CN1329460C - Lightless anion electrophoresis coating - Google Patents
Lightless anion electrophoresis coating Download PDFInfo
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- CN1329460C CN1329460C CNB2005100057960A CN200510005796A CN1329460C CN 1329460 C CN1329460 C CN 1329460C CN B2005100057960 A CNB2005100057960 A CN B2005100057960A CN 200510005796 A CN200510005796 A CN 200510005796A CN 1329460 C CN1329460 C CN 1329460C
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Abstract
The invention provides an anionic matted electro-deposition paint having 60 DEG gloss of less than 10, as well as having excellent performance in lower temperature curing capability, hardness of coating film and coverage of dies mark. An anionic matted electro-deposition paint comprising an emulsion formed by dispersing a resin (A) having a blocked isocyanate group and a hydroxyl group both presented simultaneously in a molecule, which is obtained by reacting a part of a free isocyanate group of a vinyl copolymer (a1) having 2 or more free isocyanate groups in one molecule with a part of hydroxyl group of a vinyl copolymer (a2) having hydroxyl group, carboxyl group and alkoxysilyl group, subsequently reacting all of the residual free isocyanate group with a blocking agent, and wherein the difference of solubility parameter (SP value) between the vinyl copolymer (a1) and vinyl copolymer (a2) is 0.4 to 1.0; and then further adding and dispersing a curing catalyst (B); which is characterized in comprising 0.1 to 10 weight parts of curing catalyst (B) with respect to 100 weight parts of total amount of resin (A).
Description
Technical field
The present invention relates to curability at low temperatures, hardness of film, mould scar (the ダ イ ス マ one Network) Lightless anion electrophoresis coating that covering property is good.
Background technology
Aluminium is in light weight, and processing easily, and good corrosion resistance utilizes these character to be widely used as particularly relevant with building materials material.
The hot-extrudable method of aluminium, normally with columniform aluminium ingot bar heating and melting, this melts flows into forcing machine then, is expressed in the mould in the hole with regulation cross-sectional shape, and similar production bean jelly formula ground makes the section bar with regulation shape by the hole.
In addition, usually owing to the rust-preventing characteristic of aluminium own, wear resistant, chemical proofing equal difference, so after generally aluminium being carried out anodic oxidation treatment, utilize unglazed unglazed the filming of anion electrophoresis coating lining.
Yet the occasion of the above-mentioned unglazed anion electrophoresis coating of electrophoretic painting on the aluminium section bar of anodic oxidation treatment exists the mould scar as the aluminium section bar of base material to appear and the problem of commodity value difference easily.
Past, in order to make this mould scar be difficult for appearing, invented about making two kinds of different acrylic resins of solubility parameter and not having the melamine resin of consistency to be dispersed in anion electrophoresis coating [patent documentation 1: the spy opens flat 10-46065 communique] in the water with these acrylic resins; In addition, contain in addition water-dispersed resin and melamine resin, utilize the difference of the SP value of resin to obtain the invention [patent documentation 2: the spy opens the 2001-131494 communique] of unglazed coating.
These inventions are because must be in baking more than 170 ℃, and so anodic oxidation coating is easy to generate be full of cracks, ornamental and film performance reduces, or the energy of consumption increases, so also be problem economically.
In addition, the occasion of the resin of use hydroxyl and carboxyl, the coating of blocked polyisocyanates compound, though can obtain the solidified nature of gel fraction more than 90% or high hardness of film (more than the pencil hardness 4H) 140 ℃ of bakings, gloss low (60 ° of gloss are below 10) or covering property of mould scar not enough [patent documentation 3: the spy opens flat 8-41380 communique].
In addition, there is the part of this hydroxyl in the acrylic resin of 2 above hydroxyls to react, make then in 1 molecule that the whole and end-capping reagent of residual free isocyanate groups reacts in a part that also has the relevant free isocyanate groups that makes the vinyl polymer that 2 above free isocyanate groups are arranged in 1 molecule and 1 molecule and has the invention [patent documentation 4: the spy opens flat 5-247175 communique] of the resin of blocked isocyanate base and hydroxyl.When this invention only is applicable to anion electrophoresis coating, can not obtain curability at low temperatures, hardness of film, no optical coating that covering property of mould scar is good.Moreover if there is not optical coating, then covering property of mould scar is good.
Summary of the invention
The problem to be solved in the present invention is to find curability at low temperatures, hardness of film, the good Lightless anion electrophoresis coating of covering property of mould scar.
The inventor finds by making the ethylenic copolymer (a that the free isocyanate groups more than 2 is arranged in 1 molecule in order to address the above problem with great concentration the result of research repeatedly
1) the part of this free isocyanate groups, with the ethylenic copolymer (a that hydroxyl, carboxyl and alkoxysilyl are arranged
2) in the part reaction of this hydroxyl, make the whole and end-capping reagent reaction of residual free isocyanate groups then, use in 1 molecule obtain like this and deposit the resin (A) of blocked isocyanate base and hydroxyl and the Lightless anion electrophoresis coating of curing catalysts (B) composition, can address the above problem, thereby finish the present invention.
That is, the present invention relates to
1. Lightless anion electrophoresis coating, it is characterized in that, carry out water-dispersion, add curing catalysts (B) again and carry out the dispersive emulsion and constitute by resin (A), total amount 100 weight parts with respect to resin (A), contain curing catalysts (B) 0.1～10 weight part, described resin (A) is to make the ethylenic copolymer (a that 2 above free isocyanate groups are arranged in 1 molecule
1) this free isocyanate groups a part with the ethylenic copolymer (a of hydroxyl, carboxyl and alkoxysilyl is arranged
2) the part reaction of hydroxyl, make whole and the end-capping reagent of residual free isocyanate groups react in 1 molecule that obtains then and have the resin of blocked isocyanate base and hydroxyl, and ethylenic copolymer (a
1) and ethylenic copolymer (a
2) the difference of solubility parameter (SP value) be 0.4～1.0.
2. the 1st described Lightless anion electrophoresis coating is characterized in that curing catalysts (B) is at least a compound that is selected from organo-tin compound and amine compound.
