CN101583681B - A method for preparing cationic microgel for electrodepositable coating and an electrodepositable coating composition comprising cationic microgel prepared from the same - Google Patents
A method for preparing cationic microgel for electrodepositable coating and an electrodepositable coating composition comprising cationic microgel prepared from the same Download PDFInfo
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- CN101583681B CN101583681B CN2008800022573A CN200880002257A CN101583681B CN 101583681 B CN101583681 B CN 101583681B CN 2008800022573 A CN2008800022573 A CN 2008800022573A CN 200880002257 A CN200880002257 A CN 200880002257A CN 101583681 B CN101583681 B CN 101583681B
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/18—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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The present invention relates to a method for preparing a cationic microgel for electrodepositable coating and an electrodepositable coating composition comprising cationic microgel prepared by the same method. More specifically, the present invention relates to the method for preparing a cationic microgel for electrodepositable coating and the electrodepositable coating composition comprising cationic microgel prepared from by same method, wherein the method for preparing cationic microgel for electrodepositable coating comprises the steps of (1) preparing tertiary amine salt by reacting a tertiary amine having a hydroxy group with diisocyanate followed by neutralizing the resulting mixture with acid; and (2) dispersing the tertiary amine salt resin and polyepoxy resin polymer in a dispersion media, and then reacting the tertiary amine salt resin and polyepoxy resin polymer in the presence of diamine. The cationic microgel for electrodepositable coating exhibits excellent mechanical properties when applied to electrodepositable coating. The electrodepositable coating with the cationic microgel is excellent for edge coating and provides a good smooth coating film by inhibiting the formation of craters by adequately controlling the flowability during the hardening of the coating film.
Description
Technical field
The present invention relates to be used for electrodepositable coating cationic microgel the preparation method and comprise electrodepositable coating composition by the cationic microgel of this method preparation, more particularly, the present invention relates to be used for electrodepositable coating cationic microgel the preparation method and comprise electrodepositable coating composition by the cationic microgel of method preparation of the present invention, the wherein said preparation method who is used for the cationic microgel of electrodepositable coating may further comprise the steps: (1) prepares tertiary ammonium salt by the mixture that tertiary amine with hydroxyl and di-isocyanate reaction are followed with acid and gained; (2) with tertiary ammonium salt resin and poly epoxy resin polymer dispersed in dispersion medium, described tertiary ammonium salt resin and poly epoxy resin polymkeric substance are reacted in the presence of diamines.The electrodepositable coating of being made up of cationic microgel shows excellent mechanical property, the edge is applied excellent and suppresses arc crater by controlling the flowable during the curing of coating fully effectively form filming of good smooth is provided.
Background technology
Usually, cationic electrodepositable applies and is meant coating method, for example ammonium salt or sulfonium salt are incorporated in the resin wherein will to have cationic amine salt or salt, in solution, be moved to negative electrode then at electric field, side by side, hydroxide radical anion reduction that the resin of positively charged is produced by the hydrolysis of water and segregation and coated cathode, i.e. base material.
Under certain temperature, make the resin solidification that is coated on the base material.During this time, the resin of this coating because temperature improves that the viscosity cause reduces at edge thinning or peel off.The attenuation or when peeling off of filming when the edge, this edge owing to be exposed in the external environment is corroded easily.With than in other parts place faster rate development, this causes the base material weather resistance to be confronted with a grave question in edge in corrosion.
The amount of mineral dye had been used for preventing because the edge that the viscosity reduction causes peels off during the molecular weight of raising resin or coating were bathed.Yet aforesaid method is not effectively, and it is not too smooth to cause filming.
U.S. Patent number 5,096,556 and Korean Patent Publication No. 94-9035 a kind of method is disclosed, it comprises: positively charged ion polyepoxide-amine reaction product and polyepoxide linking agent are mixed, and make this mixture crosslinked and form cationic microgel, then the cationic microgel that is obtained is used for cationic electrodepositable and has good edge coated with preparation and cover the electrodepositable coating of keeping the photocatalytic coating film slippery simultaneously.In these patents, be prepared as follows the aqueous dispersion that is suitable for galvanic deposit: positively charged ion polyepoxide-amine reaction product and polyepoxide linking agent are dispersed in reaction medium for example in the water, make the crosslinked cationic microgel dispersion that forms of this mixture by heat, then with dispersions obtained and electrodepositable not gel resin cation (R.C.) combination.
