CN1704453A - Electrophoresis paint - Google Patents
Electrophoresis paint Download PDFInfo
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- CN1704453A CN1704453A CNA2005100740971A CN200510074097A CN1704453A CN 1704453 A CN1704453 A CN 1704453A CN A2005100740971 A CNA2005100740971 A CN A2005100740971A CN 200510074097 A CN200510074097 A CN 200510074097A CN 1704453 A CN1704453 A CN 1704453A
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- casio
- 2sio
- 2caco
- electrophoretic paint
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The present invention provided a pollution-free electrodeposition coating which is excellent in corrosion resistance, finishing property, etc. without containing harmful substances such as a lead compound or a chromium compound. The electrodeposition coating contains at least one silica-modified phosphorus compound chosen from the group consisting of formula (1): (xMHPO<SB>4</SB>3H<SB>2</SB>O)-(ySiO<SB>2</SB>)-(mCaSiO<SB>3</SB>)-(nCaCO<SB>3</SB>) and formula (2)(Ca<SB>3</SB>(PO<SB>4</SB>)<SB>2</SB>3H<SB>2</SB>O)-(ySiO<SB>2</SB>)-(mCaSiO<SB>3</SB>)-(nCaCO<SB>3</SB>) (wherein M is Mg or Ca; x, y and m are each an integer of 1-3; and n is an integer of 0-3) as a rust preventive agent.
Description
Technical field
The present invention relates to that a class is used to form non-corrosibility, the finishability of filming, be coated with the good and nuisanceless type electrophoretic paints of filming that do not contain leadization thing and chromium compounds such as membrane stability.
Background technology
Electrophoretic paint is widely used being the field of main purposes with car body and trolley part, opens so far and has sent the electrophoretic paint with various characteristics.
For example, except the electrophoretic paint of the such baking vanish type of the coating of car body, the coated article that heat big for thermal capacity, drying oven can not fully be transmitted or, added the electrophoretic paint of the normal temperature cured type that coated article plastics or rubber, that can not heat (for example, tractor etc. industrial machinery) uses.
In the past,,, cooperated lead compound and chromium cpd in order to improve the non-corrosibility of filming for electrophoretic paint, but in recent years because the protection of environment has limited the use in electrophoretic paint of lead compound and chromium cpd.
Open the spy and to disclose the instead nontoxicity and even the hypotoxic rust-preventive agent of lead compound and chromium cpd in the flat 7-331129 communique, use aluminium dihydrogen tripolyphosphate.This compound sees it is no problem from the hazardous property viewpoint, but because non-corrosibility is insufficient, thus must heavy addition in electrophoretic paint, when adding so in large quantities, the problem of finishability that infringement films and the stability of filming is arranged.
In addition, open the spy and to disclose a kind of electrophoretic paint that does not use the normal temperature cured type of poisonous metal in the flat 2003-277679 communique, it is to have cooperated zinc phosphate as rust-preventive agent, zinc phosphite calcium, zinc phosphite strontium, calcium molybdate, phospho-molybdic acid aluminium etc., though these compounds are less expensive, non-corrosibility is insufficient, in order to ensure the non-corrosibility of filming, when containing a large amount of above-claimed cpds in electrophoretic paint, also has the problem of infringement finishability of filming and the stability of filming.
Summary of the invention
The object of the present invention is to provide the electrophoretic paint of nuisanceless type, it is to contain nuisanceless type, the good rust-preventive agent of non-corrosibility, and non-corrosibility, the finishability of filming, to be coated with membrane stability etc. good and do not contain leadization thing and chromium compounds.
The inventor etc. are in order to address the above problem, carried out meticulous research, found that, certain specific silica modified phosphate cpd do not have toxicity and also have very strong non-corrosibility, the anticorrosive agent used as electrophoretic paint is exceedingly useful, thereby finished the present invention.
Therefore, the invention provides electrophoretic paint, it is characterized in that containing at least a silica modified phosphate cpd from the thing group of following formula (1) and (2), selected as rust-preventive agent,
(xMHPO
43H
2O)·(ySiO
2)·(mCaSiO
3)·(nCaCO
3)????????(1)
(Ca
3(PO
4)
23H
2O)·(ySiO
2)·(mCaSiO
3)·(nCaCO
3)?????(2)
In the formula,
M is Mg or Ca, and x, y and m are respectively 1～3 integers, and n is 0～3 integer.
Electrophoretic paint of the present invention does not contain lead compound and chromium cpd, be nontoxic, do not produce environmental pollution, the applicator that can provide non-corrosibility, the finishability of filming is good.
The compound of above-mentioned formula (1) and (2) is owing to can suitably suppress dissolving the separate out amount of ion to coating or in filming, so contain the electrophoretic paint of the present invention of formula (1) and (2) compound, can not damage the stability of coating and the finishability of filming even accept the vibration or long stirring of machinery for a long time yet, in addition, the film anticorrosion erosion persistence that forms is good, shows long non-corrosibility.
Below, electrophoretic paint of the present invention is described in further detail.
Be engaged in material in the coating as rust-preventive agent; general solubilized is separated out and is used for antirust needed ion and forms protective membrane in the metallic surface; the effect that perhaps suppresses metallic corrosion by the shock absorption performance of pH in the metallic surface; but dissolving is separated out and is used for antirust needed ionic weight when very few; the non-corrosibility of filming is low; when the amount that ionic dissolving is on the contrary separated out is too much, the stability decreases of coating.
The silica modified phosphate cpd that is engaged in above-mentioned formula (1) in the electrophoretic paint and (2) according to the present invention is nontoxic, and, be to dissolve in right amount to separate out between over a long time to be used for the needed ion of anticorrosive metal, and, has the few over time distinguishing feature of its dissolving amount of separating out, and then the dispersiveness in electrophoretic paint is also good, is only as the non-harmful rust-preventive agent that is engaged in the electrophoretic paint.
The compound of above-mentioned formula (1) for example can be with following method manufacturing.
(a) by an amount of lime carbonate or the magnesiumcarbonate of in reactor, packing into, add entry, be warmed up to about 50～80 ℃ after, approximately stirred 1～3 hour, be mixed with " dispersion liquid A ".
(b) phosphoric acid of packing in other container adds entry, is diluted to 1～30%, is mixed with phosphate aqueous solution.Then, to having added the reactor of dispersion liquid A, under the state that its temperature is remained under 50～80 ℃, stir on one side, in about 10～60 minutes, splash into above-mentioned phosphate aqueous solution equably on one side, then, reacted about 30 minutes～about 3 hours down about 60 ℃ greatly.
(c) in other reactor, add an amount of lime carbonate, stir after adding entry, and then add nitric acid, water, be mixed with " dispersion liquid B " with stirring rake.
(d) in the reacted reactor of above-mentioned (b) record, under about 50～80 ℃ of maintenance temperature, in about 30～about 120 minutes, splash into dispersion liquid B, fully stir, be mixed with " dispersion liquid C ".
(e) in the container that has stirring rake in addition, add an amount of water glass, add entry, stir on one side, be warmed up to about 50～about 80 ℃ on one side, then stirred about 1～about 3 hours, be mixed with " dispersion liquid D ".
(f) in the reactor of the dispersion liquid C that has added above-mentioned (d) record, under about 50～about 80 ℃ of maintenance temperature, stir on one side, in about 30～120 minutes, splash into dispersion liquid D on one side, then, stir fully.
(g) take out resultant from reactor, fully washing, filter, the filter cake that generates after about 100～120 ℃ of following dryings, is pulverized.
Can obtain the compound of above-mentioned formula (1) so with high yield.As the concrete example of formula (1) compound, can enumerate following compound.For example:
2MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
3MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2MgHPO
4·3H
2O·2SiO
2·CaSiO
3·CaCO
3
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
3CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2CaHPO
43H
2O2SiO
2CaSiO
32CaCO
3Deng.
In addition, above-mentioned formula (2) compound, except in the compound manufacturing process (a) of formula (1), using lime carbonate, and the phosphoric acid addition in the operation (b) compare with the compound of formula (1) have some change outside, the compound of all the other and manufacturing formula (1) is made in the same manner.
As the concrete example of formula (2) compound, can enumerate following compound.For example:
Ca
3(PO
4)
2·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Ca
3(PO
4)
2·3H
2O·2SiO
2·CaSiO
3·3CaCO
3
Ca
3(PO
4)
2·3H
2O·2SiO
2·2CaSiO
3·2CaCO
3
Ca
3(PO
4)
23H
2O3SiO
2CaSiO
32CaCO
3Deng.
As the preferred compound of formula (1) and formula (2), can enumerate following compound.
3CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Ca
3(PO
4)
23H
2O2SiO
2CaSiO
32CaCO
3Deng.
The content of these silica modified phosphate cpds in electrophoretic paint, can change according to the difference of the kind that is engaged in electrophoretic paint, but, common total solids component 100 weight parts with respect to the resinous principle in the coating (basic resin and solidifying agent), be at 0.1～50 weight part, preferably, be more preferably in the scope of 2～10 weight parts at 1～20 weight part.