3. the 1st or the 2nd described Lightless anion electrophoresis coating is characterized in that ethylenic copolymer (a1) is the multipolymer of being made by vinyl monomer that contains isocyanate group and other vinyl monomer.
4. each described Lightless anion electrophoresis coating of the 1st～3 of application and 60 ° of gloss of the coated surface that obtains are the unglazed coated article below 10 on the aluminium base of anodic oxidation treatment.
Lightless anion electrophoresis coating of the present invention adopted 140 ℃ of low-temperature bakes dry 20 minutes, can obtain hardness of film (more than the pencil hardness 4H), 60 ° of gloss that covering property of mould scar is good are the no optical coating below 10.
The present composition is owing to have the anion electrophoresis coating inaccessiable curability at low temperatures of use melamine resin as cure component, produce be full of cracks thereby ornamental or film performance reduction and the big problem of energy consumption so can solve the anodic oxidation coating of the baking of adopting 170 ℃ in the past, in addition, can obtain to use the anion electrophoresis coating irrealizable no optical coating of blocked polyisocyanates compound as cure component in the past.
Lightless anion electrophoresis coating of the present invention is to contain the good Lightless anion electrophoresis coating of curability at low temperatures that resin (A) and curing catalysts (B) is scattered in the emulsion that obtains in the water.Below at length describe.
Resin (A): resin (A) has the vinyl polymer of 2 above free isocyanate groups (a by making in 1 molecule
1) the part of this free isocyanate groups and the ethylenic copolymer (a that side chain has hydroxyl, carboxyl and alkoxysilyl
2) (below, be called for short " water dispersible ethylenic copolymer (a
2) ") in the part reaction of hydroxyl, make in 1 molecule of whole and end-capping reagent reaction formation of residual free isocyanate groups then and have the resin formation of blocked isocyanate base and hydroxyl.
Ethylenic copolymer (a
1) be to use the vinyl monomer that contains isocyanate group (below, be called for short " monomer that contains the NCO base ") as must composition, also use the multipolymer of other vinyl monomer system, main end and/or side chain at straight chain polymer has isocyanate group.
The monomer that contains the NCO base is that at least 1 not compound of end-blocking free isocyanate groups and free-radical polymerised pair of key is arranged respectively in 1 molecule, for example, can use be selected between-or right-pseudoallyl-α, more than a kind or 2 kinds of the affixture of 1: 1 (mol ratio) of alpha-alpha-dimethyl phenmethyl isocyanic ester, 2-isocyanate group ethyl-methyl acrylate, hydroxyl vinyl monomer and diisocyanate cpd etc.
Contain the above-mentioned hydroxyl vinyl monomer that uses in the monomeric preparation of NCO base, it is the compound that 1 above hydroxyl and free-radical polymerised pair of key are arranged respectively in 1 molecule, for example, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylformic acid hydroxyl butyl ester, vinylformic acid 2,3-dihydroxyl propyl ester, vinylformic acid 2-hydroxyl-3-phenoxy ethyl, vinylformic acid 2-hydroxyl-3-ethoxy ethyl ester etc.Also can enumerate the material such as addition such as mole such as grade of acrylic or methacrylic acid and glycol (carbonatoms 2～20) etc.
In addition, containing the above-mentioned diisocyanate cpd that uses in the monomeric preparation of NCO base is the compound that 2 isocyanate group are arranged in 1 molecule, for example, can enumerate tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysinediisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (2,6)-vulcabond, the aliphatics of isophorone diisocyanate and trimethyl cyclohexane vulcabond etc., aromatic series and alicyclic diisocyanate cpd.
As the monomer that contains the NCO base, among above-mentioned preferred use have third stage isocyanate group between-pseudoallyl-α, the α-Er Jiajibianji isocyanic ester prevents and ethylenic copolymer (a from described later
2) reaction in the viewpoint of gelation consider, preferred especially.
In addition, other vinyl monomer, free-radical polymerised pair of key arranged in preferred 1 molecule and do not have can with the compound of isocyanate group reactive activity hydrogen, can enumerate the aromatic vinyl base system monomer of vinylbenzene, alpha-methyl styrene, Vinyl toluene etc. particularly; (methyl) esters of acrylic acid of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate etc.;
VI SCOAT 3F (Osaka organic chemistry society system, trade(brand)name, the following same meaning of expression), VISCOAT 3MF, VISCOAT 8F, VISCOAT 8MF, (methyl) vinylformic acid perfluor cyclohexyl, N-2-propyl group perfluorooctane sulfonate acid amides ethyl (methyl) acrylate, vinyl fluoride, vinylidene etc. to contain fluoride-based be monomer;
(methyl) vinylformic acid N, N '-lignocaine ethyl ester, (methyl) vinylformic acid N, N '-lignocaine ethyl ester, (methyl) vinylformic acid N, N '-lignocaine ethyl ester), N, the nitrogenous ethene base system monomer of N '-diethyl (methyl) acrylamide etc.; The vinyl ether of ethyl vinyl ether, vinyl-n-butyl ether etc. is a monomer; Reach (methyl) glycidyl acrylate, (methyl) vinylformic acid 3, the alkyl etherate of 4-epoxycyclohexyl methyl esters, arylolycidyl ethers, n-methylolacrylamide, (methyl) acrylamide, (methyl) acrylate chloride, vinylchlorid, vinylidene chloride, (methyl) vinyl cyanide, γ-methacryloxypropyl alkyl trimethoxysilane etc., these can use to mix more than a kind or 2 kinds and use.
The ratio that contains monomer and other vinyl monomers of NCO base is so long as ethylenic copolymer (a
1) 1 molecule in have the scope of 2 above free isocyanate groups to get final product, do not have particular restriction, according to the monomer that contains the NCO base/other vinyl monomer (weight ratio), 100/0～1/99, preferred 65/35～30/70 scope suits.
In addition, just contain the monomer of NCO base or contain the polyreaction of the monomer and other the vinyl monomer of NCO base, usually preferably do not have can with the inert organic solvents of isocyanate group reactive activity hydrogen in carry out.
