CN101522823A - Conductivity control agent for cationic electrodeposition coating material and method of regulating electric conductivity of cationic electrodeposition - Google Patents
Conductivity control agent for cationic electrodeposition coating material and method of regulating electric conductivity of cationic electrodeposition Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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Abstract
The invention provides a technology that prevents any deterioration of conductivity and throwing power in a cationic electrodeposition coating material composition of low solid and low ash contents. For example, there is provided a conductivity control agent for cationic electrodeposition coating material for use in a cationic electrodeposition coating material of solid content as low as 0.5 to 9.0 wt.%, comprising an aminated compound of 500 to 20,000 molecular weight and 200 to 500 mmol/100g amine value so as to attain a regulation of electric conductivity to 900 to 2000 [mu]S/cm. Further, there is provided a method of regulating the electric conductivity of cationic electrodeposition coating material, comprising the steps of mixing a conductivity control agent with a cationic electrodeposition coating material of solid content as low as 0.5 to 9.0 wt.%; and regulating the electric conductivity of the cationic electrodeposition coating material of low solid content after the mixing step to 900 to 2000 [mu]S/cm, wherein the conductivity control agent contains an aminated compound of 200 to 500 mmol/100g amine value.
Description
Technical field
The present invention relates to be used for the specific conductivity control agent of cation electric deposition paint composition and be used to use this control agent to regulate the method for the specific conductivity of cation electric deposition paint composition.
Background technology
Because even object has complicated profile, cation electrodeposition coating also can apply at detail section, and can be automatically and coating is provided continuously, so cation electrodeposition coating is widely used as the primer base of object big and that have complicated shape, in particular for vehicle body etc.Cation electrodeposition coating is by object to be coated is immersed in the cation electric deposition paint composition as negative electrode, and applies voltage and carry out.
Conventional cation electric deposition paint composition is that solids content is the water-based paint compositions of about 20% weight.Said composition is left standstill and do not stir component (such as the pigment) sedimentation that can make wherein, and this can cause producing throw out in containing the galvanic deposit pond of said composition.Usually, stir, prevent that cation electric deposition paint composition from producing throw out by the pump circulation or by agitator.
Yet the cationic electrodeposition pond is the main equipment that vehicle body can be immersed coating composition.Be accompanied by circulation or stir the required energy of said composition, required equipment or the maintenance of equipment and need high cost.It obviously is favourable reducing or do not carry out such circulation or stirring for energy-conservation in the cationic electrodeposition coating procedure.Therefore, do not have sedimentation or almost do not have settled cation electric deposition paint composition, particularly, the cation electric deposition paint composition that solids content is lower or ash content is lower is effective.Such cation electric deposition paint composition is studied.
For example, TOHKEMY 2004-231989 (patent documentation 1) public use pigment ash content be that 3-10% weight and solids content are the ecological friendly galvanic deposit coating method of the cation electric deposition paint composition of 5-12% weight.This cation electric deposition paint composition is useful, because this composition only has a spot of sedimentation, thereby and reduces and stirs or the round-robin cost of energy.Disadvantageously, the solids content of reduction coating composition descends the specific conductivity of said composition.But also can make said composition " throwing power " variation, in this article, throwing power is the ability that forms coat film in the galvanic deposit coating procedure on the details position of object.
The known specific conductivity of suitably adjusting coating composition of those skilled in the art can provide required throwing power.As patent documentation, TOHKEMY 2004-269627 (patent documentation 2) discloses the specific conductivity of coating composition and the relation of throwing power.The cation electric deposition paint composition of describing in the document contains the sulfonium modified epoxy, so said composition needs controlling diaphragm resistance.
After deliberation the amine value of the matrix resin in the cation electric deposition paint composition [referring to TOHKEMY 2005-232397 (patent documentation 3), Japanese kokai publication hei 7-150079 (patent documentation 4) etc.].The amine value that patent documentation 3 openly need make polyurethane resin (matrix resin) is at 20-60mg KOH/g (that is, in scope 35.7-107.0mmol/100g).The amine value that patent documentation 4 also openly need make the cationic electrodeposition resin is at 3-200mg KOH/g (that is, in scope 5.3-356mmol/100g).These amine value scopes are routine and lower substantially.
Patent documentation 1: TOHKEMY 2004-231989
Patent documentation 2: TOHKEMY 2004-269627
Patent documentation 3: TOHKEMY 2005-232397
Patent documentation 4: Japanese kokai publication hei 7-150079
Summary of the invention
Invent the problem of required solution
Compare with traditional cation electric deposition paint composition, the cation electric deposition paint composition that solids content is lower and/or ash content is lower tends to have lower specific conductivity.The specific conductivity that the invention provides the cation electric deposition paint composition that prevents that solids content is lower and/or ash content is lower descends, and prevents the technology that throwing power descends with specific conductivity.
Solve the means of problem
Therefore, the invention provides and be used for the specific conductivity control agent that solids content is the low solid content type cation electric deposition paint composition of 0.5-9.0% weight, it is 500-20 that described control agent comprises molecular weight, 000 and the amine value be containing of 200-500mmol/100g of amino compound, be 900-2000 μ S/cm with conductivity adjustment with described composition.Described cation electric deposition paint composition contains the specific conductivity control agent as milk sap outside the cation epoxy resin, solidifying agent and the pigment that contain as coat film formation property component, in fact described milk sap add as the 3rd component.
The aminocompound that contains as the specific conductivity control agent can be an amine-modified epoxy resin.Described amine-modified epoxy resin is preferably epoxy group(ing) by the Resins, epoxy of amine compound modification.
Perhaps, containing aminocompound can be that amine is acrylic resin modified.The acrylic resin modified preferably epoxy group(ing) of this amine is through the acrylic resin of amine compound modification.
Described Resins, epoxy can be bisphenol type, tert-butyl catechol type, phenol novolac resin type (Off ェ ノ-Le ノ ボ ラ Star Network type phenol novolak type) or cresols novolac resin type (Network レ ゾ-Le ノ ボ ラ Star Network type cresol novolak type), and its molecular-weight average is 500-20,000.
It is the low solid content type cation electric deposition paint composition of 0.5-9.0% weight that the present invention also provides solids content, it comprises and contains the specific conductivity control agent that contains aminocompound that the amine value is 200-500mmol/100g, and the specific conductivity of described composition is 900-2,000 μ S/cm.
The present invention further provides the method for the specific conductivity that is used to regulate cation electric deposition paint composition, it may further comprise the steps:
To solids content is to add the specific conductivity control agent in the low solid content type cation electric deposition paint composition of 0.5-9.0% weight, and
Conductivity adjustment with cation electric deposition paint composition in above-mentioned steps is 900-2,000 μ S/cm,
Wherein, described specific conductivity control agent comprises the aminocompound that contains that the amine value is 200-500mmol/100g.