According to the present invention, for the electrophoretic paint that can cooperate with above-mentioned formula (1) and/or (2) compound, have no particular limits, any electrophoretic paint for cationic or anionic, perhaps any electrophoretic paint for Air drying type or heat curing-type all is suitable for, for example can enumerate particularly, Air drying type electrophoretic paint, heat curing-type anion electrophoresis coating, heat curing-type cation electrophoretic coating etc. below further specify these electrophoretic paint.
Air drying type electrophoretic paint:
As Air drying type electrophoretic paint, comprise those for example placements 24 hours～10 days under normal temperature (below 50 ℃), preferably just can make the electrophoretic paint of curing of coating on the 3rd～7, preferably contain the electrophoretic paint of fatty acid modified acrylic resin as resinous principle.
About can be used as the fatty acid modified acrylic resin that resinous principle uses, can enumerate the multipolymer that for example forms by fatty acid modified acrylic monomer (a), the free-radical polymerised unsaturated monomer (b) that contains carboxyl and other free-radical polymerised unsaturated monomer (c).
Above-mentioned fatty acid modified acrylic monomer (a) can obtain with the reaction that contains the acrylic acid series ester of hydroxyl by for example unsaturated fatty acids.
As this unsaturated fatty acids, comprise that those contain 2 aliphatic monocarboxylic acids that do not have two keys of conjugate relation mutually at least in 1 molecule, specially suitable is drying oil fatty acid and semi-drying oil lipid acid.Here, drying oil fatty acid generally is meant iodine number at the unsaturated fatty acids more than 130, and semi-drying oil lipid acid is meant that generally iodine number is 100～130 unsaturated fatty acids.As such unsaturated fatty acids, can enumerate for example Thistle oil lipid acid, linseed oil fatty acid, soya fatty acid, the acid of sesame oil fat, poppyseed oil lipid acid, perilla oil lipid acid, hempseed oil lipid acid, raisin seed oil lipid acid, corn oil fatty acid, ready denier oil acid, sunflower oil lipid acid, cottonseed oil fatty acid, walnut oil fat acid etc., these lipid acid can be used in combination separately individually or more than two kinds.
The usage quantity of these unsaturated fatty acidss can require performance and suitably variation according to what film, but, usually with respect to the total amount of the monomeric solids component that constitutes fatty acid modified acrylic resin, preferably at 5～65 weight %, in the scope particularly preferably in 10～60 weight %.In addition, as required, also can and with below the 30 weight %, the unsaturated fatty acids with conjugated double bond of the tung oil lipid acid of the following ratio of 20 weight %, foul smell arbor fatty acid oil, dehydrated castor oil fatty acid, senior diene (Ha イ ジ エ Application) lipid acid etc. preferably.
As contain can with the acrylate or the methacrylic ester (hereinafter referred to as the acrylic acid series ester that contains hydroxyl) of the hydroxyl of unsaturated fatty acids acid-respons, the ester residue that can enumerate at vinylformic acid or methacrylic acid partly has a hydroxyl, and this ester residue partly contains 2～24, preferred 2～8 carbon atoms.Contain the acrylate of hydroxyl as this class, can enumerate for example acrylic acid hydroxy alkyl ester or the hydroxyalkyl methacrylate of vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate etc.
Above-mentioned fatty acid modified acrylic monomer (a) can by with unsaturated fatty acids and the acrylic acid series ester that contains hydroxyl in inert solvent, in the presence of esterifying catalyst, react and make.Temperature of reaction is usually at about 100～about 180 ℃, and preferably in about 120～about 160 ℃ scope, and the reaction times approximately is 0.5～about 10 hours, preferably about 1～about 6 hours.
The usage quantity that contains the acrylic acid series ester of hydroxyl is 0.5～1.9 mole with respect to 1 mole of unsaturated fatty acids usually, preferably 1.0～1.5 moles.
As the ester catalyst that can in above-mentioned reaction, use, can enumerate, sulfuric acid, Tai-Ace S 150, sal enixum, tosic acid, hydrochloric acid, methyl sulfate, phosphoric acid etc., the usage quantity of these catalyzer, with respect to unsaturated fatty acids and the total amount that contains the acrylic acid series ester of hydroxyl, preferably in the scope of 0.05～2.0 weight %.
In addition, as above-mentioned solvent, preferably those non-water-soluble organic solvents that can reflux, for example aromatic hydrocarbons of benzene,toluene,xylene etc. in about temperature below 180 ℃; The aliphatic hydrocarbon of heptane, hexane, octane etc.In addition, can add stopper as required, for example Resorcinol, methoxyphenol, tert-butyl catechol, benzoquinones etc. can suppress to contain the polymerization of the fatty acid modified acrylate of the acrylic acid series ester of hydroxyl and/or generation like this.
In above-mentioned reaction, between the carboxyl of the hydroxyl of the acrylic acid series ester that contains hydroxyl and unsaturated fatty acids, cause esterification, the acrylic acid series ester that can obtain by the unsaturated fatty acids modification.
And then, as other method, by the acrylate or the methacrylic ester that will contain glycidyl, for example glycidyl methacrylate and unsaturated fatty acids carry out sour epoxidation reaction, the acrylic monomer (a) that also can obtain by the unsaturated fatty acids modification.At this moment, with similarly above-mentioned, can use polymerization inhibitor when needing.
As the free-radical polymerised unsaturated monomer (b) that contains carboxyl, can enumerate for example vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid etc., these monomers can be used in combination individually or more than two kinds.
Free-radical polymerised unsaturated monomer (c) as other can use following cited monomer.
The ester of acrylic or methacrylic acid: the C of the acrylic or methacrylic acid of methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, Ethyl acrylate, Octyl acrylate, lauryl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, Octyl methacrylate, lauryl methacrylate(LMA) etc. for example
1～C
18Alkyl ester; The alkoxy alkyl of the acrylic or methacrylic acid of vinylformic acid methoxyl group butyl ester, methacrylic acid methoxy base butyl ester, vinylformic acid methoxyl group ethyl ester, methacrylic acid methoxy base ethyl ester, vinylformic acid oxyethyl group butyl ester, methacrylic acid oxyethyl group butyl ester etc.; The C of the acrylic or methacrylic acid of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 etc.
2～C
8Hydroxy alkyl ester; The alkene oxygen base alkyl ester of the acrylic or methacrylic acid of vinylformic acid allyloxy ethyl ester, vinylformic acid allyloxy methyl esters etc. etc.
Vinyl aromatic compounds: for example vinylbenzene, alpha-methyl styrene, Vinyl toluene, to chloro-styrene, vinyl pyridine etc.
Polyolefin compound: for example divinyl, isoprene, chlorobutylene etc.
The acid amides of acrylic or methacrylic acid: for example acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide etc.
Other, vinyl cyanide, methacrylonitrile, methyl isopropenyl ketone etc.
As other free-radical polymerised unsaturated monomer (c), also can use to have nitrogenous heterocyclic vinyl monomer (d).Be included in and contain 1～3, the monocycle of preferred 1 or 2 nitrogen-atoms or polycyclic heterocycle in the vinyl monomer (d) and be combined in monomer on the vinyl, can enumerate following monomer particularly.
Vinyl pyrrolidone class: for example l-vinyl-2-pyrrolidone, 1-vinyl-3-pyrrolidone etc.
Vinyl pyridine class: for example 2-vinyl pyridine, 4-vinylpridine, 5-methyl-2-vinyl pyridine, 5-ethyl-2-vinyl pyridine etc.
Vinyl imidazole class: for example 1-vinyl imidazole, 1-vinyl-glyoxal ethyline etc.
Vinylcarbazole class: N-vinylcarbazole etc. for example.
Vinylquinoline class: 2-vinylquinoline etc. for example.
Vinyl piperidines: for example 3-vinyl piperidines, N-methyl 3-vinyl piperidines etc.
In above-mentioned vinyl monomer, particularly preferably be theheterocyclic nitrogen atom by the aminating monomer of uncle.These monomers can be used in combination respectively individually or more than 2 kinds or 2 kinds.
The copolymerization of fatty acid modified acrylic monomer (a), carboxylic free-radical polymerised unsaturated monomer (b) and other free-radical polymerised unsaturated monomer (c) for example can use solution polymerization process, emulsion polymerization, suspension polymerization etc. to carry out.
The monomeric usage ratio of when carrying out copolymerization each, with monomer (a) and (b) and (c) total weight as benchmark, common fatty acid modified acrylic monomer (a) can be 7～94 weight %, 10～80 weight % preferably, carboxylic free-radical polymerised unsaturated monomer (b) can be 3～20 weight %, 5～15 weight % preferably, and other free-radical polymerised unsaturated monomer (c) can be 1～88 weight %, preferably in the scope of 18～78 weight %.
Usage ratio with nitrogenous heterocyclic vinyl monomer (d) as benchmark, can be 1～80 weight %, with monomer (a) and (b) and (c) total weight preferably in the scope of 25～65 weight % usually.
These monomeric copolyreaction for example can be in solvent, in the presence of polymerizing catalyst, under about 30～about 180 ℃, preferably under about 40～about 170 ℃ temperature, carry out about 1～20 hour, preferably carried out about 6～about 10 hours.
The fatty acid modified acrylic resin that obtains generally can have 20～150mgKOH/g, the acid number in 25～120mg KOH/g scope preferably.In addition, this fatty acid modified acrylic resin generally can have 500～100,000, preferably have the number-average molecular weight in 2,000～20,000 scope.