As such inert organic solvents, for example, can use the single solvent or the mixed solvent of the aliphatic hydrocarbon, ester class, ketone etc. of hexane, heptane, octane etc.Specifically, for example can use the mixed solvent of the acetate methoxyl group propyl ester and the peroxidation isobutyl carbonate propyl group tert-butyl ester, these solvents are owing to containing moisture sometimes, so preferably dewater in advance as required.
These polyreactions use radical polymerization initiator to carry out ethylenic copolymer (a usually under 50～180 ℃ temperature
1) molecular weight can utilize reaction density, amount of initiator etc. to regulate, with regard to reaction density,, carry out polyreaction in the scope of 20-80 weight % as polymkeric substance.
Especially in order to improve percent polymerization, preferably use the initiator of superoxide or carbonates, carry out polyreaction more than 100 ℃ in temperature of reaction.More preferably use the acrylic ester monomer simultaneously, then obtain the high polymkeric substance of percent polymerization easily.The concentration of polymerization starter can be used in the scope of 0.01～15 weight % of total monomer, but the scope of preferred 0.1～10 weight %.
Such ethylenic copolymer (a
1) weight-average molecular weight (annotate 1) preferred 500～50,000, preferred especially 1,500～30,000 scope.In addition, isocyanate value is suitably 30～200mgNCO/10g.Ethylenic copolymer (a in addition
1) 2 above free isocyanate group are arranged in its 1 molecule, but preferably do not have fully can with this isocyanate group reactive activity hydrogen.
(annotating 1) weight-average molecular weight: measure according to JIS K0124-83, separator column uses TSKGEL4000 H
XL+ G3000 H
XL+ G2500 H
XL+ G2000 H
XL(Japan Cao Da corporate system), under 40 ℃, flow velocity is the 1.0ml/ branch, and eluant uses the GPC tetrahydrofuran (THF), and the chromatogram that is obtained by the RI refractometer and the calibration curve calculating of polystyrene are obtained.
Ethylenic copolymer (a
2):
Ethylenic copolymer (a
2), suitable to use the unsaturated monomer, (2) hydroxyl unsaturated monomer, (3) that contain alkoxysilyl with (1) to contain the carboxyl unsaturated monomer be necessary composition, as required the multipolymer that obtains with (4) other unsaturated monomer copolymerization.As these monomer components, can enumerate following monomer.
(1) contain the alkoxysilyl unsaturated monomer: for example, r-(methyl) acryloyl-oxy propyl trimethoxy silicane, r-(methyl) acryloyl-oxy propyl group methyl dimethoxysilane, r-(methyl) acryloyl-oxy propyl-triethoxysilicane, vinyltrimethoxy silane etc.
(2) hydroxyl unsaturated monomer: for example, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, and PLACCEL FM1 (DAICEL CHEMICALINDUSTRIES in addition, LTD. make, trade(brand)name, caprolactone modification (methyl) crylic acid hydroxy ester class), PLACCEL FM2 (the same), the hydroxyl unsaturated monomer of PLACCEL FM3 (the same), PLACCEL FA1 (the same), PLACCELFA2 (the same), PLACCEL FA3 (the same) etc. etc.
(3) contain the carboxyl unsaturated monomer: for example, (methyl) vinylformic acid, toxilic acid etc.
(4) other unsaturated monomer: for example, can enumerate (methyl) acrylic acid C of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate etc.
1～C
18Alkyl or cycloalkyl ester class, the aromatic vinyl monomer class of vinylbenzene etc., (methyl) acrylamide and the derivatives class thereof of (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-methylol (methyl) acrylamide etc., (methyl) acrylonitrile compound class or the like.
Such ethylenic copolymer (a
2) weight-average molecular weight preferred 500～50,000, preferred especially 2,000～35,000 scope, it is the scope of 20～200mg KOH/g that hydroxyl is suitable for especially according to hydroxyl value.
In the manufacturing of resin (A), ethylenic copolymer (a
1) and ethylenic copolymer (a
2) reaction be the urethane reaction of isocyanate group and hydroxyl, specifically, at ethylenic copolymer (a
1) organic solution in mixed ethylene base co-polymer (a
2), usually under 20～100 ℃, preferred 25～60 ℃ temperature, carry out the urethane reaction,
It is that isocyanate value is controlled that reaction utilizes the reduction of isocyanate group.In order to obtain curability at low temperatures or hardness of film, in this reaction, also preferably use the curing catalysts of organo-tin compound etc. in addition.
Ethylenic copolymer (a
2) combined amount, press ethylenic copolymer (a
1) the weight-average molecular weight meter, at least can import average 0.1 urethane bond in 1 molecule of per 500～50,000 and get final product so long as make, preferably by weight-average molecular weight per 500～30, import average 0.5～1.5 urethane bond, most preferably ethylenic copolymer (a in 1 molecule of 000 scope
1) import 1 urethane bond in per 1 molecule.
Then, make as above-mentioned ethylenic copolymer (a
2) reaction, import urethane bond, the water dispersible ethylenic copolymer (a that made addition
2) ethylenic copolymer (a
1) contained residual free isocyanate groups and following end-capping reagent, end-blocking is carried out in reaction under common 20～100 ℃ temperature, makes resin (A).
As end-capping reagent, for example, can enumerate the phenols of phenol, cresols, xylenol, right-ethylphenol, neighbour-isopropyl-phenol, p-tert-butylphenol, right-tert-octyl phenol, thymol, right-naphthols, right-nitrophenols, right-chlorophenol etc.;
The alcohol system of methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methylcyclohexane, ethylene glycol butyl ether, methyl carbitol, benzylalcohol, ethyleneglycol monophenylether, furfuryl alcohol, hexalin etc.; The active methylene group class of dimethyl malonate, methyl aceto acetate etc.;
The thio-alcohol of butyl sulfhydryl, thiophenol, uncle's lauryl mercaptan etc.; Monoacetylaniline, acetyl replace the amides of anisidine, ethanamide, benzamide etc.; The acid imide of succinimide, maleimide etc.;
The amine of pentanoic, phenyl naphthyl amines, aniline, carbazole etc.; The imidazoles of imidazoles, 2-ethyl imidazol(e) etc.; The urea class of urea, thiocarbamide, ethylidene-urea etc.; The Carbamates of N-phenylcarbamic acid phenyl ester, 2- oxazolidone etc.; The imines class of ethylenimine etc.;
The oxime system of formoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone-oxime etc.; The sulphite system of sodium bisulfite, Potassium hydrogen sulfite etc.;
The lactams of ε-Ji Neixianan, δ-Valerolactim, butyrolactam, azetidinone etc. etc.; The pyrazoles of 3,3-methylpyrazole, 4-nitro-3 and 4-bromo-3 etc. etc.
