦公司 | Cathodic electrocoating compositions having improved appearance, improved edge converage and reduced craters |
-
2004
- 2004-03-30 CN CNB2004800096333A patent/CN100383174C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5209871A (en) * | 1990-11-28 | 1993-05-11 | Ford Motor Company | Self-sealing liquid electrolyte useful in electrochromic device |
| US5789468A (en) * | 1997-03-27 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Internal anticratering agent for cathodic electrocoating compositions |
| CN1374991A (en) * | 1999-09-23 | 2002-10-16 | 纳幕尔杜邦公司 | Cathodic electrocoating compositions having improved appearance, improved edge converage and reduced craters |
| JP2003510399A (en) * | 1999-09-23 | 2003-03-18 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Cathodic electrodeposition coating composition with improved appearance, improved edge coating and reduced craters |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433046A (en) * | 2010-09-29 | 2012-05-02 | 关西涂料株式会社 | Pigment dispersion pulp for electrophoretic coating and cationic electrophoretic coating composition |
| CN102433046B (en) * | 2010-09-29 | 2014-12-10 | 关西涂料株式会社 | Pigment dispersion pulp for electrophoretic coating and cationic electrophoretic coating composition |
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| CN1771305A (en) | 2006-05-10 |
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