The present invention also further provides method from the specific conductivity control agent to cation electric deposition paint composition that supply with, and it may further comprise the steps:
To solids content is to supply with the specific conductivity control agent in the low solid content type cation electric deposition paint composition of 0.5-9.0% weight, and
Conductivity adjustment with cation electric deposition paint composition in above-mentioned steps is 900-2,000 μ S/cm,
Wherein, described specific conductivity control agent comprises the aminocompound that contains that the amine value is 200-500mmol/100g.
The invention effect
By in cation electric deposition paint composition, adding certain specific conductivity control agent that is used for cation electric deposition paint composition, the present invention can solve the problem relevant with cation electric deposition paint composition, for example the specific conductivity of cation electric deposition paint composition reduces and consequent throwing power reduces, and described cation electric deposition paint composition is than low grey somatotype and/or than the low solid content type.
Description of drawings
Fig. 1 is the side-view of the example of the illustration casing that is used to estimate throwing power.
Fig. 2 is the cross-sectional view of an embodiment of the schematic illustration method that is used to estimate throwing power.
Label declaration
10: casing
11-14: the steel plate of handling with zinc phosphate
15: opening
20: the galvanic deposit container
21: electrodeposition coating composition
22: counter electrode
Embodiment
According to the present invention, the specific conductivity control agent that is used for cation electric deposition paint composition comprises the aminocompound that contains that the amine value is 200-500mmol/100g.Any aminocompound that contains can be as the specific conductivity control agent of cation electric deposition paint composition of the present invention, as long as this specific conductivity control agent has the amine value scope that is defined as above.Usually, this specific conductivity control agent preferred amines modified epoxy and amine are acrylic resin modified.The specific conductivity control agent that can be used for if necessary, cation electric deposition paint composition with the acid neutralization.Described amine value is preferably 250-450mmol/100g, most preferably is 300-400mmol/100g.If the amine value, then need increase the necessary amounts of reagent to be added less than 200mmol/100g so that the specific conductivity optimization of the lower cationic liquid electrodeposition coating composition of solids content, this can cause the erosion resistance variation.If the amine value greater than 500mmol/100g, then some problems can occur, for example deposition property decline and can not get required throwing power.Like this, the consistency to the zinc steel plate is reduced.
Specific conductivity control agent as cation electric deposition paint composition of the present invention contain that aminocompound comprises lower molecular weight or high-molecular weight contains aminocompound.Usually, can use high-molecular weight to contain amino composition, for example amine-modified epoxy resin and amine are acrylic resin modified.The low-molecular-weight example that contains amino composition comprises Monoethanolamine MEA BASF, diethanolamine, dimethyl butylamine etc.
The present invention preferably adopts high-molecular weight to contain amino composition, most preferably adopts amine-modified epoxy resin and amine acrylic resin modified.Amine-modified epoxy resin can promptly, carry out modification with amine compound to epoxy group(ing) wherein by the modification of used for epoxy resin amine compound is obtained.Can use conventional Resins, epoxy, preferred molecular weight is 500-20,000 Resins, epoxy is such as bisphenol-type epoxy resin, tert-butyl catechol type Resins, epoxy, phenol novolac resin type Resins, epoxy and cresols novolac resin type Resins, epoxy.In these Resins, epoxy, especially preferred phenol novolac resin type Resins, epoxy and cresols novolac resin type Resins, epoxy.Particularly, these Resins, epoxy can commercially availablely obtain, and for example comprise phenol novolac resin type Resins, epoxy DEN-438 available from Dow Chemical JapanLtd.; Cresols novolac resin type Resins, epoxy YDCN-703 changes into society etc. available from Dongdu.
Available resin such as the alkylphenol of polyester polyol, polyether glycol and simple function group comes Resins, epoxy is carried out modification.Perhaps, can be with the Resins, epoxy chain extension, it comprises the reaction with the epoxy group(ing) in the Resins, epoxy and dibasic alcohol or dicarboxylic acid.
Acrylic resin modified example comprises: the unmodified homopolymer of dimethylaminoethyl methacrylate (it is to contain amino monomers) or the unmodified multipolymer of dimethylaminoethyl methacrylate and other polymerisable monomers, and the modified copolymer (wherein with aminated compounds glycidyl being carried out modification) of the modified homopolymer of glycidyl methacrylate (wherein with aminated compounds glycidyl being carried out modification) or glycidyl methacrylate and other polymerisable monomers.
Can or have at Resins, epoxy and introduce amino compound in the acrylic resin of epoxy group(ing) and comprise primary amine, secondary amine, tertiary amine, for example butylamine, octylame, diethylamine, dibutylamine, dimethyl butylamine, Monoethanolamine MEA BASF, diethanolamine, N-methyl-thanomin, Triethylammonium chloride, N, the mixture and the secondary amine of N-dimethylethanolamine acetate, diethyl disulphide and acetate, described secondary amine is the end-blocking primary amine, for example two ketoimines of two ketoimines of N-aminoethyl ethanolamine (ジ ケ チ ミ Application diketimine) and diethylamine etc.Can use one or more amine.
As mentioned above, every kind of amine-modified epoxy resin and the acrylic resin modified number-average molecular weight of amine are preferably 500-20,000.If number-average molecular weight less than 500, then can make erosion resistance descend, and owing to undetermined reason still, can find that throwing power descends and descend with the consistency of zinc steel plate.If number-average molecular weight greater than 20,000, then can cause the finished product outward appearance relatively poor.
Above-mentioned specific conductivity control agent of the present invention is applicable to cation electric deposition paint composition, and it includes but not limited to that solids content is the low solid content type cation electric deposition paint composition of 0.5-9.0% weight.This specific conductivity control agent is applicable to that also solids content is the conventional cation electric deposition paint composition of about 20% weight.Under the situation that the specific conductivity of conventional cation electric deposition paint composition descends, the throwing power deficiency that the gained electrodeposited coating provides.In view of this deficiency, adding specific conductivity control agent of the present invention in the cation electric deposition paint composition of routine can be controlled at specific conductivity in the suitable scope, and this causes guaranteeing the throwing power that provides enough.
Can be in advance acrylic resin modified with neutralize amine-modified epoxy resin of the present invention and amine of neutralizing acid.Described neutralizing acid comprises mineral acid and organic acid, for example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, formic acid, acetate, lactic acid etc.
Electrodeposition coating composition
With regard to the specific conductivity control agent, regulate the specific conductivity that the amount of the reagent in cation electric deposition paint composition to be added can suitably be regulated electrodeposition coating composition with regard to cation electric deposition paint composition of the present invention.This cation electric deposition paint composition comprises cation epoxy resin and solidifying agent, and if needed, also comprises pigment and/or additive.Hereinafter these components will be described respectively.