With regard to resin (A), ethylenic copolymer (a
1) and ethylenic copolymer (a
2) by the urethane reaction of isocyanate group and hydroxyl, utilize urethane bond to carry out combination.
Have average at least one blocked isocyanate base and at least one hydroxyl in the resin that makes like this (A) molecule, the weight-average molecular weight of resin (A) is 1,000～120, about 000, particularly 5,000～50, about 000, hydroxyl value (mgKOH/g) is suitably 25～250 scope.
Especially, in order to obtain the no optical coating of low gloss (60 ° of gloss are below 10), ethylenic copolymer (a
1) and ethylenic copolymer (a
2) solubility parameter (SP value (annotate 2)) difference be 0.4～1.0 scope, preferably 0.5～0.8.
(annotating 2) solubility parameter: so-called SP value is the abbreviation of solubility parameter, the yardstick of the molecular interaction of express liquid molecule.This SP value is at ethylenic copolymer (a
1) and water dispersible ethylenic copolymer (a
2) during composition, relate to the occasion that changes monomeric SP value, use following formula (1) to ask the SP value of multipolymer, this SP value is substituted the SP value of making multipolymer.
Monomeric SP value is summarized in J.Paint technology, and vol.42 is in 176 (1970).
SP=SP
1* fw
1+ SP
2* fw
2+ ... SP
n* fw
nFormula (1)
(SP
1, SP
2SPn represents each monomeric SP value, fw
1, fw
2... fwn represents the weight fraction of each monomer with respect to the monomer total amount.)
In addition, relate to the constant occasion of monomeric SP value, can adopt the cloud point titration to measure, particularly, can be according to following formula (2), the formula of K.W.SUH, J.M.CORBETT (Journalof Applied Polymer Science, 12,2359,1968) calculate.
(in the formula, V
HThe appearance integration rate of expression normal hexane, V
DThe appearance integration rate of expression deionized water, δ
HThe SP value of expression normal hexane, δ
DThe SP value of expression deionized water).
The cloud point titration, be in the solution that in 10ml acetone, is dissolved with as the resin 0.5g (solids component) of sample, slowly add normal hexane, titer H (ml) when reading cloud point, titer D (ml) when similarly reading the cloud point that adds deionized water in acetone soln, these titers use following formula to calculate V
H, V
D, δ
H, δ
DMoreover the SP value of each solvent is an acetone: 9.75, normal hexane: 7.24, deionized water: 23.43.
[V
H＝H/(10+H)、V
D＝D/(10+D)、δ
H＝9.75×10/(10+H)+7.24×H/(10+H)、δ
D＝9.75×10/(10+D)+23.43×D/(10+D)]
In addition, ethylenic copolymer (a
1), and ethylenic copolymer (a
2) second-order transition temperature (Tg) be more than 10 ℃, help improving film performance.
Curing catalysts (B): the coating that anion electrophoresis coating of the present invention is a curability at low temperatures, hardness of film is good, contain curing catalysts (B) as necessary composition.Curing catalysts (B), as organo-tin compound, for example be fit to use stannous octoate, dibutyltin diacetate, two sad dibutyl tins, dibutyl tin laurate, two oxysuccinic acid dibutyl tins, tetrabutyl tin, Dibutyltin oxide, dibenzoic acid oxygen (dibenzoateoxy) dibutyl tin, dibenzoic acid oxygen dioctyl tin etc.;
As amine compound, for example, be fit to use Trimethylamine 99, triethylamine, dimethylcyclohexylamine, N-tetramethyl--1,6-hexanediamine, N-five methyl diethylentriamine, 2-methyl isophthalic acid, the tertiary amine of 4-diazabicyclo [2,2,2] octane etc.
These curing catalysts (B) are by using separately, and preferred the mixing more than 2 kinds uses, and helps the raising of curability at low temperatures or hardness of film.The total amount of curing catalysts (solids component conversion) is complied with its kind and difference, but usually, total amount 100 weight parts with respect to resin (A), solid component meter by curing catalysts (B) contains 0.1～10 weight part, considers preferably to contain 0.5～8 weight part from catalyst performance and paint stability aspect.
Following the carrying out of manufacturing of the emulsion that anion electrophoresis coating of the present invention uses: in resin (A), add curing catalysts (B), after mixing 0.1～1.5 equivalent, preferred 0.2～1.2 normal neutralizing agent (basic cpd) with respect to the carboxyl of resin (A), carry out blending dispersion, and then adding deionized water, make solids component reach 10～60 weight %, preferred 10～40 weight % use neutralizing agent to regulate pH then, and making pH is 7.0～8.0.
As above-mentioned neutralizing agent, uncle's monoamine of ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol etc. is arranged; The secondary monoamine of diethylin diethanolamine, two n-propyl alcohol amine or diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine, N-ehtylethanolamine etc.; Uncle's monoamine of dimethylethanolamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, methyldiethanolamine, dimethylaminoethanol etc.; The polyamine triethylamine of diethylenetriamine, hydroxyethylamino ethamine, ethylamino ethamine, methylamino-propylamine etc. etc.
In the Lightless anion electrophoresis coating of the present invention, can add pigment, dyestuff, curing catalysts, flowing regulator as required, carry out pH regulator, add deionized water, obtain the anion electrophoretic coating of solids component 5～20 weight %.In addition, by cooperating UV light absorber, photostabilizer again, also can make filming of high-weatherability.