And then, when requiring the electrophoretic paint of high non-corrosibility as film performance, as resinous principle, also can use by epoxy equivalent (weight) 180～2 epoxy resin modification/fatty acid modified acrylic resin that Resins, epoxy in 500 scopes and above-mentioned for example fatty acid modified reactive acrylic resin obtain.
Above-mentioned Resins, epoxy can be by making polyphenolic substance and epoxyhalopropane, for example epichlorohydrin reaction and obtaining.As forming the polyphenolic substance that this Resins, epoxy uses, for example can enumerate two (4-hydroxy phenyls)-2,2-propane (dihydroxyphenyl propane), 4,4-dihydroxy benaophenonel, two (4-hydroxy phenyl) methane (Bisphenol F), two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl-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, phenol phenolic aldehyde, cresols phenolic aldehyde etc.
In addition, as the Resins, epoxy that the reaction by polyphenolic substance and epoxy chloropropane obtains, wherein, preferably use the compound of representing from the following formula of dihydroxyphenyl propane deutero-:
Wherein, n=1～3.
As the commercially available product of such Resins, epoxy, for example can enumerate and sell with the trade(brand)name of Epikote 828EL, Epikote 1002, Epikote 1004, Epikote 1007 by japan epoxy resin (strain).
When making epoxy resin modification/fatty acid modified acrylic resin, fatty acid modified acrylic resin and epoxy equivalent (weight) are 180～2, the usage ratio of 500 Resins, epoxy, usually with respect to solids component 100 weight parts of fatty acid modified acrylic resin, Resins, epoxy is 0.01～50 weight %, special preferably in the scope of 0.1～35 weight %.
Its reaction for example can mix fatty acid modified acrylic resin and Resins, epoxy in organic solvent, carried out about 0.2～about 30 hours under room temperature and even about 200 ℃ temperature.In addition, as catalyzer, in acid-epoxy reaction, can use normally used tertiary amine, quaternary ammonium salt etc.The carrying out of reaction can be controlled by the minimizing of following the trail of the acid number of resin with titration.
The compound of formula (1) and/or (2) carries out by the following method to the importing of Air drying type electrophoretic paint, promptly, compound method according to common electrophoretic paint, for example use as above-mentioned fatty acid modified acrylic resin or epoxy resin modification/fatty acid modified acrylic resin etc. as disperseing to use resin, disperse with in the resin at these, with the compound and the pigment of formula (1) and/or (2), for example painted pigment such as titanium oxide, carbon black, red iron oxide; The pigment extender of clay, mica, barium oxide, lime carbonate, silicon-dioxide etc.; The rust-stabilising pigment of phospho-molybdic acid aluminium, aluminium triphosphate etc.; The curing catalysts of zinc octoate or zinc formate etc.; The bismuth compound of bismuth, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate, bismuth silicate etc.; The mixing that surface conditioner, tensio-active agent etc. suit, use Ball milling or sand milling to disperse to carry out dispersion treatment, be mixed with pigment dispersion paste, mix with emulsion with the electrophoretic paint that contains above-mentioned fatty acid modified acrylic resin or epoxy resin modification/resinous principle that fatty acid modified acrylic resin conduct prepares in addition again.
Above-mentioned electrophoretic paint emulsion, can prepare by following method, for example, in fatty acid modified acrylic resin or epoxy resin modification acrylic resin, as required, add organic solvent, prevent scolding agent, surface conditioner, membrane-forming agent etc., carboxyl with respect to fatty acid modified acrylic resin or epoxy resin modification acrylic resin, add 0.1～1.1 equivalent, preferred 0.5～1.1 normal neutralizing agent, for example ammonia, diethylamine, ehtylethanolamine, diethanolamine, monoethanolamine, single Propanolamine, Yi Bingchunan, ethylamino ethamine, aminoethyle alcohol, triethylamine, Tributylamine, the organic amine of diethylenetriamine etc.; The alkali metal hydroxide of caustic soda, Ke Xingjia etc. adds deionized water, and use decollator etc. disperses and makes.By in this emulsion, being mixed into above-mentioned pigment dispersion paste, add deionized water, pH regulator is become 7.0～10.0, the coating solids component is diluted to 5～30 weight %, 10～20 weight % preferably, can makes the compound that contains formula (1) and/or (2) Air drying type electrophoretic paint as rust-preventive agent.
The content of the compound of formula (1) and/or (2) in Air drying type electrophoretic paint, film performance that can be as requested etc. changes in wide region, but usually for per 100 weight parts of the solids component of the resinous principle in the Air drying type electrophoretic paint, 0.1～50 weight part preferably, be more preferably 1～20 weight part, special preferably in the scope of 2～8 weight parts.
Electrophoretic coating can will be bathed temperature and be adjusted to 15～40 ℃, preferred 20～35 ℃ by the Air drying type electrophoretic paint of above-mentioned preparation is bathed as electrophoretic paint, at load voltage 20～400V, preferably switch under 30～300V and carried out in 1～10 minute.
The thickness that electrophoretic paint is filmed is not particularly limited, but according to general cured coating film, preferably in the scope of 10～40 μ m.Coated article is pulled from the electrophoretic paint bath, will be coated with the face washing as required, sometimes, in order to improve the solidified nature of filming, carry out forced drying below 100 ℃ after about 5～about 40 minutes about, about 50 ℃ place down 24 hours～about 10 days, preferably placed 3～7 days, can make curing of coating.
Coated article is as long as its surface is to constitute with conductive metal at least, be not particularly limited for its size and shape, can be any size and shape, as its material, comprise iron for example, aluminium, steel and material that chemical treatment forms etc. is carried out on the surface of these materials, it is big to enumerate thermal capacity particularly, its film article that can not fully heat, the article that made up plastics and rubber etc., building machinery etc.
The heat curing-type anion electrophoresis coating:
In the heat curing-type anion electrophoresis coating that can cooperate, comprise that containing the negatively charged ion with carboxyl class forms the anionic resin of property functional group and the solidifying agent coating as resinous principle with the compound of formula of the present invention (1) and/or (2).
As above-mentioned anionic resin, can use those itself known resin that can cooperate with common anion electrophoresis coating, for example can use the resin of acrylic resin with carboxyl and hydroxyl, vibrin, urethane resin etc. particularly.
This anionic resin can pass through with its carboxyl usefulness the organic amine of ammonia, diethylamine, ehtylethanolamine, diethanolamine, monoethanolamine, single Propanolamine, Yi Bingchunan, ethylamino ethamine, aminoethyle alcohol, diethylenetriamine etc.; The neutralizing agent neutralization of the alkali metal hydroxide of caustic soda, Ke Xingjia etc. etc. reaches water-solubleization or water-dispersionization.
As the acrylic resin with above-mentioned carboxyl and hydroxyl, for example can enumerate the unsaturated monomer that contains carboxyl, contain hydroxyl acrylic is that monomer and other polymerizable monomers of using as required make it carry out radical polymerization and the multipolymer that generates.
As above-mentioned monomeric concrete example, can enumerate following monomer.
The unsaturated monomer that contains carboxyl: be the compound that in 1 molecule, has 1 above carboxyl and polymerizability unsaturated link(age) respectively, for example can enumerate (methyl) vinylformic acid, toxilic acid, contain (methyl) acrylic monomer (Daicel chemistry society system, trade(brand)name, プ ラ Network セ Le FM1A, プ ラ Network セ Le FM4A, プ ラ Network セ Le FM10A) of caprolactone modification carboxyl etc.
Containing hydroxyl acrylic is monomer: be the compound that has 1 above hydroxyl and polymerizability unsaturated link(age) in 1 molecule respectively, for example can enumerate (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, (gathering) (methyl) vinylformic acid ethylene glycol ester, (gathering) (methyl) vinylformic acid propylene glycol monoester; Contain the reactant etc. of the lactone compound of the acrylic monomer of hydroxyl and beta-propiolactone, dimethyl propylene lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-lauryl lactone, 6-caprolactone, δ-caprolactone etc. by these, as commercially available product, can enumerate プ ラ Network セ Le FM1, プ ラ Network セ Le FM2, プ ラ Network セ Le FM3, プ ラ Network セ Le FA1, プ ラ Network セ Le FA2, プ ラ Network セ Le FA3 (above all is Daicel chemistry society system, trade(brand)name, caprolactone modification (methyl) crylic acid hydroxy ester) etc.
Other polymerizable monomer: be at the above-mentioned acrylic monomer polymerizable monomer in addition that those contain the unsaturated monomer of carboxyl and contain hydroxyl, at least the compound that has 1 polymerizability unsaturated link(age) in 1 molecule for example can be enumerated (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
18The alkyl or cycloalkyl ester; The vinyl aromatic compounds of vinylbenzene, Vinyl toluene etc.; (methyl) acrylamide and the derivative thereof of (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-methylol (methyl) acrylamide etc.; (methyl) acrylonitrile compound; The polymerizable monomer that contains alkoxysilyl of γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, γ-(methyl) acryloyl-oxy propyl group methyl dimethoxysilane, γ-(methyl) acryloyl-oxy propyl-triethoxysilicane, vinyltrimethoxy silane etc. etc.