Yet, when forming by the water dispersion that contains the microgel by method for preparing when filming, may have the reduction of dispersibility according to difference with the content of epoxide reactive amine and molecular weight aspect.In addition, if the reaction tempestuously during the preparation of microgel of linking agent and polyepoxide-amine reaction product then will exist because the sedimentary problem of dispersion soln that the high crosslink density of reactant causes.In addition, in the case, because the large size of the discrete particles of dispersion soln, the slickness of coating is deterioration seriously.On the other hand, if linking agent and polyepoxide-amine reaction product react deficiently, then will exist owing to what particulate lower crosslink density in dispersion soln caused to die down and density is reduced the insufficient problem of control in edge's mechanical property.
Summary of the invention
In making great efforts to solve the aforementioned problems in the prior, the purpose of this invention is to provide the preparation method and the electrodepositable coating composition that comprises by the cationic microgel of this method preparation of the cationic microgel that is used for electrodepositable coating, wherein this cationic microgel shows excellent mechanical property when being applied to electrodepositable coating.Electrodepositable coating with cationic microgel applies the edge and is excellent and forms by the arc crater of controlling fully flowable provides good slickness and is suppressed at curing of coating like this for filming during.
According to an aspect of the present invention, be provided for the preparation method of the cationic microgel of electrodepositable coating, this method may further comprise the steps:
(1) by making tertiary amine with hydroxyl and di-isocyanate reaction then with preparing tertiary ammonium salt with the mixture of gained in the acid; With
(2) with described tertiary ammonium salt resin and poly epoxy resin polymer dispersed in dispersion medium, described tertiary ammonium salt resin and poly epoxy resin polymkeric substance are reacted in the presence of diamines.
According to another aspect of the present invention, provide electrodepositable coating composition, it comprises the water dispersion by the cationic microgel of the inventive method preparation.
Detailed Description Of The Invention
Describe the present invention below in detail.
In step (1), by making tertiary amine with hydroxyl and di-isocyanate reaction then with preparing the tertiary ammonium salt resin with the mixture of gained in the acid according to the preparation method of cationic microgel of the present invention.
Described tertiary amine is for example dimethylethanolamine, N-Mono Methyl Ethanol Amine, 2-(ethylamino) ethanol, 2-(propyl group amino) ethanol, 2-(butyl amino) ethanol or their derivative of alkanolamine, and preferably use in the described alkanolamine one or more for example below those of formula 1.
[formula 1]
(wherein, R
1Be alkylidene group with 1-4 carbon atom, R
2And R
3Be alkyl, have the aryl of 5-18 carbon atom, have the ether of 1-10 carbon atom or contain the ester group of 1-10 carbon atom or their derivative) with 1-10 carbon atom
Described vulcabond is aliphatic series or aromatic diisocyanate, and the preferred aliphatic series vulcabond is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), isocyanuric acid ester etc. for example; Aromatic diisocyanate is tolylene diisocyanate (TDI), methane diphenyl vulcabond (MDI), polymkeric substance MDI, hydrogenation MDI, Xylene Diisocyanate (XDI), tetramethyl--Xylene Diisocyanate (TMXDI) etc. for example; Or their mixture, more preferably MDI.
In step (1) according to the preparation method of cationic microgel of the present invention, have the tertiary amine of hydroxyl and the reaction mol ratio of vulcabond and be not particularly limited, and preferred, tertiary amine and vulcabond are by 1: the molar ratio reaction of 0.8-1.2.The side reaction that the water-dispersion stability of non-reacted tertiary amine and difference causes if the reaction mol ratio of vulcabond/1 mole tertiary amine less than 0.8, then may take place.If the reaction mol ratio of vulcabond/1 mole tertiary amine surpasses 1.2, the problem of the water-dispersion stability such as difference, the mechanical property of difference etc. may take place.