As above-mentioned UV light absorber, can enumerate the salicyclic acid derivatives of salol, p-octylphenyl salicylate, Whitfield's ointment 4-tertiary butyl phenyl ester etc.; 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-methoxyl group-5-sulfo group-benzophenone Trihydride (ト リ ヒ De レ one ト), 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-octadecane oxygen base benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-sodium sulfonate benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 4-dodecyloxy-2-dihydroxy benaophenonel, 5-chloro-2-dihydroxy benaophenonel, resorcinol monobenzoate, 2, the 4-dibenzoyl resorcinol, 4, the 6-dibenzoyl resorcinol, hydroxyl dodecyl benzophenone, 2, the benzophenone of 2 '-dihydroxyl-4 (3-methacryloxy-2-hydroxyl propoxy-) benzophenone etc.; The benzotriazole category of 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole etc. and the compound of other (oxanilide, cyanoacrylates etc.) etc.
As mix the photostabilizer that uses with UV light absorber, be the hindered amine derivative, specifically can enumerate two (2,2 ', 6,6 '-tetramethyl--4-piperidyl) sebates, 4-benzoyloxy-2,2 ', 6,6 '-tetramethyl piperidine etc.These can suitably select to use more than a kind or 2 kinds.
Film in order to use Lightless anion electrophoresis coating of the present invention to form, with the above-mentioned anion electrophoresis coating that obtains as bathing (being added in the groove), after being immersed in this aluminium in this bath, use painted or non-coloring anodic oxidation aluminium as coated article, carry out the anionic electrodeposition electrophoresis painting dressing, making dry film thickness is about 5～30 μ m, do not wash (not rinsing), or wash (rinsing), after at room temperature condensing then, by at 60～150 ℃, preferred 80～140 ℃ down baking carried out drying in about 20～40 minutes, can form and film.
The hardness of film of the coated article that the Lightless anion electrophoresis coating application obtains, 4H is above, the high hardness of film of figure health hardness (annotating 4) more than 4 to present pencil hardness (annotating 3).
(annotating 3) pencil hardness: according to JIS K5600-5-4, be 45 ° angle placement pencil-lead approximately, exert oneself by moving forward about 10mm with even velocity to test coated plate face limit with the degree limit that pen core does not fracture with test coated plate face.Change testing position, should operate repetition 5 times, the hardness mark of the hardest pencil when cannot not filming brokenly is as pencil hardness.
(annotating 4) figure health (Tukon) hardness: coated plate after 20 ℃ thermostatic chamber is placed 4 hours, is used American Chain ﹠amp; The TUKON microhardness tester of Cable Company corporate system is measured.
In addition, Lightless anion electrophoresis coating by being used in combination to 2 kinds of emulsions of major general, can easily be regulated unglazed degree.
For example can use the anion electrophoresis coating that contains following emulsion (1) and emulsion (2), emulsion (1) is with respect to ethylenic copolymer (a
1) and ethylenic copolymer (a
2) total amount 100 weight parts, adopt ethylenic copolymer (a
1)/ethylenic copolymer (a
2The cooperation ratio of)=30～90 weight part/10～70 weight parts carries out that water-dispersion obtains, and emulsion (2) is to adopt the cooperation ratio different with emulsion (1), at ethylenic copolymer (a
1)/ethylenic copolymer (a
2The scope of)=30～90 weight part/10～70 weight parts carries out that water-dispersion obtains.
For example, when wishing on the paint line to obtain to make the coated article of unglazed degree variation, can anion electrophoresis coating be replenished, in time regulate by changing the cooperation ratio of emulsion (1)/emulsion (2).
Description of drawings
Fig. 1 is the synoptic diagram of facial mask tack test.
Nomenclature
1 films
2 aluminium as coated article
3 supporting plates
4 are used for fixing the part of test board
Embodiment
Below enumerate embodiment and illustrate in greater detail the present invention.The present invention is not subjected to the qualification of embodiment.Moreover " part " reaches " % " expression " weight part " and reaches " weight % ".
Preparation example 1 ethylenic copolymer (a
1) preparation example of solution No.1
In the reactor that has stirrer, reflux exchanger and thermometer, add 65 parts of acetate methoxyl group propyl ester, heating remains on 130 ℃, with pseudoallyl-α between dropping in 3 hours, the mixture of 25 parts of α-Er Jiajibianji isocyanic ester (m-TMI), 40 parts of Propenoic acid, 2-methyl, isobutyl esters, 4 parts of n-butyl acrylates, 31 parts of vinylformic acid methoxyl group ethyl esters.
Then, with the mixed solution that dripped 35 parts of acetate methoxyl group propyl ester, 5.0 parts of the peroxidation isobutyl carbonate propyl group tert-butyl esters in 1 hour, recurring 3 hours, make the ethylenic copolymer (a of solids component 50%
1) solution No.1.
Ethylenic copolymer (a
1) ethylenic copolymer (a among the solution No.1
1) weight-average molecular weight is about 5,000, the SP value is 9.0, Tg is 24.1 ℃.
Preparation example 2～5
With preparation example 1 similarly according to the content that cooperates of table 1, use the solvent adjustment solids component, make ethylenic copolymer (a
1) solution No.2～No.5.