Cation epoxy resin (forming the cation-modified Resins, epoxy of component as coat film)
Cation epoxy resin of the present invention comprises the Resins, epoxy with the amine modification.This cation epoxy resin is prepared as follows usually: by open whole oxirane rings of bisphenol-type epoxy resin with the active dydrogen compounds that can introduce cation group; Or, open remaining oxirane ring with the active dydrogen compounds that can introduce cation group then by opening a part of oxirane ring with other active dydrogen compounds.The Resins, epoxy preferred amines value that cation electric deposition paint composition comprised is 50-200mmol/100g, and this amine value is less than the amine value (being 200-500mmol/100g) of specific conductivity control agent.If the amine value less than 50mmol/100g, then is difficult to guarantee the dispersiveness of cation-modified Resins, epoxy in water.If the amine value greater than 200mmol/100g, then can make the water-repellancy variation of the coat film that obtains.Therefore, these situations are not preferred.
The representative instance of bisphenol-type epoxy resin comprises bisphenol A type epoxy resin and bisphenol f type epoxy resin.The former commercially available prod comprises that Epikote 828 is (by Yuka-Shell EpoxyCo., Ltd. make, epoxy equivalent (weight): 180-190), Epikote 1001 (same manufacturers, epoxy equivalent (weight): 450-500), Epikote 1010 (same manufacturers, epoxy equivalent (weight): 3,000-4,000) etc., the latter's commercially available prod comprises Epikote 807 (same manufacturers, epoxy equivalent (weight): 170) etc.
The Resins, epoxy of Han oxazolidone ring is represented by following formula 1, and is disclosed in Japanese kokai publication hei 5-306327:
Formula 1 compound can be used as cation epoxy resin
Wherein R is the residue that forms by the glycidoxypropyl of removing the 2-glycidyl epoxy compounds, and R ' is the residue that forms by the isocyanate group of removing diisocyanate cpd, and n is a positive integer.This is because the coating that obtains has excellent thermotolerance and erosion resistance.
The example that Yong Yu introduces the method for Resins, epoxy Jiang the oxazolidone ring comprises: in the presence of basic catalyst, make the reaction of polyepoxide and end capped polymeric polyisocyanate, heating and insulation, and from system, distillating lower alcohol as by product to obtain product, described polymeric polyisocyanate carries out end-blocking by the lower alcohol such as methyl alcohol.
Such Resins, epoxy can be via the resin modified that is fit to, and suitable resin is polyester polyol, polyether glycol and simple function group alkylphenol for example.In addition, can utilize the chain of the reaction extended loop epoxy resins of epoxy group(ing) and dibasic alcohol or dicarboxylic acid.
The ring of Resins, epoxy need be opened with active dydrogen compounds, so that the amine value is 50-200mmol/100g after the open loop, more preferably primary amine fiduciary point 5-50% wherein.
Can introduce the acid salt that active dydrogen compounds in the cation group comprises primary amine, secondary amine and tertiary amine, the mixture of sulfide and acid.Use one or more primary amine, secondary amine or/and the acid salt of tertiary amine as the active dydrogen compounds of introducing positively charged ion group, contains one or more primary amine, secondary amine or/and the Resins, epoxy of tertiary amine groups thereby prepare.
Particular instance comprises butylamine, octylame, diethylamine, dibutylamine, methylbutylamine, Monoethanolamine MEA BASF, diethanolamine, N-methyl-thanomin, Triethylammonium chloride, N, the mixture and the secondary amine of N-dimethyl-thanomin acetate, diethyl disulphide and acetate, described secondary amine is the end-blocking primary amine, for example two ketoimines of the ketoimine of N-aminoethyl ethanolamine and diethylenetriamine etc.Can use one or more amine.
Solidifying agent
The preferred blocked polyisocyanate of solidifying agent that the present invention adopts, it is to carry out end capped polymeric polyisocyanate with encapsulant.The polymeric polyisocyanate that the present invention adopts is meant the compound that has 2 or a plurality of isocyanate group in the molecule.The example of polymeric polyisocyanate comprises the polymeric polyisocyanate of any type, for example aliphatic type, alicyclic ring type, aromatics type, aromatic-aliphatic type.
The specific examples of polymeric polyisocyanate comprises: aromatic diisocyanate, for example tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), to phenylene vulcabond and naphthalene diisocyanate; Carbonatoms is the aliphatic vulcabond of 3-12, hexamethylene diisocyanate (HDI), 2,2 for example, 4-trimethyl cyclohexane vulcabond and lysinediisocyanate; Carbonatoms is the alicyclic diisocyanate of 5-18, for example 1,4-cyclohexyl diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (hydrogenation MDI), methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4 '-vulcabond and methylcyclohexane-1,3-vulcabond (hydrogenation XDI), hydrogenation TDI and 2,5-or 2, two (isocyanide acyl methyl)-dicyclo [2.2.1] heptane (being also referred to as norborneol alkane vulcabond) of 6-; Aliphatic vulcabond with aromatic ring, for example xylylene vulcabond (XDI) and tetramethylxylylene diisocyanate (TMXDI); The modified product of these vulcabond (polyurethane ester products, carbodiimide, urethodione, urethoimine, biuret and/or isocyanurate-modified product) etc.These materials can use separately or with 2 kinds or multiple being used in combination.
Also can be used as solidifying agent by polyisocyanates and polyvalent alcohol with adducts or the prepolymer that the reaction of the NCO/OH ratio more than 2 obtains, described polyvalent alcohol is ethylene glycol, propylene glycol, TriMethylolPropane(TMP) and hexanetriol for example.
Because the coated membrane that obtains has excellent weathering resistance, so polymeric polyisocyanate preferred aliphatic series polymeric polyisocyanate and alicyclic polymeric isocyanate.
The concrete preferred embodiment of aliphatic polymeric isocyanate and alicyclic polymeric isocyanate comprises hexamethylene diisocyanate, hydrogenation TDI, hydrogenation MDI, hydrogenation XDI, IPDI, norborneol alkane vulcabond, and their dimer (biuret) and tripolymer (isocyanuric acid ester) etc.
The encapsulant that is added to polyisocyanate-based is at room temperature stable, but the free isocyanate group of when being heated to decomposition temperature or higher temperature, can regenerating.
Implement down under the situation of solidification process at low temperature (for example, not being higher than 160 ℃) at needs, preferably the encapsulant that uses is lactan type encapsulant, such as ε-Ji Neixianan, δ-Valerolactim, butyrolactam and azetidinone; And oxime type encapsulant, such as formoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketoxime, Diacetylmonoxime and cyclohexanone-oxime.
The content that contains the tackiness agent of cation epoxy resin and solidifying agent accounts for the 25-85% weight of the total solids level of electrodeposition coating composition usually, preferred 40-70% weight.