These are monomeric free-radical polymerized, for example can wait by the method for himself known solution polymerization and carry out.The acrylic resin that obtains generally can have below 10,000, preferably 4,000～8, the number-average molecular weight in 000 scope; 20～200mg KOH/g, the preferred hydroxyl value in 25～150mg KOH/g scope; And 20～150mg KOH/g, the preferred acid number in 25～120mg KOH/g scope.
As the solidifying agent that uses with the anionic resin combination, for example can enumerate melamine resin, block polyisocyanate compound, Ju oxazoline compound etc., but wherein, preferably melamine resin.
As melamine resin, can suit to use part or all of methylol of the methylolation melamine resin that formaldehyde etc. is obtained with the melamine reaction to use a kind of C at least
1～C
10The monohydroxy-alcohol modification etherification melamine resin.As such melamine resin, preferably 1 ring body～many (about 2～5) ring body accounts for more than the 50 weight %.In addition, melamine resin also can contain imido grpup, methylol, other functional group.
The isocyanate group that the block polyisocyanate compound is sealed polyisocyanate compounds with the block agent generates, and can suit to use the block polyisocyanate compound that exemplifies in cation electrophoretic coating described later particularly.If, the block agent is dissociated, and regeneration free isocyanate group with block polyisocyanate compound heating, this isocyanate group then with the anionic resin in hydroxyl etc. carry out crosslinking reaction.
Above-mentioned anionic resin and solidifying agent, generally be as benchmark with both total solids component, the anionic property resin preferably uses in 50～95 weight %, scope particularly preferably in 65～85 weight %, and solidifying agent preferably uses in 5～50 weight %, scope particularly preferably in 15～35 weight %.
The heat curing-type cation electrophoretic coating:
In the heat curing-type cation electrophoretic coating that can cooperate, comprise and contain cation type resin as matrix resin with contain the coating of block polyisocyanate compounds as solidifying agent with the compound of formula of the present invention (1) and/or (2).In the cation type resin that uses as matrix resin, for example can enumerate in molecule, have amino, the resin of the group of the cationicallyization of ammonium salt base, sulfonium salt Ji, phosphonium salt base etc., as the resin kind, it can be the common resin that uses as the matrix resin of electrophoretic paint, the resin of any a kind of form in epoxy system, acrylic acid series, polyhutadiene system, Synolac system, the polyester system etc. for example, suitable especially what use is by amine and polyepoxides are carried out the amine addition Resins, epoxy that addition reaction obtains.
As amine addition Resins, epoxy, for example can enumerate (1) by polyepoxides and uncle monoamine and polyamines, secondary monoamine and polyamines or primary, the secondary affixture (for example, with reference to No. 3984299 specification sheets of United States Patent (USP)) that mixes the polyamines generation; (2) by polyepoxide and the secondary monoamine of primary amine groups and the affixture (for example, with reference to No. 4017438 specification sheets of United States Patent (USP)) of polyamines generation with ketoimineization; (3) carry out etherificate by polyepoxide and the oxy-compound with primary amine groups of ketoimineization and the reactant (for example, opening clear 59-43013 communique) that obtains etc. with reference to the spy.
Can be used for making the polyepoxides of above-mentioned amine addition Resins, epoxy, is that a class has more than 1 the compound of preferred epoxy group(ing) more than 2 in 1 molecule; Generally, at least have 200, preferably 400～4000, be more preferably the number-average molecular weight (annotating 1) in 800～2500 scopes and have 160 at least, preferably 180～2500, the epoxy equivalent (weight) that is more preferably in 400～1500 scopes suits, especially the compound that preferably obtains by polyphenolic substance and epichlorohydrin reaction.
(annotating 1) number-average molecular weight: the method according to JIS K0124-83 is carried out, as separator column, use TSK GEL 4000HXL+G3000HXL+G2500HXL+G2000HXL (TOSOH Co., Ltd's system), 40 ℃ of following flow velocity 1.0ml/ minutes, use GPC with tetrahydrofuran (THF) as elutriant, according to the calibration curve of chromatogram that obtains from the RI refractometer and polystyrene, obtain by calculating.
As the polyphenolic substance that can be used for forming this Resins, epoxy, for example 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-tert-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, phenol phenolic aldehyde, cresols phenolic aldehyde etc.
This Resins, epoxy, also can be to react and the polymkeric substance of formation with parts such as polyvalent alcohol, polyether polyols, polyester polyalcohols, polyamidoamines, polycarboxylic acid, polyisocyanate compounds, and then, also can be to carry out graft polymerization with the caprolactone of 6-caprolactone etc., Acrylic Acid Monomer etc. and the polymkeric substance that forms.
As the polyphenolic substance that can be used for forming this Resins, epoxy, for example 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-Bai or tert-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, phenol phenolic aldehyde, cresols phenolic aldehyde etc.
As uncle's monoamine of the amine addition Resins, epoxy that can be used for making above-mentioned (1) and polyamines, secondary monoamine and polyamines or primary, the secondary polyamines that mixes, for example can enumerate the list of Monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, Diisopropylamine, monobutylamine (MBA), dibutylamine etc. or two alkylamine; The alkanolamine of Monoethanolamine MEA BASF, diethanolamine, list (2-hydroxypropyl) amine, Monomethylamine ethanol etc.; The alkylene polyamine of quadrol, propylene diamine, butanediamine, hexanediamine, diethylenetriamine, Triethylenetetramine (TETA) etc. etc.
Secondary monoamine and polyamines as amine addition primary amine groups Resins, epoxy, that have ketoimineization that can be used for making above-mentioned (2), for example can enumerate uncle's monoamine that can in the manufacturing of the amine addition Resins, epoxy of above-mentioned (1), use and polyamines, secondary monoamine and polyamines or primary, the secondary mixing in the polyamines, the ketoimine thing that compound (for example, Monomethylamine, Monoethanolamine MEA BASF, quadrol, diethylenetriamine etc.) with primary amine groups obtains with the ketone compound reaction.
Oxy-compound as amine addition primary amine groups Resins, epoxy, that have ketoimineization that can be used for making above-mentioned (3), for example can enumerate uncle's monoamine that can in the manufacturing of the amine addition Resins, epoxy of above-mentioned (1), use and polyamines, secondary monoamine and polyamines or primary, the secondary mixing in the polyamines, the ketoimine thing that contains hydroxyl that compound (for example, Monoethanolamine MEA BASF, list (2-hydroxypropyl) amine etc.) with primary amine groups and hydroxyl obtains with the ketone compound reaction.
In above-mentioned amine addition epoxy resin compound, also comprise, polyol compound that obtains by having the compound addition caprolactone of the group that contains reactive hydrogen more than 2 in above-mentioned Resins, epoxy and 1 molecule and the compound that contains amido react and the polyalcohol modified amine addition Resins, epoxy that obtains, and the very suitable use of these resins.
In 1 molecule, has a compound that contains the group of reactive hydrogen more than 2 as above-mentioned, it generally is the molecular weight that has in 62～5000 the scope, contain 2～30 groups that contain reactive hydrogen in preferably per 1 molecule, contain the group of reactive hydrogen as this, can enumerate hydroxyl, primary amine groups, tertiary amine groups etc.
As the above-mentioned concrete example that in 1 molecule, has the compound of the group that contains reactive hydrogen more than 2, can enumerate ethylene glycol, propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1, the low-molecular-weight polyvalent alcohol of 6-hexylene glycol, glycol ether, dipropylene glycol, dimethyltrimethylene glycol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane etc.; The wire of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polymer with bis phenol A glycol ether etc. or a chain polyethers; By the organic dicarboxylic acid of Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid, toxilic acid, cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid etc. or the organic diol of its acid anhydrides and above-mentioned low molecular weight polyols etc., under the condition of organic diol surplus, carry out polycondensation and the polyester polyol that obtains; Butanediamine, hexamethylene-diamine, tetren, penten, Monoethanolamine MEA BASF, diethanolamine, trolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, 1, the amine compound of the two amino methyl pimelinketone of 3-, isophorone diamine, O-phthalic base diamines, MXDP, diaminodiphenyl-methane, phenylenediamine, quadrol, propylene diamine, diethylenetriamine, Triethylenetetramine (TETA) etc.; Piperazine or by the affixture of these amine compound deutero-polymeric amide, polyamidoamines, epoxy compounds, ketoimine, aldimine etc.
As can with above-mentioned 1 molecule in have the caprolactone that carries out addition reaction in the compound of the group that contains reactive hydrogen more than 2, for example can enumerate, γ-Ji Neizhi, 6-caprolactone, δ-caprolactone etc., specially suitable is 6-caprolactone.
The addition reaction that has the compound and the caprolactone of the group that contains reactive hydrogen more than 2 in above-mentioned 1 molecule can be undertaken by itself known method, can obtain polyvalent alcohol by this addition reaction.
Can be used for making the amino compound that contains of above-mentioned polyalcohol modified amine addition Resins, epoxy, be that a class can be amino so that make the cationic composition of giving of this cationicization of resin by importing in resin, can use those to have the compound of 1 energy and the reactive hydrogen of epoxy reaction at least.