Table 1
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | ||
| Ethylenic copolymer (a1) solution | No.1 | No.2 | NO.3 | No.4 | No.5 | |
| Cooperate | Acetate methoxyl group propyl ester | 65 | 65 | 65 | 65 | 65 |
| Between-pseudoallyl-α, the α-Er Jiajibianji isocyanic ester | 25 | 25 | 25 | 30 | 30 | |
| Propenoic acid, 2-methyl, isobutyl ester | 40 | 42 | ||||
| N-butyl acrylate | 4 | 17 | 39 | |||
| Vinylformic acid methoxyl group ethyl ester | 31 | 16 | ||||
| 2-EHA | 33.4 | |||||
| Methyl methacrylate | 41.6 | |||||
| Jia Jibingxisuanyizhi | 70 | |||||
| Acetate methoxyl group propyl ester | 35 | 35 | 35 | 35 | 35 | |
| The peroxidation isobutyl carbonate propyl group tert-butyl ester | 5 | 5 | 5 | 5 | 5 | |
| Solids component (%) | 50 | 50 | 50 | 50 | 50 | |
| Weight-average molecular weight | 5000 | 5000 | 5000 | 5000 | 5000 | |
| The SP value | 9.0 | 8.8 | 8.8 | 8.3 | 8.4 | |
| Tg(℃) | 24.1 | 38 | 24.4 | 65 | -53 | |
Preparation example 6 ethylenic copolymer (a
2) preparation example of solution No.1
In reaction vessel, add 275 parts of acetate methoxyl group propyl ester, remain on 80 ℃, use the mixture of 1 part of 75 parts of 3 hours drip styrenes, 155 parts of methyl methacrylates, 95 parts of n-butyl acrylates, 50 parts of ethyl propenoates, 75 parts of vinylformic acid 2-hydroxyl ethyl esters, 35 parts in vinylformic acid, 15 parts of gamma-methyl allyl acyloxypropyl trimethoxysilanes and azo methyl pentane nitrile then, add 3 parts of azo methyl pentane nitriles then, keep reacting in 3 hours at 80 ℃, make the water dispersible ethylenic copolymer (a of the solids component 65 weight % of alkoxysilyl
2) solution No.1.Water dispersible ethylenic copolymer (a among this solution No.1
2) the SP value be 9.54, Tg is 25 ℃.
The manufacturing of preparation example 7 resins (A) solution No.1
In the reactor that has stirrer, reflux exchanger and thermometer, add the vinyl polymer (a of solids component 50%
1) 700 parts of solution No.1 (350 parts of solids components), reach 1000 parts of water dispersible ethylenic copolymer (a2) the solution No.1 (650 parts of solids components) that preparation example 6 makes, stirred 15 minutes in room temperature (25 ℃), measure isocyanate value.The isocyanate value that mixes varnish is 47.6.
Then, heating while stirring maintains 40 ℃, after carrying out reacting in about 3 hours, at isocyanate value is moment of 45.8 to add 300 parts of methyl ethyl ketoximes, 60 ℃ of slakings 2 hours, make resin (A) the solution No.1 of solids component 50.0%, weight-average molecular weight about 16,000.
Preparation example 8～12
With preparation example 7 similarly, according to the cooperation content of table 2, make resin (A) solution No.2～resin (A) solution No.6.Expression solid component in table 2 brace.
Table 2
| Preparation example 7 | Preparation example 8 | Preparation example 9 | Preparation example 10 | Preparation example 11 | Preparation example 12 | |
| Resin (A) solution (kind) | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 |
| Ethylenic copolymer (a 1) solution No.1 | 700 (350) | 600 (300) | ||||
| Ethylenic copolymer (a 1) solution No.2 | 700 (350) | |||||
| Ethylenic copolymer (a 1) solution No.3 | 700 (350) | |||||
| Ethylenic copolymer (a 1) solution No.4 | 700 (350) | |||||
| Ethylenic copolymer (a 1) solution No.5 | 700 (350) | |||||
| Water dispersible ethylenic copolymer (a 2) solution No.1 | 1000 (650) | 1000 (650) | 1000 (650) | 1077 (700) | 1000 (650) | 1000 (650) |
| Methyl ethyl ketoxime | 300 | 300 | 300 | 323 | 300 | 300 |
| Resin (A) solution (use level) | 2000 (1000) | 2000 (1000) | 2000 (1000) | 2000 (1000) | 2000 (1000) | 2000 (1000) |
| Ethylenic copolymer (a 1) and ethylenic copolymer (a 2) the SP value difference | 0.54 | 0.74 | 0.74 | 0.54 | 1.24 | 1.14 |
Preparation example 13
In reaction vessel, add 55 parts of Virahols, remain on 80 ℃, use 15 parts of 3 hours drip styrenes then, 31 parts of methyl methacrylates, 15 parts of n-butyl acrylates, 10 parts of ethyl propenoates, 15 parts of vinylformic acid 2-hydroxy methacrylates, 7 parts in vinylformic acid, the mixture that 7 parts of N-butoxymethyl acrylamides and azo methyl pentane nitrile are 1.0 parts, after dripping end, kept 1 hour in this temperature, drip 45 parts of 1 part of azo methyl pentane nitrile and ethylene glycol butyl ethers then, continue reaction 4 hours at 80 ℃ again, make solids component 50%, weight-average molecular weight 30,000, SP value 9.60, Tg16.5 ℃ resin solution No.7.
The manufacturing of preparation example 14 emulsion No.1
The carboxyl of resin (A) the solution No.1 200 parts (100 parts of solids components) that makes with respect to preparation example 7, after mixing 0.4 normal triethylamine, carry out blending dispersion, behind the blending dispersion SCAT-7 (annotate 5) 0.5 part (solid composition), the limit is stirred the limit and is slowly dripped deionized water, adding triethylamine again, to make pH be 7.5, regulates with deionized water, makes the emulsion No.1 of solid composition 10%.
Preparation example 15～19
With preparation example 14 similarly, according to the cooperation of table 3, make the emulsion No.2～No.6 of solids component 10%.
Preparation example 20
In the resin No.7 solution 140 parts (70 parts of solids components) that preparation example 13 makes, add DURANATEMF-B 80M (annotating 6) 37.5 parts of (30 parts of solids components), SCAT-7 (annotating 5) 0.5 part (0.5 part of solids component), slowly drip deionized water while stirring, adding triethylamine again, to make pH be 7.5, regulate with deionized water, make the emulsion No.7 of solids component 10%.