Pigment
Electrodeposition coating composition of the present invention can comprise conventional one or more pigment that use.The example of operable pigment comprises:the conventional mineral dye that uses, and tinting pigment for example is such as titanium white, carbon black and colcother; Filler pigment is such as kaolin, talcum powder, pure aluminium silicate, lime carbonate, mica and clay; Anticorrosive pigment, for example zinc phosphate, tertiary iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminium triphosphate, zinc molybdate, molybdic acid aluminium, calcium molybdate and phospho-molybdic acid aluminium, aluminium zinc phosphomolybdate (リ Application モ リ Block テ Application acid ア Le ミ ニ ウ system Ami aluminum zinc phosphomolybdate), bismuth hydroxide, bismuthous oxide bismuth trioxide, Bismuth Subcarbonate, Bismuth trinitrate, bismuth benzoate, bismuth citrate, bismuth silicate etc.
The content of pigment accounts for the 1-35% weight of the total solids level of electrodeposition coating composition usually, preferred 10-30% weight.
The colo(u)rant dispersion thickener
When pigment was used as the composition of electrodeposition coating composition, this pigment was scattered in the aqueous medium to form thickener with high density in advance with the resin that is called pigment dispersing resin usually.Because pigment is Powdered, therefore being difficult to by a step is the uniform lower concentration state that is used for electrodeposition coating composition with colo(u)rant dispersion.Usually, such thickener is called as the colo(u)rant dispersion thickener.
Can prepare the colo(u)rant dispersion thickener in the aqueous medium by pigment is scattered in pigment-dispersion resin varnish.Usually, described pigment dispersing resin varnish comprises low-molecular-weight cats product or nonionogenic tenside and such as the cationic polymers of the modified epoxy with quaternary ammonium group and/or uncle's sulfonium base (3 Grade ス Le ホ ニ ウ system tertiary sulfonium group).This aqueous medium comprises ion exchanged water, contains a spot of one or more pure water etc.Usually, the solids content of the pigment dispersing resin varnish in the colo(u)rant dispersion thickener is the 5-40 weight part, and the solids content of the pigment in the colo(u)rant dispersion thickener is the 10-30 weight part.
With respect to 100 parts by weight resin solids contents, with 10-1, above-mentioned pigment dispersing resin varnish of 000 weight part and pigment mix.Subsequently, this pigment is scattered in the mixture in conventional diverting device (for example ball mill and sand mill), to produce the colo(u)rant dispersion thickener that pigment has given uniform particle size.
The cation electric deposition paint composition solids content of the invention described above is necessary for the 0.5-9.0% weight of coating composition.If the solids content of coating composition is less than 0.5% weight, then can not produce cationic electrodeposition coating.On the other hand, if the solids content of coating composition greater than 9.0% weight, when then not stirring when leaving standstill, the pigment composition that is contained in the cation electric deposition paint composition can precipitate.Therefore, these situations are not preferred.
The preparation of electrodeposition coating composition
Can prepare electrodeposition coating composition in the aqueous medium by cation epoxy resin, solidifying agent and colo(u)rant dispersion thickener are scattered in.Usually, aqueous medium can comprise neutralizing agent, to improve the dispersiveness of cation epoxy resin.This neutralizing agent comprises mineral acid and organic acid, for example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetate and lactic acid.The amount of employed neutralizing agent is the amount that is enough to reach the neutralization ratio of at least 20% neutralization ratio, preferred 30%-60%.
The amount of employed solidifying agent should be in solidification process, be enough to cation epoxy resin in one or more primary amine, secondary amine and/or tertiary amine groups or the amount that reacts of one or more hydrogen functional group of containing (for example hydroxyl), thereby excellent solidified coating film is provided.Usually, the weight ratio scope of cation epoxy resin/solidifying agent (with solid content meter) is 90/10-50/50, preferred 80/20-65/35.
Electrodeposition coating composition can comprise: as the tin compound of catalyzer, and for example dibutyl tin laurate and dibutyltin oxide, or have the conventional polyurethane(s) catalyst for cracking of using.Because these catalyzer are lead-containing compounds not substantially preferably, the amount of the therefore preferred catalyzer that uses is the 0.1-5% weight of blocked polyisocyanate compound.
Electrodeposition coating composition can comprise the additive that routine is used for coating composition, for example water Combination organic solvent, tensio-active agent, antioxidant, UV absorption agent and pigment.
Cation electric deposition paint composition of the present invention is not particularly limited, as long as described coating composition comprises above-mentioned main component.This cation electric deposition paint composition is the low solid content type, and specific conductivity control agent effectiveness wherein of the present invention is remarkable.This cation electric deposition paint composition can be low grey somatotype.
Compare (that is, about 20% weight) with the coating composition of routine, the solids content of the cation electric deposition paint composition of low solid content type is lower, particularly is 0.5-9% weight, more preferably 3-9% weight.If undesirable precipitation less than 0.5% weight, then if do not stir, then can take place in the composition in solids content.On the other hand, if acceptable solids content greater than 9% weight, then may there is no need to add the specific conductivity control agent for the specific conductivity of regulating cation electric deposition paint composition.
The method that reduces the solids content of cation electric deposition paint composition comprises the pigment content that reduces in this coating composition, and wherein the ash content in this coating composition reduces; Here, ash content calculates according to following formula: [(weight of the solids content of coating composition burning back residual ash)/(weight of the solids content of coating composition)] * 100.Therefore, the present invention can adopt the cation electric deposition paint composition of low grey somatotype.The ash content of traditional cation electric deposition paint composition is a 15-40% weight.Therefore, the ash content of the cation electric deposition paint composition of low grey somatotype is preferably 2-7% weight, more preferably 3-5% weight.
Treat that preferably galvanic deposit applies and electrodeposition coating composition to be used applies article are for carrying out the surface-treated conductor of zinc phosphate processing etc. in advance by flood or spray method etc.Perhaps, the surface of article can be unprocessed.The conductor of Shi Yonging is any material herein, and described material can become negative electrode when galvanic deposit applies, and preferably but be not particularly limited to metal base.
The condition that galvanic deposit applies and conventional those conditional likelihoods that use in galvanic deposit applies arbitrarily.The voltage that applies can considerable change in the scope of 1 volt-hundreds of volts.Current density is generally about 10 peace/m
2-160 peace/m
2In the galvanic deposit coating procedure, current density is tended to descend.
After the galvanic deposit according to the inventive method applies, make the coating that obtains carry out conventional baking process at elevated temperatures, it is included in stove or the baking oven or under the infrared heating lamp and toasts.Usually, storing temperature can change in about 140 ℃-Yue 180 ℃ scope.This is coated with the article of cation electric deposition paint composition of the present invention final rinse water, and dry and baking, to form solidified galvanic deposit coat film thereon.Thereby finished coating processes of the present invention.