As its object lesson, for example can enumerate uncle's monoamine of those amine addition Resins, epoxy that can be used for making above-mentioned (1) and polyamines, secondary monoamine and polyamines or primary, the secondary polyamines that mixes; Can be used for making the secondary monoamine with ketoimine primary amino and the polyamines of the amine addition Resins, epoxy of above-mentioned (2); Can be used for making the oxy-compound with ketoimine primary amino of the amine addition Resins, epoxy of above-mentioned (3).
In addition, when cation type resin has amino group as cationicallyization, can be by organic carboxyl acid with formic acid, acetate, propionic acid, lactic acid etc.; The acid of the mineral acid of hydrochloric acid, sulfuric acid etc. etc. neutralizes it and makes its water-solubleization and even water-dispersionization, on the other hand, at alkali during, can not neutralize and directly carry out water-solubleization and even water-dispersionization as the group of cationicallyization with ammonium salt base, mercapto alkali Huo phosphonium salt base etc.
In the block polyisocyanate compound that uses as solidifying agent with above-mentioned cationic resin combination, comprise that polyisocyanate compounds and block agent carry out the resultant of addition reaction according to stoichiometry roughly.As the polyisocyanate compounds that can be used for this purpose, for example can enumerate the benzylidene vulcabond, eylylene diisocyanate, phenylene vulcabond, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, the aromatic series of isophorone diisocyanate etc., aliphatics or alicyclic polyisocyanate compounds reach and press excess quantity and ethylene glycol by these isocyanate compound, propylene glycol, TriMethylolPropane(TMP), hexanetriol, the lower molecular weight of castor-oil plant wet goods contains the compound reaction of reactive hydrogen and the end that obtains contains the compound of isocyanic ester etc.
On the other hand, the block agent be used for addition on the isocyanate group of polyisocyanate compounds to carry out the composition of block, the block polyisocyanate compound that generates by its addition is stable at normal temperatures, but preferred uses those that block agent is dissociated and the compound of regeneration free isocyanate group.As the block agent of satisfying such condition, for example can enumerate the lactan based compound of ε-Ji Neixianan, butyrolactam etc.; The oxime compound of methyl ethyl ketoxime, cyclohexanone-oxime etc.; The phenol based compound of phenol, p-tert-butylphenol, cresols etc.; The aliphatics alcohols of propyl carbinol, 2-Ethylhexyl Alcohol etc.; The aromatic series alkyl alcohols of phenylcarbinol, methylbenzyl alcohol etc.; The ether alcohol based compound of ethylene glycol monobutyl ether etc. etc.
And then, be that 76～150 glycol or molecular weight are that block polymeric polyisocyanate that 106～500 the glycol that contains carboxyl uses as the block agent also can be used as solidifying agent and uses with molecular weight.
Above-mentioned glycol can be to 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 glycol with molecular weight of 76～150, for example, can enumerate propylene glycol, dipropylene glycol, 1,3 butylene glycol, 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-1,3-pentanediol, 1, the 5-hexylene glycol, 1, the glycol with 2 reactive different hydroxyls of 4-hexylene glycol etc.
Wherein, consider that from the reactivity of block polymeric polyisocyanate, the reduction of weight loss on heating, the viewpoints such as package stability of coating propylene glycol suits.These glycol are normally by reactive high hydroxyl and isocyanic ester radical reaction and with the isocyanate group block.
In closing the glycol of above-mentioned carboxyl, comprise that molecular weight is 106～500 the glycol that closes carboxyl, owing in molecule, have carboxyl, so can improve dissociating property of low temperature, and raising solidified nature at low temperatures, when particularly using organo-tin compound, can improve solidified nature at low temperatures greatly as curing catalysts.
As the glycol that contains carboxyl, for example can enumerate 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, dihydroxymethyl valeric acid, R-Glyceric acid etc.
The above-mentioned cation type resin and the usage quantity of solidifying agent, usually with both total solids component as benchmark, cation type resin is preferably at 50～95 weight %, special preferably in the scope of 65～85 weight %, and solidifying agent is preferably at 5～50 weight %, preferably use in the scope of 15～35 weight % especially.In addition, in the cation electrophoretic coating, can be used as and add up to solid component meter by 10～40 weight %, especially preferably contain cation type resin and solidifying agent by the concentration in 15～25 weight % scopes.
Contain the heat curing-type negatively charged ion of resinous principle or the compound of cation electrophoretic coating introducing-type (1) and/or (2) carries out as follows to above-mentioned, promptly, compound method according to common electrophoretic paint, disperseing with in the resin, the compound and the pigment of formula (1) and/or (2), for example painted pigment such as titanium oxide, carbon black, red iron oxide aptly; The pigment extender of clay, mica, barium oxide, lime carbonate, silicon-dioxide etc.; The rust-stabilising pigment of phospho-molybdic acid aluminium, aluminium triphosphate etc.; The bismuth compound of bismuth, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate, bismuth silicate etc.; The curing catalysts of di-n-octyltin oxide, dibutyltin oxide, stannous octoate, dibutyl tin laurate, oxidation dibenzoic acid dibutyl tin, zinc octoate, zinc formate etc.; Surface conditioner, tensio-active agent etc. use Ball milling or sand milling dispersive method to carry out dispersion treatment, are mixed with pigment dispersion paste, mix with emulsion with the electrophoretic paint that contains above-mentioned resinous principle of other preparation then.
The electrophoretic paint emulsion for example can be prepared as carry out water-solubleization or water-dispersionization above-mentionedly by adding solidifying agent in the above-mentioned anionic resin used to heat curing-type negatively charged ion or cation electrophoretic coating or the cation type resin.
Mix by the emulsion that the pigment dispersion paste and the electrophoretic paint of above-mentioned preparation are used, and then adding deionized water, the coating solids component is diluted to 5～30 weight %, 10～25 weight % preferably, can makes the heat curing-type negatively charged ion or the cation electrophoretic coating of the compound that contains formula (1) and/or (2).
The content of the compound of formula (1) and/or (2) in heat curing-type anion electrophoresis coating or heat curing-type cation electrophoretic coating, usually, solids component 100 weight parts with respect to the resinous principle in the electrophoretic paint, it is 0.1～50 weight part, preferably 1～20 weight part is special preferably in the scope of 2～8 weight parts.
Electrophoretic painting, common occasion at cation electrophoretic coating, be that the pH regulator that electrophoretic paint is bathed is become 5.0～7.0, and in the occasion of anion electrophoretic coating, then be adjusted to 7.0～10.0, and will bathe temperature and be adjusted to 15～40 ℃, preferably 20～35 ℃, carry out in load voltage 20～400V, the condition of preferably under 30～300V, switching on 1～10 minute.
The thickness that electrophoretic paint is filmed is not particularly limited, but generally be 10～40 μ m, preferably in the scope of 15～30 μ m.In addition, the sintering curing temperature and time of filming, generally about 110～about 220 ℃, preferably under about 120～about 170 ℃ temperature, carry out 5 minutes～120 minutes, preferably carried out 10 minutes～50 minutes.
As coated article, for example can enumerate the steel plate of two layers of steel plate of cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanizing steel plate, electro-galvanizing-iron of body of a motor car, trolley part etc., organic compositive lining steel plate etc.; Aluminium and their mixture etc.
Embodiment
Below, further specifically describe the present invention with embodiment, but the present invention is not subjected to the restriction of these embodiment.In addition, when " part " reaches " % " short of special declaration, be meant that " weight part " reaches " weight % ".
Production Example 1 rust-preventive agent No.1
(1) in having the reactor of stirring rake, adds 60 parts in magnesium oxide, add entry and make 2000 parts for 1940 parts, be warmed up to 60 ℃, be mixed with dispersion liquid A.
(2) phosphatase 11 of adding 75% in having the flask of stirring rake is 78.7 parts, adds 1021.3 parts of entry, obtains 1200 parts of phosphate aqueous solutions.
Stir the reactor that has added dispersion liquid A on one side, on one side temperature is remained under 60 ℃, behind the phosphate aqueous solution that in 30 minutes, drips equably, reacted 1 hour 30 minutes down at 60 ℃.
(3) have at another and add 217.4 parts in lime carbonate in flask of stirring rake, add 282.6 parts of entry, stir, add 152.6 parts in 67.5% nitric acid therein, and then add entry and make 1000 parts for 347.4 parts, obtain dispersion liquid B.
(4) the reacted reactor of operation (2) is remained under 60 ℃ the state, stir on one side, in 1 hour, splash into dispersion liquid B on one side, continue to stir 1 hour, be mixed with dispersion liquid C.
(5) have at another and add 458 parts of water glass in flask of stirring rake, add entry and make 2000 parts for 1542 parts, obtain dispersion liquid D.
(6) the reacted reactor with operation (4) remains under 60 ℃ of states, stir on one side, in 1 hour, splash into dispersion liquid D2000 on one side, continue again to stir 1 hour.
(7) take out resultant from reactor, fully washing, with the filter cake that obtains after the washing 120 ℃ dry down and with its pulverizing, obtain rust-preventive agent No.1.
The composition of rust-preventive agent No.1 is
2MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Production Example 2 rust-preventive agent No.2
(1) in having the reactor of stirring rake, adds 340 parts in lime carbonate, add entry and make 4500 parts for 4160 parts, be warmed up to 60 ℃, be mixed with dispersion liquid A.