Table 3
| Preparation example 14 | Preparation example 15 | Preparation example 16 | Preparation example 17 | Preparation example 18 | Preparation example 19 | Preparation example 20 | |
| Emulsion | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | No.7 |
| Resin (A) solution No.1 | 200 (100) | ||||||
| Resin (A) solution No.2 | 200 (100) | ||||||
| Resin (A) solution No.3 | 200 (100) | ||||||
| Resin (A) solution No.4 | 200 (100) | ||||||
| Resin (A) solution No.5 | 200 (100) | ||||||
| Resin (A) solution No.6 | 200 (100) | ||||||
| Resin solution No.7 | 140 (70) | ||||||
| SCAT-7 (annotating 5) | 0.5 (0.5) | 0.5 (0.5) | 0.5 (0.5) | 0.5 (0.5) | 0.5 (0.5) | 0.5 (0.5) | 0.5 (0.5) |
| DURANATE MF-B80M (annotating 6) | 37.5 (30) | ||||||
| U-CAT18X (annotating 7) | 0.4 (0.4) | ||||||
| TINUVIN 328 (annotating 8) | 2 (2) | ||||||
| TINUVIN 292 (annotating 9) | 1 (1) | ||||||
| Triethylamine | Regulate pH=7.5 | ← | ← | ← | ← | ← | ← |
| Deionized water | Be adjusted to solids component 10% | ||||||
(solids component)
(annotating 5) SCAT-7: synthetic (strain) corporate system of three total machines, trade(brand)name, dibutyl tin dimercapto carboxylicesters
(annotating 6) DURANATE MF-B80M: Asahi Chemical Industry's (strain) corporate system, trade(brand)name, the isocyanuric acid ester type of hexamethylene diisocyanate, methyl ethyl ketoxime end-capping reagent, solids component 80%.
(annotating 7) U-CAT 18X: Sanyo changes into corporate system, trade(brand)name, and amine is curing catalysts.
(annotating 8) TINUVIN 328:CIBA-GEIGY Ltd. system, trade(brand)name, UV light absorber
(annotating 9) TINUVIN 292:CIBA-GEIGY Ltd. system, trade(brand)name, photostabilizer.
Embodiment 1
Add triethylamine in the emulsion No.1 of solids component 10% 1000 parts (100 parts of solids components), making pH is 8.5, makes anion electrophoresis coating No.1.
Embodiment 2～5
Adopt operation similarly to Example 1, make anion electrophoresis coating No.2～No.5 of embodiment 2～5 according to the content of table 4.
Comparative example 1～4
Adopt operation similarly to Example 1,, make the anion electrophoresis coating No.6～No.9 of comparative example 1～4 according to the content of table 5.
Comparative example 5
Use ELECRON AG-300 (Kansai Paint Co., Ltd's system, trade(brand)name, the anion electrophoresis coating of the melamine cured type of acrylic resin).
The manufacturing of test board
The anion electrophoresis coating that embodiment and comparative example are made is as bath, in this bath the dipping to coated article implemented 2 electrolysis treatment (degreasing-etching-neutralization-anodic oxidation treatment-sealing of hole) by the anodic oxidation aluminium of the about 10 μ m of thickness (silver color: size 150 * 70 * 0.5mm), carry out electrophoretic painting, making dry film thickness is 10 μ m, after the washing, 140 ℃ of bakings 20 minutes.
Test according to following test conditions.Embodiment is shown in table 4, comparative example is shown in table 5.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |||
| Anion electrophoresis coating | No.1 | No.2 | No.3 | No.4 | No.5 | ||
| Cooperate | Emulsion | Kind | No.1 | No.2 | No.3 | No.4 | No.1 |
| Use level | 1000 | 1000 | 1000 | 1000 | 500 | ||
| Emulsion | Kind | No.2 | |||||
| Use level | 500 | ||||||
| Triethylamine | Regulate pH=8.5 | ← | ← | ← | ← | ||
| Film performance | Gel fraction (annotating 10) | 95 | 95 | 98 | 93 | 95 | |
| Pencil hardness (annotating 11) | 4H | 4H | 5H | 4H | 4H | ||
| Figure health hardness (annotating 12) | 4 | 5 | 6 | 4 | 4.5 | ||
| 60 ° of gloss (annotating 13) | 4 | 8 | 5 | 7 | 6 | ||
| Covering property of mould scar (annotating 14) | ○ | ○ | ○ | ○ | ○ | ||
| Facial mask tack (annotating 15) | ◎ | ◎ | ◎ | ◎ | ○ | ||
| Weathering resistance (annotating 16) | 90 | 94 | 91 | 96 | 92 | ||
Table 5
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |||
| Anion electrophoresis coating | No.6 | No.7 | No.8 | No.9 | ELECRON AG-300 | ||
| Cooperate | Emulsion | Kind | No.5 | No.6 | No.5 | No.7 | |
| Use level | 1000 | 1000 | 500 | 1000 | |||
| Emulsion | Kind | No.6 | |||||
| Use level | 500 | ||||||
| Triethylamine | Regulate pH=8.5 | ← | ← | ← | |||
| Film performance | Gel fraction (annotating 10) | 91 | 93 | 92 | 90 | 84 | |
| Pencil hardness (annotating 10) | 2H | 2H | 2H | 2H | 2H | ||
| Figure health hardness (annotating 12) | 3 | 3 | 3 | 2 | 2 | ||
| 60 ° of gloss (annotating 13) | 23 | 35 | 27 | 38 | 5 | ||
| Covering property of mould scar (annotating 14) | △ | △ | △ | △ | × | ||
| Facial mask tack (annotating 15) | ○ | ○ | ○ | △ | × | ||
| Weathering resistance (annotating 16) | 87 | 88 | 87 | 91 | 53 | ||
(annotating 10) gel fraction:
Filming of peeling off from latten put into the netted container of the stainless steel of 300 purposes, use the solvent of acetone/methanol=1/1 under reflux temperature, to extract after 6 hours, calculate the gel fraction of application latten according to following formula.
Gel fraction (%)=(weight of filming after the extraction)/(weight of filming before the extraction) * 100
(annotating 11) pencil hardness:
According to JIS K 5600-5-4, the angle that is 45 ° with test coated plate face is approximately placed pencil-lead, and the degree that does not fracture with the pen core rand of exerting oneself is pushed test coated plate face limit and moved forward about 10mm with even velocity.Change test position, repeats 5 times and should operate, the hardness mark of the hardest pencil when cannot not filming brokenly is as pencil hardness.
(annotating 12) figure health hardness: coated plate after 20 ℃ thermostatic chamber is placed 4 hours, is used American Chain ﹠amp; The TUKON microhardness tester of Cable Company corporate system is measured.Numerical value is high more, and expression is filmed hard more.