The adjusting of specific conductivity (conductivity)
According to the present invention, above-mentioned specific conductivity control agent is added in the cationic liquid electrodeposition coating composition to guarantee the specific conductivity of this liquid coating composition.As mentioned above, use with traditional cationic liquid electrodeposition coating composition (that is, solids content is about 20% weight) and compare, the specific conductivity of the cationic liquid electrodeposition coating composition that solids content is lower is tended to deficiency.Therefore, adding specific specific conductivity control agent in described cation electric deposition paint composition can remedy such and insufficient.Increase forms the amine value of the cation-modified Resins, epoxy of composition as coat film can be with the conductivity adjustment of said composition to the scope that is fit to, thereby guarantees the throwing power of said composition.Yet, if the amine value of this cation-modified Resins, epoxy greater than 200mmol/100g, the water-repellancy of the coat film that obtains will variation.Such condition is not preferred.The necessary specific conductivity of the throwing power that obtains expecting is 900-2,000 μ S/cm.Adding the specific conductivity control agent in than the cationic liquid electrodeposition coating composition of low solid content type can control the specific conductivity of electrodeposition coating composition and be adjusted in the scope of expectation.The preferred lower limit of specific conductivity is 1,000 μ S/cm, and is limited to 1,800 μ S/cm on preferred.If less than 900 μ S/cm, then there is the problem that can not realize desired throwing power in specific conductivity.If specific conductivity is greater than 2,000 μ S/cm, then there is defective (being so-called pore) in the coat film that forms on the zinc steel plate through regular meeting.In this article, can under 25 ℃ fluid composition temperature, measure specific conductivity with commercially available conductometer.
The amount that joins the specific conductivity control agent of the present invention in the cation electric deposition paint composition is not particularly limited, as long as can realize the specific conductivity of expectation.With respect to the solids content of coating composition, the particular instance of this amount is a 0.5-30% weight, preferred 1-30% weight, more preferably 1-15% weight.If this amount is acceptable words less than 0.5% weight, then the specific conductivity deficiency can appear.Perhaps, if this amount also is acceptable words greater than 50% weight, then the increase meeting of specific conductivity is disproportionate with the amount of adding.
As mentioned above, what have specific conductivity through regulate desiredly can be low ash content and than the cation electric deposition paint composition of low solid content type than low solid content type cation electric deposition paint composition, and preferably has definite throwing power.Even in the coating processes that applies a plurality of article continuously, use such cation electric deposition paint composition, also must in the groove that contains cation electric deposition paint composition, replenish coat film and form component.In this case, the specific conductivity of the cation electric deposition paint composition in the groove can depart from the desired 900-2 of the present invention, the scope of 000 μ S/cm undesirably.If specific conductivity is not more than 900 μ S/cm, then can in the groove that contains cation electric deposition paint composition, further add this specific conductivity control agent, thereby solids content is maintained in the scope of 0.5-9.0% weight and with the conductivity adjustment of the cation electric deposition paint composition in the groove to 900-2, in the scope of 000 μ S/cm.
Embodiment
Be described in further detail the present invention according to following examples.It will be understood by those skilled in the art that and the invention is not restricted to these embodiment.In an embodiment, unless certain illustrated is arranged in addition, " part " and " % " by weight.
Embodiment A-1
295 parts of methyl iso-butyl ketone (MIBK) (hereinafter abbreviating it as MIBK), 37.5 parts of Mono Methyl Ethanol Amines and 52.5 parts of diethanolamine are packed into be equipped with in the flask of reflux exchanger and agitator.When stirring, make the temperature of mixture remain on 100 ℃.With 205 parts of phenol novolac resin type Resins, epoxy (available from Tohto Kasei Co., Ltd., trade(brand)name: YDCN-703) add gradually in this compound.After the resin adding is finished, reaction was carried out 3 hours.The molecular weight of the amino modified resin that obtains is 2,100, and the amine value is 340mmol/100g (MEQ (B)).
Embodiment A-2
5.5 parts of formic acid and 1254.5 parts of deionized waters are joined in the amino modified resin solution of 140 parts of preparations in embodiment A-1.Make the temperature of mixture remain on 80 ℃, stirred 30 minutes.Remove organic solvent in a vacuum, obtain being used for the specific conductivity control agent A (solids content: 7.0%) of fluid composition.
Embodiment B-1
255 parts of MIBK and 75 parts of Mono Methyl Ethanol Amines are packed into be equipped with in the flask of reflux exchanger and agitator.When stirring, make the temperature of mixture remain on 100 ℃.With 180 parts of cresols novolac resins (available from Dow Chemical Japan Ltd.,, trade(brand)name: DEN-438) add gradually in this mixture.After the resin adding is finished, reaction was carried out 3 hours.The molecular weight of the amino modified resin that obtains is 1,000, and the amine value is 390mmol/100g (MEQ (B)).
Embodiment B-2
14 parts of thionamic acids and 1,247 part of deionized water are joined in the amino modified resin solution of 140 parts of preparations in Embodiment B-1.Make the temperature of mixture remain on 80 ℃, stirred 30 minutes.Remove organic solvent in a vacuum, obtain being used for the specific conductivity control agent B (solids content: 7.0%) of fluid composition.
Embodiment C-1
50 parts of methyl iso-butyl ketone (MIBK) (MIBK) are packed into be equipped with in the flask of reflux exchanger, nitrogen inlet tube, dropping funnel and agitator.When stirring, make the temperature of mixture remain on 100 ℃.Utilize dropping funnel in 2 hours, the mixture of 100 parts of glycidyl methacrylate and 2 parts of Diisopropyl azodicarboxylates (AIBN) at the uniform velocity to be added drop-wise in the flask.Make the temperature of mixture remain on 100 ℃ of stirrings 30 minutes.Subsequently, in 1 hour, 52.5 parts of MIBK and 0.5 part of AIBN are dropwise joined in the flask.When stirring, reaction was carried out 1 hour.Termination reaction.
Embodiment C-2
47.5 parts of MIBK and 52.8 parts of Mono Methyl Ethanol Amines are joined in the flask that is equipped with reflux exchanger and agitator.Make the temperature of mixture remain on 100 ℃ of stirrings 30 minutes.The reaction mixture that in this mixture, adds 205 parts of preparations in Embodiment C-1 gradually.After the reaction mixture adding is finished, reaction was carried out 3 hours.The molecular weight of the amino modified resin that obtains is 9,800, and the amine value is 450mmol/100g (MEQ (B)).
Embodiment C-3
25.2 parts of lactic acid and 1,234.8 part of deionized water are joined in the amino modified resin solution of 140 parts of preparations in Embodiment C-2.Make the temperature of mixture remain on 80 ℃ of stirrings 30 minutes.Remove organic solvent in a vacuum, obtain being used for the specific conductivity control agent C (solids content: 7.0%) of fluid composition.