(2) phosphatase 24 of adding 75% in having the flask of stirring rake is 90.4 parts, adds 1309.6 parts of entry, obtains 1800 parts of phosphate aqueous solutions.
Stir the reactor that has added dispersion liquid A on one side, on one side temperature is remained on 60 ℃, behind the phosphate aqueous solution that in 30 minutes, drips equably, reacted 1 hour down at 60 ℃.
(3) have at another and add 560 parts in lime carbonate in flask of stirring rake, add 660 parts of entry and stir, add 366 parts in 67.5% nitric acid therein, and then add entry and make 2000 parts for 414 parts, obtain dispersion liquid B.
(4) the reacted reactor with operation (2) remains under 60 ℃, stir on one side, in 1 hour, splash into dispersion liquid B on one side, continue again to stir 1 hour, be mixed with dispersion liquid C.
(5) have at another and add 1080 parts of water glass in flask of stirring rake, add entry and make 8600 parts for 7520 parts, obtain dispersion liquid D.
(6) the reacted reactor with operation (4) remains under 60 ℃, stir on one side, in 1 hour, splash into dispersion liquid D8600 part on one side, continue again to stir 1 hour.
(8) take out resultant and fully washing from reactor, with the filter cake that obtains after the washing 120 ℃ dry down and with its pulverizing, obtain rust-preventive agent No.2.
The composition of rust-preventive agent No.2 is
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Production Example 3～6 rust-preventive agent No.3～No.6
Except the kind and usage quantity thereof that change the used raw material in operation (1)～(7) as shown in table 1ly, operate in the same manner with Production Example 2, obtain rust-preventive agent No.3～No.6.
Table 1
| Production Example | ??1 | ????2 | ??3 | ??4 | ??5 | ??6 | |
| Operation | Rust-preventive agent | ??No.1 | ????No.2 | ??No.3 | ??No.4 | ??No.5 | ??No.6 |
| Operation (1) dispersion liquid A | Magnesium oxide | ??60 | |||||
| Lime carbonate | ????340 | ??510 | ??170 | ??340 | ??340 | ||
| Water | ??1940 | ????4160 | ??3990 | ??4330 | ??4160 | ??4160 | |
| Operation (2) | 75% phosphoric acid | ??178.7 | ????490.4 | ??736 | ??245.2 | ??490.4 | ??328 |
| Water | ??1021.3 | ????1309.6 | ??1064 | ??1554.8 | ??1309.6 | ??1472 | |
| Operation (3) dispersion liquid B | Lime carbonate | ??217.4 | ????560 | ??560 | ??560 | ??280 | ??560 |
| Water | ??282.6 | ????660 | ??660 | ??660 | ??940 | ??660 | |
| 67.5% nitric acid | ??152.6 | ????366 | ??366 | ??366 | ??183 | ??366 | |
| Water | ??347.4 | ????414 | ??414 | ??414 | ??597 | ??414 | |
| Operation (4) dispersion liquid c | Splash into dispersion liquid B to reactor | ||||||
| Operation (5) dispersion liquid D | Water glass | ??458 | ????1080 | ??1080 | ??1080 | ??1080 | ??1080 |
| Water | ??1542 | ????7520 | ??7520 | ??7520 | ??7520 | ??7520 | |
| Operation (6) | Splash into dispersion liquid D to reactor | ||||||
| Operation (7) | Washing, dry, pulverizing | ||||||
Unit: weight part
Rust-preventive agent No.3～the No.6's that obtains is composed as follows.
Rust-preventive agent No.3:3CaHPO
43H
2O2SiO
2CaSiO
32CaCO
3
Rust-preventive agent No.4:CaHPO
43H
2O2SiO
2CaSiO
32CaCO
3
Rust-preventive agent No.5:2CaHPO
43H
2O2SiO
2CaSiO
3CaCO
3
Rust-preventive agent No.6:Ca
3(PO
4)
23H
2O2SiO
2CaSiO
32CaCO
3
Production Example 7 aliphatics modification acrylates
236 parts of linseed oil fatty acids
119 parts of glycidyl methacrylate
0.4 part of quinhydrones
0.2 part of tetraethyl-ammonium bromide
Above-mentioned each composition is joined in the reaction vessel, stir on one side, under 140～150 ℃ temperature, react on one side.Follow the trail of the addition reaction of epoxy group(ing) and carboxyl in the amount of measuring remaining carboxyl, stopped reaction after 4 hours obtains reactant (1).
Then, ethylene glycol monobutyl ether is joined in the reaction vessel for 54 parts, be heated to 120 ℃.On one side temperature is remained on 120 ℃, about 2 hour in drip following monomer mixture on one side.
(1) 30 part of reactant
40 parts of vinylbenzene
15 parts of n-BMAs
8 parts of methacrylic acid 2-ethylhexyls
7 parts in vinylformic acid
3 parts of Diisopropyl azodicarboxylates
After drip finishing, Diisopropyl azodicarboxylate is joined in the reaction vessel for 1 part, then, keeping carrying out 3 hours reaction under 120 ℃ of states, obtain acid number 55mg KOH/g and solids component and be 65% fatty acid modified acrylate.
Production Example 8 epoxy resin modifications/fatty acid modified acrylate
In 1500 parts of fatty acid modified acrylate that obtains in the same manner with above-mentioned Production Example 7, add Epikote 1001 (japan epoxy resin society system, trade(brand)name, Resins, epoxy) 50 parts, be warmed up to 120 ℃, reaction is proceeded to acid number reach 48mg KOH/g, obtain solids component and be epoxy resin modification/fatty acid modified acrylate of 66%.
Production Example 9 pigment dispersion paste No.1
With 12.3 parts of the fatty acid modified acrylic resins that obtain in the Production Example 7 (dividing 8 parts), 3 parts of Hydrate PXN (annotating 2), 2 parts of carbon MA-7 (annotating 3), rust-preventive agent No.16 part, mix for 13.7 parts as 1 part of the triethylamine and the deionized water of neutralizing agent Gu form, this mixture joined in the ball mill stirred 20 hours, obtain solids component and be 50% pigment dispersion paste No.1.
Production Example 10～18 pigment dispersion paste No.2～No.10
Except using the gradation composition shown in the table 2 with the ratio shown in the table 2, operate in the same manner with Production Example 9, obtain pigment paste No.2～No.10.
Table 2
| Production Example | |||||||||||
| ????9 | ????10 | ????11 | ????12 | ????13 | ????14 | ????15 | ????16 | ????17 | ????18 | ||
| Pigment dispersion paste | ????No.1 | ????No.2 | ????No.3 | ????No.4 | ????No.5 | ????No.6 | ????No.7 | ????No.8 | ????No.9 | ????No.10 | |
| Dispersion resin | Expression solids component in the fatty acid modified acrylic resin () | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) | ????12.3 ????(8) |
| Pigment extender | Ha イ De ラ イ De PXN (annotating 2) | ????3 | ????3 | ????12 | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
| Tinting pigment | カ-ボ Application MA-7 (annotating 3) | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 |
| Rust-stabilising pigment | Rust-preventive agent No.1 | ????6 | |||||||||
| Rust-preventive agent No.2 | ????6 | ||||||||||
| Rust-preventive agent No 3 | ????6 | ||||||||||
| Rust-preventive agent No 4 | ????6 | ||||||||||
| Rust-preventive agent No 5 | ????6 | ||||||||||
| Rust-preventive agent No.6 | ????6 | ||||||||||
| P-W-2 (annotating 4) | ????6 | ||||||||||
| NP-1020C (annotating 5) | ????6 | ||||||||||
| KW-840E (annotating 6) | ????6 | ||||||||||
| Neutralizing agent | Triethylamine | ????1.0 | ????10 | ????1.0 | ????1.0 | ????1.0 | ????1.0 | ????1.0 | ????1.0 | ????1.0 | ????1.0 |
| Dilution water | Deionized water | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 |
| Expression solids component in 50% the pigment dispersion paste () | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | ????38 ????(19) | |
(annotating 2) Hydrate PXN:Georgia Kaolin society system, trade(brand)name, pure aluminium silicate
(annotating 3) carbon MA-7: Mitsubishi Chemical society system, trade(brand)name, carbon black
(annotating 4) P-W-2: chrysanthemum ground pigment society system, trade(brand)name, zinc phosphate
(annotating 5) NP-1020C: pigment society of eastern nation system, trade(brand)name, phosphorous acid calcium zinc
(annotating 6) KW-840E: Supreme Being Ka She system, trade(brand)name, aluminium dihydrogen tripolyphosphate
Production Example 19 emulsion No.1
Fatty acid modified acrylic resin 154 parts of (100 parts of solids components), 20 parts of ethylene glycol monobutyl ether that Production Example 7 is obtained, 15 parts of benzylalcohols, as 140 parts of 10 parts of the triethylamines of neutralizing agent and deionized waters, mix while stirring with decollator, obtain solids component and be 30% emulsion No.1.
Production Example 20 emulsion No.2
Epoxy resin modification/fatty acid modified acrylic resin 151 parts of (100 parts of solids components), 20 parts of ethylene glycol monobutyl ether that Production Example 8 is obtained, 15 parts of benzylalcohols, as 137 parts of 10 parts of the triethylamines of neutralizing agent and deionized waters, mix while stirring with decollator, obtain solids component and be 30% emulsion No.2.