(annotating 13) 60 ° of gloss:
According to the 60 degree mirror surface lusters of JIS K-5400 7.6 (1990), measure input angle and acceptance angle and be respectively 60 reflectivity when spending, be that 100 o'clock percentage is represented the gloss intensity of filming with the glossiness of the reference plane of mirror surface luster.
(annotating 14) covering property of mould scar: the visual evaluation.
Zero covering property of mould scar is good
Covering property of △ mould scar is poor
Covering property of * mould scar is very poor
(annotating 15) facial mask tack: the otch (reaching the degree of depth of aluminium face) of processing the parallel lines of wide 25mm along the middle body length direction of test board.Peel off about 90mm thin film layer from a side end, bending 180 degree.(with reference to Fig. 1)
Use Autograph S-D type (society of Shimadzu Seisakusho Ltd. system, trade(brand)name, the universal tensile testing machine of band thermostatic bath), the about 30mm (25 ℃ ± 5 ℃ of envrionment temperatures) that under draw speed 50mm/ divides, stretches, the stripping strength of mensuration film.
More than ◎: the stripping strength 39.2N (4kgf)
Zero: stripping strength 29.4～39.2N
△: stripping strength 20～29.4N
*: the not enough 20N of stripping strength
(annotating 16) weathering resistance:
Use the sunlight weatherometer, estimate with 2000 hours gloss retention (%) of irradiation.
The possibility of utilizing on the industry
Use Lightless anion electrophoresis coating of the present invention can obtain 60 good degree gloss of curability at low temperatures, hardness of film, covering property of mould scar below 10 without optical coating and unglazed coated article.
Claims (4)
1. Lightless anion electrophoresis coating, it is characterized in that, contain resin (A) is dispersed in the water, adds that curing catalysts (B) disperses and the emulsion that obtains again, total amount 100 weight parts with respect to resin (A), contain curing catalysts (B) 0.1～10 weight part, described resin (A) makes by following method: make the ethylenic copolymer (a that 2 above free isocyanate groups are arranged in 1 molecule
1) this free isocyanate groups a part with the ethylenic copolymer (a of hydroxyl, carboxyl and alkoxysilyl is arranged
2) the part reaction of hydroxyl, the whole and end-capping reagent of residual free isocyanate groups is reacted, in 1 molecule of the resin that makes like this (A) and have blocked isocyanate base and hydroxyl, and ethylenic copolymer (a
1) and ethylenic copolymer (a
2) the difference of solubility parameter be 0.4～1.0, ethylenic copolymer (a
2) the combined amount scope make by ethylenic copolymer (a
1) weight-average molecular weight count in per 1 molecule of 500～50000 and import average 0.1 urethane bond at least.
2. the described Lightless anion electrophoresis coating of claim 1 is characterized in that, curing catalysts (B) is at least a compound that is selected from organo-tin compound and amine compound.
3. claim 1 or 2 described Lightless anion electrophoresis coatings is characterized in that ethylenic copolymer (a
1) be the multipolymer of making by vinyl monomer that contains isocyanate group and other vinyl monomer.
4. each described Lightless anion electrophoresis coating of application claim 1～3 obtains on the aluminium base of anodic oxidation treatment, 60 ° of gloss of coated surface are the unglazed coated article below 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004096697 | 2004-03-29 | ||
| JP2004096697 | 2004-03-29 | ||
| JP2004361124 | 2004-12-14 | ||
| JP2004361124A JP2005314645A (en) | 2004-03-29 | 2004-12-14 | Matting anionic electrodeposition coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1676553A CN1676553A (en) | 2005-10-05 |
| CN1329460C true CN1329460C (en) | 2007-08-01 |
Family
ID=35049315
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100057960A Expired - Fee Related CN1329460C (en) | 2004-03-29 | 2005-01-25 | Lightless anion electrophoresis coating |
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| Country | Link |
|---|---|
| JP (1) | JP2005314645A (en) |
| CN (1) | CN1329460C (en) |
| TW (1) | TWI264452B (en) |
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| JP5220525B2 (en) * | 2008-09-11 | 2013-06-26 | 株式会社シミズ | Thermosetting anion electrodeposition coating composition and aqueous electrodeposition coating composition |
| JP5588269B2 (en) * | 2010-08-19 | 2014-09-10 | 株式会社Ｌｉｘｉｌ | Powder coating aluminum building materials for outdoor use |
| CN102337073B (en) * | 2011-08-18 | 2013-12-25 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
| CN103469277B (en) * | 2013-08-15 | 2016-06-22 | 嘉兴兴禾汽车零部件有限公司 | A kind of anodic oxidation method for sealing of car aluminum or aluminium alloy part |
| CN105778047A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of terminated polyisocyanate curing agent specially used for 120DEG C low temperature-curable electrophoresis paint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167789A (en) * | 1996-05-28 | 1997-12-17 | 北美埃尔夫爱托化学股份有限公司 | Catalyst for low temp. cure of blocked isocyanates |
| DE19715427A1 (en) * | 1997-04-14 | 1998-10-15 | Bayer Ag | Aqueous 2-component binders and their use |
| CN1306550A (en) * | 1998-06-24 | 2001-08-01 | 纳幕尔杜邦公司 | Coating contg. hydroxy acrylosilane polymer to improve mar and acid etch resistance |
-
2004
- 2004-12-14 JP JP2004361124A patent/JP2005314645A/en active Pending
-
2005
- 2005-01-25 CN CNB2005100057960A patent/CN1329460C/en not_active Expired - Fee Related
- 2005-03-23 TW TW94108894A patent/TWI264452B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167789A (en) * | 1996-05-28 | 1997-12-17 | 北美埃尔夫爱托化学股份有限公司 | Catalyst for low temp. cure of blocked isocyanates |
| DE19715427A1 (en) * | 1997-04-14 | 1998-10-15 | Bayer Ag | Aqueous 2-component binders and their use |
| CN1306550A (en) * | 1998-06-24 | 2001-08-01 | 纳幕尔杜邦公司 | Coating contg. hydroxy acrylosilane polymer to improve mar and acid etch resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005314645A (en) | 2005-11-10 |
| TWI264452B (en) | 2006-10-21 |
| CN1676553A (en) | 2005-10-05 |
| TW200536903A (en) | 2005-11-16 |
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