Comparative Example D
463.4 parts of deionized waters and 13.5 parts of formic acid are joined in the glass beaker.Stir the mixture.While stirring with 23.1 parts of dimethylethanolamines (molecular weight: 89) add gradually in this mixture, with the specific conductivity control agent D that obtains being used for fluid composition (active component content: 7%, the amine value of activeconstituents (MEQ (B)): 740mmol/100g).
Preparation example 1: the preparation of cation electric deposition paint composition
Preparation example 1-1: the preparation of amine-modified epoxy resin
With 92 part 2,4-/2,6-tolylene diisocyanate (2,4-type/2,6-type=8/2, weight ratio), 95 parts of methyl iso-butyl ketone (MIBK) (hereinafter abbreviating it as MIBK) and 0.5 part of dibutyl tin laurate are packed into and are equipped with in the flask of agitator, condenser, nitrogen inlet tube, thermometer and dropping funnel.In reaction mixture, dropwise add 21 parts of methyl alcohol while stirring.Reaction is at room temperature carried out.The heat that produces owing to reaction makes temperature of reaction be increased to 60 ℃.Reaction continues 30 minutes.Utilize dropping funnel that 50 parts of glycol monomethyls-2-ethylhexyl ether is added drop-wise in the reaction mixture.Propylene oxide (5mol) adducts that further in reaction mixture, adds 53 parts of dihydroxyphenyl propanes.Reaction is mainly carried out in 60-65 ℃ temperature range.Continue to react, disappear until absorption peak in the IR spectrometry based on isocyanate group.
Subsequently, be that 188 Resins, epoxy join in reaction mixture according to currently known methods by dihydroxyphenyl propane and epoxy chloropropane synthetic epoxy equivalent (weight) with 365 parts.Temperature of reaction is increased to 125 ℃.In this mixture, add 1.0 parts of benzyldimethylamines.To be reflected under 130 ℃ and carry out, so that epoxy equivalent (weight) is adjusted to 410.
Subsequently, it is sad to add 61 parts of dihydroxyphenyl propanes and 33 parts in this mixture.Be reflected under 120 ℃ and carry out,, then reaction mixture is cooled off so that epoxy equivalent (weight) is 1,190.The MIBK solution of the ketoimine of the N-aminoethyl ethanolamine of adding 11 parts of diethanolamine, 24 parts of N-ethyl-thanomins and 25 part of 79% weight in reaction mixture.Make to be reflected at and carried out under 110 ℃ 2 hours.Dilute this reaction mixture (non-volatile content: 80%) with MIBK.The solids content of the amine-modified epoxy resin that obtains is 80%.
Preparation example 1-2: the preparation of blocked isocyanate solidifying agent
1,250 part of diphenylmethanediisocyanate and 266.4 parts of MIBK are packed in the reaction vessel.With this mixture heating up to 80 ℃.In this mixture, add 2.5 parts of dibutyl tin laurates.226 parts of ε-Ji Neixianan are dissolved in 944 parts of ethylene glycol butyl ethers, to obtain solution.Under 80 ℃, in 2 hours, drips of solution is added in the mixture.Reaction mixture further is heated to 100 ℃ continues 4 hours.Affirmation disappears in the IR spectrometry based on the absorption peak of isocyanic ester.Reaction mixture is cooled off.336.1 parts of MIBK are added in the reaction mixture to obtain blocked isocyanate solidifying agent (glass transition temp: 0 ℃).
Preparation example 1-3: the preparation of pigment dispersing resin
222.0 parts of isophorone diisocyanates (hereafter is IPDI) are joined in the reaction vessel that is equipped with agitator, condenser, nitrogen inlet tube and thermometer.39.1 parts of MIBK are joined in this container with dilution IPDI, in reaction mixture, add 0.2 part of dibutyl tin laurate then.Subsequently, temperature is increased to 50 ℃, and, dropwise adds 131.5 parts of 2-Ethylhexyl Alcohols while stirring under the exsiccant nitrogen atmosphere, in 2 hours.Suitably cooling makes temperature of reaction remain on 50 ℃, to obtain 2-Ethylhexyl Alcohol half end-blocking IPDI (solid resin content: 90.0%).
Subsequently, 87.2 parts of dimethylethanolamines, lactic acid aqueous solution and 39.2 parts of ethylene glycol monobutyl ethers of 117.6 part 75% are joined in the suitable reaction vessel with said sequence.At 65 ℃ reaction mixture is continued stir about 30 minutes, to obtain quaternizing agent.
Subsequently, with 710.0 parts of EPON 829 (bisphenol A type epoxy resin, available from ShellChemical Company, epoxy equivalent (weight): 193-203) and 289.6 parts of dihydroxyphenyl propanes pack in the suitable reaction vessel.Under nitrogen atmosphere, reaction mixture is heated to 150-160 ℃.The reaction of generation initial exotherm.Reaction mixture is remained on 150-160 ℃ so that reaction continues 1 hour, be cooled to 120 ℃ then.The 2-Ethylhexyl Alcohol half end-blocking IPDI (MIBK solution) of 498.8 parts of previous preparations is joined in the reaction mixture.
Reaction mixture was kept 1 hour at 110-120 ℃.Subsequently, add 463.4 parts of ethylene glycol monobutyl ethers.Mixture is cooled to 85-95 ℃.After the homogenizing, 196.7 parts of previous quaternizing agents that prepare are joined in the reaction mixture.Make reaction mixture remain on 85-90 ℃, so that acid number is adjusted to 1.964 parts of deionized waters are joined in the reaction mixture, and quaternized with quencher epoxy-bisphenol a resin obtains having the pigment dispersing resin (resin solid content: 50%) of quaternary ammonium salt structure.
Preparation example 1-4: the preparation of colo(u)rant dispersion thickener
100 parts of pigment dispersing resins that prepare in preparation example 1-3,100.0 parts of titanium dioxide and 100.0 parts of ion exchanged waters are joined in the sand mill.With colo(u)rant dispersion, with particle size adjustment for being not more than 10 μ m, thereby obtain colo(u)rant dispersion thickener (solids content: 50%).
Preparation example 1-5: the preparation of milk sap
Amine-modified epoxy resin that will in preparation example 1-1, prepare and the blocked isocyanate solidifying agent uniform mixing (with solid content meter, Resins, epoxy/solidifying agent=80/20) that in preparation example 1-2, prepares.Add Glacial acetic acid so that ratio (MEQ (A)) in mixture: (equivalent of mg acid)/(solids content of 100g resin) is 30.In this mixture, add ion exchanged water with the diluted mixture thing.Remove MIBK in a vacuum, to obtain milk sap (solids content: 36%).