Reaction conditions with reaction of the tertiary amine of hydroxyl and vulcabond is not particularly limited.For example, in reaction medium, under 60-90 ℃ temperature, reacted 8-9 hour.According to embodiment of the present invention, the following reaction: methyl iso-butyl ketone (MIBK) and vulcabond are added in the reaction vessel as reaction medium, then dropwise add tertiary amine dimethylethanolamine for example with hydroxyl.Dropwise after the interpolation reaction mixture is heated to 80 ℃ described, and feasible the reaction 4 hours.When reaction is finished, introduce ethylene glycol butyl ether.Neutralize with the reaction mixture cooling and with acetate or analogue then.
The kind and the amount of reaction mixture neutral acid that is used for having the tertiary amine of hydroxyl and vulcabond is unrestricted.For example, can be with sour, for example formic acid, lactic acid, acetate, sulfonic acid etc. are by the amount neutralization reaction mixture that is fit to.
In step (2) according to the preparation method of cationic microgel of the present invention, be prepared as follows cationic microgel: make the tertiary ammonium salt resin that obtains in the above-mentioned steps (1) and poly epoxy resin reaction and preparation contains the poly epoxy resin of quaternary ammonium salt, the poly epoxy resin that makes is dispersed in the dispersion medium, and in the presence of diamines, reacts.
Poly epoxy resin is the polymerisate of polyvalent alcohol and polyepoxide, and preferably one or more aliphatic series or aromatic polyol and epoxy equivalent (weight) weight (EEW) are the polymkeric substance of the bisphenol A-type diglycidylether of 180-700.
Preferably, in the above-mentioned steps (1) usage quantity of tertiary ammonium salt resin in step (2) of preparation be with respect to poly-epoxide resin in 100% equivalent weight of epoxide group be the 15-90% equivalent weight.If described amount is less than 15% equivalent weight, then dispersity may reduce significantly.If above-mentioned amount surpasses 90% equivalent weight, the gelation of then worrying reactant.
As for using what dispersion medium is hard-core, preferably uses deionized water.
Diamines as linking agent preferably can be ethylene diamine, hexamethylene-diamine, five methylene diamine, tetramethylene-diamine, 2-methyl pentamethylene diamine or their mixture.The amount of employed diamines is preferably the 10-99% equivalent weight with respect to residual epoxide group 100% equivalent weight in the main chain, more preferably 30-90% equivalent weight.If above-mentioned amount is less than 10% of equivalent weight, then the improvement of the preservative effect at edge and inhibition arc crater may reduce.If should amount surpass 99% of equivalent weight, the deterioration of then worrying appearance of film.
Making tertiary ammonium salt resin and poly epoxy resin after reaction in the presence of the diamines, is preferred so that improve the storage stability of microgel water dispersion and electrodepositable coating composition with sour neutralization reaction mixture preferably.At this moment, as being used for neutral acid, formic acid, lactic acid, acetate, sulfonic acid etc. are available.The amount that is used for neutral acid is preferably by 0.2 or the mol ratio of the amido of more/1 mole diamines.
The reaction conditions of tertiary ammonium salt resin and poly epoxy resin is not particularly limited.For example, in reaction medium, under 40-60 ℃ temperature, reacted 1-3 hour.According to one embodiment of the invention, be prepared as follows the cationic microgel water dispersion: the reactant of tertiary ammonium salt resin and poly epoxy resin is dispersed in the water, to wherein adding ethylene diamine, and make this mixture, then with acetate this reaction product that neutralizes 45 ℃ of reactions 5 hours down.
According to the present invention, electrodepositable coating composition is provided, it comprises the water dispersion of cationic microgel prepared in accordance with the present invention.
To the amount that is included in the cationic microgel in the electrodepositable coating composition of the present invention without limits.Preferably, the 0.1-10wt% cationic microgel is included in the 100wt% coating composition.
Cationic microgel of the present invention is included in according in the electrodepositable coating composition of the present invention.This microgel is owing to the quaternary ammonium salt in the main chain has cationic characteristic, and this causes the improved dispersity of microgel dispersion soln.In addition, because can easily control pH by using neutralizing acid, so the advantage that exists is can use cationic microgel and the stability degradation that can not make electrodeposition bath solution with the crosslinked back of diamines.In addition, cationic microgel prevents that by the flowable of control during the curing of coating arc crater from producing.