Embodiment 1
The pigment dispersion paste No.1 (19 parts of solids components) that adds 38 parts in 333 parts emulsion No.1 (100 parts of solids components), and then add 422 parts of deionized waters obtains solids component and is 15% electrophoretic paint No.1.
Embodiment 2～7, comparative example 1～4
With emulsion shown in table 3 and the table 4 and pigment dispersion paste combination, obtain electrophoretic paint No.2～No.7 (embodiment 2～7) and electrophoretic paint No.8～No.10 (comparative example 1～4) in the same manner with embodiment 1.
Coated test
With organic solvent the surface is immersed among electrophoretic paint No.1～No.11 that the foregoing description and comparative example obtain through the cold rolling unglazed steel plate of degreasing, it as anode, bathing under 25 ℃ of temperature, the load voltage 150V, was switched on 3 minutes, carry out electrophoretic coating.
The thickness that electrophoresis is filmed is 20 μ m, after the washing, uses electric hot air dryer, carries out 30 minutes forced drying under 80 ℃, then at room temperature dry 7 days.The film performance of electrophoretic paint No.1～No.7 (embodiment) is shown in Table 3, and the film performance of electrophoretic paint No.8～11 (comparative example) is shown in Table 4.
In addition, performance test is implemented according to method described later.
Table 3
| Embodiment | ||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ||
| Electrophoretic paint | ??No.1 | ??No.2 | ??No.3 | ??No.4 | ??No.5 | ??No.6 | ??No.7 | |
| Emulsion No.1 | ??333 ??(100) | ??333 ??(100) | ??333 ??(100) | ??333 ??(100) | ??333 ??(100) | ??333 ??(100) | ||
| Emulsion No.2 | ??333 ??(100) | |||||||
| Pigment dispersion paste No.1 | ??38 ??(19) | |||||||
| Pigment dispersion paste No.2 | ??38 ??(19) | ??38 ??(19) | ||||||
| Pigment dispersion paste No.3 | ??38 ??(19) | |||||||
| Pigment dispersion paste No.4 | ??38 ??(19) | |||||||
| Pigment dispersion paste No.5 | ??38 ??(19) | |||||||
| Pigment dispersion paste No.6 | ??38 ??(19) | |||||||
| Deionized water | ??422 | ??422 | ??422 | ??422 | ??422 | ??422 | ??422 | |
| 15% coating | ??793 ??(119) | ??793 ??(119) | ??793 ??(119) | ??793 ??(119) | ??793 ??(119) | ??793 ??(119) | ??793 ??(119) | |
| Film performance | Salt tolerant sprayability (annotating 7) | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??◎ |
| Paint stability (annotating 8) | ??○ | ??◎ | ??◎ | ??◎ | ??◎ | ??◎ | ??◎ | |
| Finishability (annotating 9) | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
Expression solids component in ()
Table 4
| Comparative example | |||||
| ????1 | ????2 | ????3 | ????4 | ||
| Electrophoretic paint | ????No.8 | ????No.9 | ????No.10 | ????No.11 | |
| Emulsion No.1 | ????333 ????(100) | ????333 ????(100) | ????333 ????(100) | ????333 ????(100) | |
| Pigment dispersion paste No.7 | ????38 ????(19) | ||||
| Pigment dispersion paste No.8 | ????38 ????(19) | ||||
| Pigment dispersion paste No.9 | ????38 ????(19) | ||||
| Pigment dispersion paste No.10 | ????38 ????(19) | ||||
| Deionized water | ????422 | ????422 | ????422 | ????422 | |
| 15% coating | ????793 ????(119) | ????793 ????(119) | ????793 ????(119) | ????793 ????(119) | |
| Film performance | Salt tolerant sprayability (annotating 7) | ????△ | ????△ | ????△ | ????× |
| Paint stability (annotating 8) | ????△ | ????△ | ????○ | ????○ | |
| Finishability (annotating 9) | ????△ | ????△ | ????△ | ????○ | |
Expression solids component in ()
(annotating 7) salt tolerant sprayability
On each electrophoretic coating plate, otch and the dark matrix that arrives with electrophoresis is filmed and is cut into cross by knife according to JIS Z2371, carry out 120 hours salt spray testing, according to the rust of knife wound place generation, the width of bubbling, estimate according to following standard.
◎: the maximum width of rust, bubbling is apart from the not enough 2mm of otch (one-sided)
Zero: the maximum width of rust, bubbling is apart from more than the otch 2mm but not enough 3mm (one-sided)
△: the maximum width of rust, bubbling is apart from more than the otch 3mm but not enough 4mm (one-sided)
*: the maximum width of rust, bubbling is apart from (one-sided) more than the otch 4mm
The stability of (annotating 8) coating
Electrophoretic paint joined in the container and airtight after, stirred for 4 weeks down at 30 ℃, with the bath coating of the filtering net full dose filter 23 L in 400 mesh sieve holes.
◎: the not enough 5mg/L of filtered residue,
Zero: the not enough 10mg/L of filtered residue,
Above but the not enough 20mg/L of △: filtered residue 10mg/L,
*: more than the filtered residue 20mg/L.
(annotating 9) finishability
Visual valuation is coated with the outward appearance of face
Zero: smoothness is well no problem,
△: see a little because the decline of the precision work performance of ripple, delustring, uneven surface etc.,
*: owing to the precision work performance of ripple, delustring, uneven surface etc. descends very big.
Production Example 21 acrylic resin solns
In reactor, add 210 parts of mixed solvent A (annotating 10), keep 85 ℃ temperature on one side, in 3 hours, drip following monomer mixture on one side, then add 3 parts of azo methyl pentane nitriles, keep down reacting in 4 hours at 85 ℃, make the acrylic resin soln that solids component is 70 weight %.
Monomer mixture
10.5 parts of vinylbenzene
36.8 parts of methyl methacrylates
3.7 parts of n-butyl acrylates
20.0 parts of ethyl propenoates
4.0 parts of 2-ethylhexyl methacrylic esters
5.5 parts in vinylformic acid
12.0 parts of vinylformic acid 2-hydroxyl ethyl esters
7.5 parts of methacrylic acid 2-hydroxyl ethyl esters
2.1 parts of azo methyl pentane nitriles
(annotating 10) mixed solvent A: propylene glycol monomethyl ether (121 ℃ of boiling points)/Virahol (82 ℃ of boiling points)/propyl carbinol (118 ℃ of boiling points)/ethylene glycol monobutyl ether (171 ℃ of boiling points)=42 parts/42 parts/42 parts/84 parts.
Production Example 22 pigment dispersion paste No.11
Add 13.7 parts of 3 parts of acrylic resin soln 7.1 parts of (5 parts of solids components), Hydrate PXN (annotating 2), 2 parts of carbon MA-7 (annotating 3), rust-preventive agent No.16 part, 0.24 part of the triethylamine of the solids component 70% that Production Example 21 obtains and deionized waters, it is mixed the back disperse, obtain the pigment dispersion paste No.11 that 50% thermoset anion electrophoresis coating is used with ball mill.
Production Example 23～28 pigment dispersion paste No.12～No.17
With Production Example 22 in the same manner, except using the gradation composition shown in the table 5 according to the ratio shown in the table 5, all the other and Production Example 22 are operated in the same manner, obtain pigment dispersion paste No.12～No.17.
Table 5
| Production Example | ||||||||
| ????22 | ????23 | ????24 | ????25 | ????26 | ????27 | ????28 | ||
| Pigment dispersion paste | ????No.11 | ????No.12 | ????No.13 | ????No.14 | ????No.15 | ????No.16 | ????No.17 | |
| Dispersion resin | Expression solids component in the acrylic resin soln () that Production Example 21 obtains | ????7.1 ????(5) | ????7.1 ????(5) | ????7.1 ????(5) | ????7.1 ????(5) | ????7.1 ????(5) | ????7.1 ????(5) | ????7.1 ????(5) |
| Pigment extender | Ha イ De ラ イ De PXN (annotating 2) | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 | ????3 |
| Tinting pigment | カ-Port Application MA-7 (annotating 3) | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 |
| Rust-stabilising pigment | Rust-preventive agent No.1 | ????6 | ||||||
| Rust-preventive agent No.2 | ????6 | |||||||
| Rust-preventive agent No.3 | ????6 | |||||||
| P-W-2 (annotating 4) | ????6 | |||||||
| NP-1020C (annotating 5) | ????6 | |||||||
| KW-840E (annotating 6) | ????6 | |||||||
| Neutralizing agent | Triethylamine | ????0.24 | ????0.24 | ????0.24 | ????0.24 | ????0.24 | ????0.24 | ????0.24 |
| Dilution water | Deionized water | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????13.7 | ????7.7 |
| Expression solids component in 50% the pigment dispersion paste () | ????32 ????(16) | ????32 ????(16) | ????32 ????(16) | ????32 ????(16) | ????32 ????(16) | ????32 ????(16) | ????20 ????(10) | |
Production Example 29 emulsion No.3
Add 1.9 parts of 70% acrylic resin soln 85.7 parts of (60 parts of solids components), サ イ メ Le 232 (annotating 11) that Production Example 21 obtains 40 parts (40 parts of solids components) and triethylamines, after 184.9 parts of dispersions of deionized water, obtain the emulsion No.3 that 32% heat curing-type anion electrophoresis coating is used.