Comparative example 1
The milk sap for preparing among 319 parts of preparation example 1-5,133 parts of colo(u)rant dispersion thickeners, 543 parts of ion exchanged waters, 2 part of 10% cerous acetate aqueous solution and 3 parts of dibutyltin oxides are mixed, to obtain electrodeposition coating composition F (solids content: 20%).The solids content of cation electric deposition paint composition comprises that concentration is the pigment of 23% weight.Can calculate the solids content of coating composition herein, by following formula (according to JIS K 5601): [(composition is heated to 180 ℃ continues remaining quality after 30 minutes)/(quality of original composition)] * 100 (%).The electrodeposition coating composition F that obtains 1 is directly used as a comparative example.The specific conductivity of fluid composition is 1,600 μ S/cm.
Comparative example 2
The milk sap for preparing among 158 parts of preparation example 1-5,8 parts of colo(u)rant dispersion thickeners, 831 parts of ion exchanged waters, 2 part of 10% cerous acetate aqueous solution and 1 part of dibutyltin oxide are mixed, to obtain electrodeposition coating composition G (solids content: 7%).The concentration of pigment is 5% weight.The electrodeposition coating composition F that obtains 2 is directly used as a comparative example.The specific conductivity of fluid composition is 890 μ S/cm.
Embodiment 1
The specific conductivity control agent A of preparation in 6 parts of embodiment A-2 is joined among the electrodeposition coating composition G of 1,000 part of previous preparation, be 1,200 μ S/cm with conductivity adjustment, thereby obtain electrodeposition coating composition H composition.This electrodeposition coating composition H is used as embodiment 1.
Embodiment 2
The specific conductivity control agent B of preparation in 8 parts of Embodiment B-2 is joined among the electrodeposition coating composition G of 1,000 part of previous preparation, be 1,300 μ S/cm with conductivity adjustment, thereby obtain electrodeposition coating composition I composition.This electrodeposition coating composition I is used as embodiment 2.
Embodiment 3
The specific conductivity control agent C of preparation in 3 parts of Embodiment C-3 is joined among the electrodeposition coating composition G of 1,000 part of previous preparation, be 1,100 μ S/cm with conductivity adjustment, thereby obtain electrodeposition coating composition J composition.This electrodeposition coating composition J is used as embodiment 3.
Embodiment 4
400 parts of ion exchanged waters are joined among 1,000 part of previous electrodeposition coating composition G for preparing so that solids content (7%) reduces to 5%.This operation makes the specific conductivity (890 μ S/cm) of composition reduce to 640 μ S/cm.In said composition, add the specific conductivity control agent A of preparation in 8 parts of embodiment A-2, be 1,100 μ S/cm with conductivity adjustment, thereby obtain electrodeposition coating composition K composition.This electrodeposition coating composition K is used as embodiment 4.
Comparative example 3
The specific conductivity control agent D for preparing in 1 part of Comparative Example D is joined among the electrodeposition coating composition G of 1,000 part of previous preparation, be 1,200 μ S/cm with conductivity adjustment, thereby obtain electrodeposition coating composition L composition.This electrodeposition coating composition L 3 uses as a comparative example.
Estimate the cation electric deposition paint composition for preparing in embodiment and the comparative example and solidified cationic electrodeposition coat film thus according to following method.
Throwing power
Estimate the throwing power of cation electric deposition paint composition by so-called 4 box methods (4 pieces of ボ Star Network ス methods).Particularly, as shown in Figure 1, will be with zinc phosphate (SURFDINESD-5000, available from Nippon Paint K.K.) the 4 block plate 11-14 (JIS G3141SPCC-SD) that handled place side by side so that the interval of 20mm is vertical, cover two lateral bottoms and bottom surface by insulating material such as cloth rubber belt etc., thus preparation box 10.Except that plate 14, steel plate 11-13 all has 8mm in the bottom
Opening 15.
4 liters of cation electric deposition paint compositions are packed in the vinylchlorid container to obtain the first galvanic deposit pond.As shown in Figure 2, will be equipped with in the galvanic deposit container 20 of electrodeposition coating composition 21 as box 10 immersions of article to be coated.In the case, coating composition 21 only is penetrated into the inside of box 10 by opening 15.
After galvanic deposit applied, water washed these steel plates, 170 ℃ with coating curing 25 minutes, in air, cool off then.The coat-thickness that measurement forms on the surfaces A of the nearest steel plate 11 of distance counter electrode 22.Then, measure the coat-thickness that on the surperficial G of distance counter electrode 22 steel plate 14 farthest, forms.Estimate the throwing power of cation electric deposition paint composition with following ratio: the coat-thickness on the coat-thickness/surfaces A on the surperficial G (ratio G/A).Metewand is as follows.
Excellent: G/A〉50% (characterizing) by rank A
Bad: G/A=50% or G/A＜50% (characterizing) by rank B
Consistency with the zinc steel plate
In 5 seconds, voltage is increased to 220V and the alloy galvanized steel plate of handling through chemical conversion is applied 175 seconds, to obtain electrodeposited coating thereon.Water flushing steel plate is then 170 ℃ of bakings 25 minutes.The coating that following observation and evaluation obtain.
Rank A: zero defect on the coating, excellent state
Rank B: have minor defects on the coating, exist unusual
Rank C: have open defect on the coating, defective mode
The outward appearance of horizontal plane
Steel plate is lain in a horizontal plane in the cation electric deposition paint composition, do not stir, carry out galvanic deposit then and toast, to obtain having the plate of cured electrodeposition coating.The outward appearance of this coating can followingly be carried out visual valuation.
Rank A: no problem, outward appearance is good
Rank B: since the pigment small amount of precipitate, the little rough quality
Rank C: pigment precipitation, bad order
Specific conductivity
Be under 25 ℃ the condition in the temperature of fluid composition, measure the specific conductivity of the cation electric deposition paint composition for preparing in each embodiment and the comparative example with electrical conductivity meter (CM-305 is available from DKK-TOA CORPORATION).
Table 1
With regard to the cation electric deposition paint composition of embodiment 1-4, each all contains specific conductivity control agent of the present invention, and the specific conductivity of composition is in the scope that is fit to.Therefore, these compositions provide enough appearance of coat and throwing power.The cation electric deposition paint composition of comparative example 1 has conventional solids content, i.e. 20% weight.The specific conductivity of said composition is in institute of the present invention restricted portion.Yet the solids content of composition is higher, so said composition provides relatively poor horizontal plane outward appearance.The solids content of the cation electric deposition paint composition of comparative example 2 is 7% weight, and it is than the low solid content type.The specific conductivity deficiency of this electrodeposition coating composition, so throwing power is low.With regard to the cation electric deposition paint composition of comparative example 3, wherein will contain in the cation electric deposition paint composition that aminocompound is incorporated into comparative example 2, this amine value that contains aminocompound departs from institute of the present invention restricted portion.The throwing power of said composition and all relatively poor with the consistency of zinc steel plate.