(annotating 11) サ イ メ Le 232: the complex etherified melamine resin of Mitsui サ イ テ Star Network society system, trade(brand)name, methyl/butyl.
Embodiment 8 electrophoretic paint No.12
After in 312.5 parts of 32% emulsion No.3 that Production Example 29 obtains (dividing 100 parts), fitting into 32 parts of pigment dispersion paste No.11 (16 parts of solids components) Gu form, add 428.5 parts of deionized waters after, obtain electrophoretic paint No.12.
Production Example 9 and 10 electrophoretic paint No.13 and No.14
With emulsion shown in the table 6 and pigment dispersion paste combination, obtain electrophoretic paint No.13 and No.14 in the same manner with embodiment 8.
Comparative example 5～8 electrophoretic paint No.15～No.18
With emulsion shown in the table 6 and pigment dispersion paste combination, obtain electrophoretic paint No.15～No.18 in the same manner with embodiment 8.
Coated test
To be immersed among the electrophoretic paint No.15～No.18 that obtains in the foregoing description and the comparative example through the cold-rolled steel sheet that zinc phosphate is handled, as anode, energising is 3 minutes under 25 ℃ of bath temperatures, load voltage 150V, carries out electrophoretic coating with this steel plate.The thickness that electrophoresis is filmed is 20 μ m, after the washing, uses electric hot air dryer, carries out 20 minutes the drying of curing under 170 ℃.
The film performance of electrophoretic paint No.12～No.18 has been shown in table 6.
In addition, performance test is carried out according to method described later.
Table 6
| Embodiment | Comparative example | |||||||
| ????8 | ????9 | ????10 | ????5 | ????6 | ????7 | ????8 | ||
| Electrophoretic paint | ????No.12 | ????No.13 | ????No.14 | ????No.15 | ????No.16 | ????No.17 | ????No.18 | |
| Emulsion No.3 | ????312.5 ????(100) | ????312.5 ????(100) | ????312.5 ????(100) | ????312.5 ????(100) | ????312.5 ????(100) | ????312.5 ????(100) | ????312.5 ????(100) | |
| Pigment dispersion paste No.11 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.12 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.13 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.14 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.15 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.16 | ????32 ????(16) | |||||||
| Pigment dispersion paste No.17 | ????20 ????(10) | |||||||
| Deionized water | ????428.5 | ????428.5 | ????428.5 | ????428.5 | ????428.5 | ????428.5 | ????400.5 | |
| 15% coating | ????773 ????(116) | ????773 ????(116) | ????773 ????(116) | ????773 ????(116) | ????773 ????(116) | ????773 ????(116) | ????733 ????(110) | |
| Film performance | Salt tolerant sprayability (annotating 11) | ????○ | ????○ | ????○ | ????△ | ????△ | ????△ | ????× |
| Paint stability (annotating 12) | ????○ | ????◎ | ????◎ | ????△ | ????△ | ????○ | ????○ | |
| Finishability (annotating 13) | ????○ | ????○ | ????○ | ????△ | ????△ | ????△ | ????○ | |
Expression solids component in ()
(annotating 11) salt tolerant sprayability
On the electrophoretic coating plate that obtains, otch and the dark matrix that arrives with electrophoresis is filmed and is cut into cross by knife according to JIS Z2371, carry out 480 hours salt spray testing, according to the rust of knife wound place generation, the width of bubbling, estimate according to following standard.
Zero: the maximum width of rust, bubbling is apart from the not enough 3mm of otch (one-sided)
△: the maximum width of rust, bubbling is apart from more than the otch 3mm but not enough 4mm (one-sided)
*: the maximum width of rust, bubbling is apart from (one-sided) more than the otch 4mm.
The stability of (annotating 12) coating
Coating joined in the container and airtight after, stirred for 4 weeks down at 30 ℃, with the bath coating of the filtering net full dose filter 23 L in 400 mesh sieve holes.
◎: the not enough 5mg/L of filtered residue,
Zero: the not enough 10mg/L of filtered residue,
Above but the not enough 20mg/L of △: filtered residue 10mg/L,
*: more than the filtered residue 20mg/L.
(annotating 13) finishability
Be coated with the outward appearance of face with the eyes evaluation
Zero: smoothness is well no problem,
△: see that a little the finishability owing to ripple, delustring, uneven surface etc. descends.
*: owing to the processibility of ripple, delustring, uneven surface etc. descends very big.
Industrial applicibility
Can find out that from the above embodiments electrophoretic coating of the present invention does not contain the poisonous metal of lead or chromium etc., is non-harmful electrophoretic coating, and, anticorrosive property can be provided, the good coated article such as the finishability of filming.
Claims (8)
1. an electrophoretic paint is characterized in that, contains at least a silica modified phosphate cpd selected as rust-preventive agent from the group that following formula (1) and (2) constitute:
(xMHPO
43H
2O)·(ySiO
2)·(mCaSiO
3)·(nCaCO
3)?????(1)
(Ca
3(PO
4)
23H
2O)·(ySiO
2)·(mCaSiO
3)·(nCaCO
3)??(2)
In the formula,
M is Mg or Ca, and x, y and m are respectively 1～3 integers, and n is 0～3 integer.
2. electrophoretic paint according to claim 1, wherein, the silica modified phosphate cpd of formula (1) is selected from:
2MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
3MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
MgHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2MgHPO
4·3H
2O·2SiO
2·CaSiO
3·CaCO
3
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
3CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3。
3. electrophoretic paint according to claim 1, wherein, the silica modified phosphate cpd of formula (2) is selected from:
Ca
3(PO
4)
2·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Ca
3(PO
4)
2·3H
2O·2SiO
2·CaSiO
3·3CaCO
3
Ca
3(PO
4)
2·3H
2O·2SiO
2·2CaSiO
3·2CaCO
3
Ca
3(PO
4)
2·
3H
2O·3SiO
2·CaSiO
3·2CaCO
3。
4. electrophoretic paint according to claim 1, wherein, silica modified phosphate cpd is selected from:
3CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
2CaHPO
4·3H
2O·2SiO
2·CaSiO
3·2CaCO
3
Ca
3(PO
4)
2·3H
2O·2SiO
2·CaSiO
3·2CaCO
3。
5. electrophoretic paint according to claim 1 wherein, with respect to total solids component 100 weight parts of the resinous principle in the coating, contains silica modified phosphate cpd 0.1～50 weight part.
6. electrophoretic paint according to claim 1 wherein, with respect to total solids component 100 weight parts of the resinous principle in the coating, contains silica modified phosphate cpd 1～20 weight part.
7. electrophoretic paint according to claim 1, wherein, electrophoretic paint is Air drying type electrophoretic paint, heat curing-type anion electrophoresis coating or heat curing-type cation electrophoretic coating.
8. the article of an electrophoretic coating, it is to use each described electrophoretic paint of claim 1～7 to carry out electrophoretic coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004160395 | 2004-05-31 | ||
| JP160395/04 | 2004-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1704453A true CN1704453A (en) | 2005-12-07 |
| CN100432158C CN100432158C (en) | 2008-11-12 |
Family
ID=35576431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100740971A Expired - Fee Related CN100432158C (en) | 2004-05-31 | 2005-05-31 | Electrophoresis paint |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20060046327A (en) |
| CN (1) | CN100432158C (en) |
| TW (1) | TW200613484A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101974529B1 (en) * | 2017-09-22 | 2019-05-02 | 한국과학기술연구원 | A solid lubicant for waterborne air-curable coating |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5827999A (en) * | 1981-08-13 | 1983-02-18 | Nippon Paint Co Ltd | Temporary rust preventing treatment prior to electrodeposition painting |
| JPS5881995A (en) * | 1981-11-09 | 1983-05-17 | Mitsui Toatsu Chem Inc | Formation of metal oxide film |
| CN1101363A (en) * | 1993-10-08 | 1995-04-12 | 张展洪 | Production of multifunctional water-soluble non-toxic fast-dried anti-rust primer used on rusty surfaces |
| JP4568386B2 (en) * | 1997-05-14 | 2010-10-27 | 日本ペイント株式会社 | Rust prevention coating agent and rust prevention treatment method |
| EP1109867B1 (en) * | 1998-08-21 | 2002-05-02 | Sachtleben Chemie GmbH | Inorganic anti-corrosive pigments and method for the production thereof |
| JP3548979B2 (en) * | 2000-07-12 | 2004-08-04 | 日新製鋼株式会社 | Painted metal plate using non-chromium compound rust preventive pigment for coating film |
-
2005
- 2005-05-27 TW TW094117361A patent/TW200613484A/en unknown
- 2005-05-31 KR KR1020050046194A patent/KR20060046327A/en not_active Application Discontinuation
- 2005-05-31 CN CNB2005100740971A patent/CN100432158C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| TW200613484A (en) | 2006-05-01 |
| CN100432158C (en) | 2008-11-12 |
| KR20060046327A (en) | 2006-05-17 |
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