Claims (8)
1. being used for solids content is the specific conductivity control agent of the low solid content type cation electric deposition paint composition of 0.5-9.0% weight, described control agent comprises and contains aminocompound is 900-2 with the conductivity adjustment with described composition, 000 μ S/cm, the described molecular weight that contains aminocompound is 500-20,000, the amine value is 200-500mmol/100g.
2. the specific conductivity control agent of claim 1, wherein, the described aminocompound that contains is that amine-modified epoxy resin or amine are acrylic resin modified.
3. the specific conductivity control agent of claim 2, wherein, described amine-modified epoxy resin is that epoxy group(ing) is by the Resins, epoxy of amine compound modification.
4. the specific conductivity control agent of claim 2, wherein, described amine is acrylic resin modified to be that epoxy group(ing) is by the acrylic resin of amine compound modification.
5. the specific conductivity control agent of claim 3, wherein, described Resins, epoxy is bisphenol type, tert-butyl catechol type, phenol novolac resin type or cresols novolac resin type.
6. solids content is the low solid content type cation electric deposition paint composition of 0.5-9.0% weight, described composition comprises and contains the specific conductivity control agent that contains aminocompound that the amine value is 200-500mmol/100g, and the specific conductivity of described composition is 900-2,000 μ S/cm.
7. be used to regulate the method for the specific conductivity of cation electric deposition paint composition, said method comprising the steps of:
To solids content is to add the specific conductivity control agent in the low solid content type cation electric deposition paint composition of 0.5-9.0% weight; And
In above-mentioned steps, be 900-2 with the conductivity adjustment of cation electric deposition paint composition, 000 μ S/cm;
Wherein, described specific conductivity control agent comprises the aminocompound that contains that the amine value is 200-500mmol/100g.
8. be used for supplying with the method for specific conductivity control agent, said method comprising the steps of to cation electric deposition paint composition:
To solids content is the low solid content type cation electric deposition paint composition supply specific conductivity control agent of 0.5-9.0% weight; And
In above-mentioned steps, be 900-2 with the conductivity adjustment of cation electric deposition paint composition, 000 μ S/cm;
Wherein, described specific conductivity control agent comprises the aminocompound that contains that the amine value is 200-500mmol/100g.
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| Application Number | Priority Date | Filing Date | Title |
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| JP209954/2006 | 2006-08-01 | ||
| JP2006209954A JP2008037889A (en) | 2006-08-01 | 2006-08-01 | Electroconductivity-controlling agent for cation electrodeposition coating, and method for controlling electroconductivity of electrodeposition coating by using the same |
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| CN101522823A true CN101522823A (en) | 2009-09-02 |
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| US (1) | US20090321270A1 (en) |
| JP (1) | JP2008037889A (en) |
| KR (1) | KR20090046905A (en) |
| CN (1) | CN101522823A (en) |
| AU (1) | AU2007279812A1 (en) |
| GB (1) | GB2454123A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108717040A (en) * | 2018-05-31 | 2018-10-30 | 廊坊立邦涂料有限公司 | A kind of device and analogy method in laboratory simulation scene electrophoretic paint throwing power |
| CN111057408A (en) * | 2019-12-05 | 2020-04-24 | 广东科德环保科技股份有限公司 | Cationic modification auxiliary agent of electrophoretic coating and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5325658B2 (en) * | 2009-06-03 | 2013-10-23 | 日本ペイント株式会社 | Method for improving throwing power of cationic electrodeposition paint |
| CN102912400A (en) * | 2012-10-25 | 2013-02-06 | 奥捷五金(江苏)有限公司 | Stainless steel multicolor electrophoretic coating technology |
| JP6406842B2 (en) * | 2014-03-25 | 2018-10-17 | 日本ペイント・オートモーティブコーティングス株式会社 | Electrodeposition coating composition and electrodeposition coating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03188298A (en) * | 1989-12-14 | 1991-08-16 | Kansai Paint Co Ltd | Formation of coating film by electrodeposition |
| JPH06346290A (en) * | 1993-06-11 | 1994-12-20 | Kansai Paint Co Ltd | Coating method |
| CA2128843C (en) * | 1993-07-30 | 1997-10-07 | Susumu Midogohchi | Electrodepositable coating composition |
| JP4035836B2 (en) * | 1995-09-26 | 2008-01-23 | 日本ペイント株式会社 | Matte cationic electrodeposition coating composition |
| CA2231574C (en) * | 1996-07-12 | 2005-08-30 | Kansai Paint Company, Limited | Cationic electrodeposition coating composition |
| JP2002126618A (en) * | 2000-10-26 | 2002-05-08 | Nippon Paint Co Ltd | Method for forming multilayered coating film and multilayered coating film |
| JP2002129099A (en) * | 2000-10-26 | 2002-05-09 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition, and method of forming multilayer film using the same. |
| JP2002126640A (en) * | 2000-10-26 | 2002-05-08 | Nippon Paint Co Ltd | Method for forming coating film, coating film, and waterbase coating material composition |
| JP2003313495A (en) * | 2002-02-21 | 2003-11-06 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
| JP3817674B2 (en) * | 2003-01-28 | 2006-09-06 | 関西ペイント株式会社 | Environment-friendly electrodeposition coating method and coated article |
| JP4959114B2 (en) * | 2004-03-01 | 2012-06-20 | 日本ペイント株式会社 | Electrodeposition coating composition, electrodeposition bath management method and electrodeposition coating system |
-
2006
- 2006-08-01 JP JP2006209954A patent/JP2008037889A/en active Pending
-
2007
- 2007-07-25 TW TW096127081A patent/TW200813177A/en unknown
- 2007-07-27 WO PCT/JP2007/064743 patent/WO2008015968A1/en active Application Filing
- 2007-07-27 US US12/309,809 patent/US20090321270A1/en not_active Abandoned
- 2007-07-27 KR KR1020097004330A patent/KR20090046905A/en not_active Application Discontinuation
- 2007-07-27 CN CNA2007800370543A patent/CN101522823A/en active Pending
- 2007-07-27 AU AU2007279812A patent/AU2007279812A1/en not_active Abandoned
- 2007-07-27 GB GB0901963A patent/GB2454123A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108717040A (en) * | 2018-05-31 | 2018-10-30 | 廊坊立邦涂料有限公司 | A kind of device and analogy method in laboratory simulation scene electrophoretic paint throwing power |
| CN111057408A (en) * | 2019-12-05 | 2020-04-24 | 广东科德环保科技股份有限公司 | Cationic modification auxiliary agent of electrophoretic coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200813177A (en) | 2008-03-16 |
| WO2008015968A1 (en) | 2008-02-07 |
| US20090321270A1 (en) | 2009-12-31 |
| GB2454123A (en) | 2009-04-29 |
| GB0901963D0 (en) | 2009-03-11 |
| JP2008037889A (en) | 2008-02-21 |
| AU2007279812A1 (en) | 2008-02-07 |
| KR20090046905A (en) | 2009-05-11 |
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