Explain the present invention in more detail by following examples, but the invention is not restricted to these embodiment.
Preparation embodiment 1: the preparation of poly epoxy resin
The polymkeric substance for preparing polyepoxide and polyvalent alcohol by the mixture of ingredients shown in the following table 1.
The preparation component of table 1 poly epoxy resin
| Composition | Weight part |
| YD-128 1 | 680.9 |
| Tone0201 2 | 534.0 |
| The ethoxylation dihydroxyphenyl propane | 199.3 |
| Dimethylbenzene | 68.8 |
| Methyl proxitol (first) | 74.4 |
| BDMA (benzyl dimethyl amine) | 3.5 |
| R9787 3 | 118.89 |
| Ketoimine (ketimine) | 102.18 |
| NMEA (N-Mono Methyl Ethanol Amine) | 42.51 |
| Methyl proxitol (second) | 1012.2 |
1. Resins, epoxy (Kukdo Chemical Co.)
2. polyvalent alcohol (Dow Chemical Co.)
3. amine intermediate (KCC Co.)
Resins, epoxy (YD-128), polyvalent alcohol (Tone0201), ethoxylation dihydroxyphenyl propane and dimethylbenzene are added reaction vessel, be heated to 120 ℃, then under vacuum, reclaim dimethylbenzene.After adding methyl proxitol (first) and BDMA (benzyl dimethyl amine), reaction mixture is heated to 145 ℃.Note giving birth to heat, reaction mixture was remained on this temperature following 3.5 hours, be cooled to 90-100 ℃ then.Then, add amine intermediate (R9787), ketoimine (by two ketoimines (diketimine) derivative of methyl iso-butyl ketone (MIBK) and diethylenetriamine preparation) and N-Mono Methyl Ethanol Amine.With the temperature regulation to 100 of reaction mixture ℃ and remained on this temperature following 2.5 hours.Add methyl proxitol (second) with diluted reaction mixture.
Preparation embodiment 2: the preparation of aromatic polyisocyanate
By the preparation of the mixture of ingredients shown in the following table 2 polyfunctional alcohol and the end capped aromatic polyisocyanate of monofunctional alcohol.
The preparation component of table 2 aromatic polyisocyanate
| Composition | Weight part |
| MDI (methane diphenyl vulcabond) | 1325.6 |
| MIBK (methyl iso-butyl ketone (MIBK)) (first) | 647 |
| DBTDL (dibutyl tin laurate) | 0.2 |
| Diethylene glycol monobutyl ether | 1223.7 |
| TMP (TriMethylolPropane(TMP)) | 134.5 |
| MIBK (second) | 22.8 |
MDI, MIBK (first) and DBTDL are added reaction vessel, and be heated to 50 ℃.Notice that temperature is no more than 50 ℃, in 1.5 hours, add diethylene glycol monobutyl ether lentamente.Keep this reaction mixture 50 ℃ following 30 minutes, reach 9-10% up to NCO%.By a part interpolation TMP, note giving birth to heat.Reaction mixture is heated to 80 ℃ then.Keep reaction mixture 80 ℃ following 1 hour, and when NCO% reaches 0%, interpolation MIBK (second) is to dilute this mixture.
Preparation embodiment 3: the preparation of tertiary ammonium salt resin
Prepare the tertiary ammonium salt resin by the mixture of ingredients shown in the following table 3.
The preparation component of table 3 tertiary ammonium salt resin
| Composition | Weight part |
| M80 (polymkeric substance methane diphenyl vulcabond) | 319.3 |
| Dimethylethanolamine | 227.6 |
| Methyl iso-butyl ketone (MIBK) | 130 |
| Ethylene glycol butyl ether | 70 |
| Acetate | 153.3 |
M80 (polymkeric substance MDI) and methyl iso-butyl ketone (MIBK) are added reaction vessel, dropwise add dimethylethanolamine then lentamente in this reaction vessel.dropwise add finish after, reaction mixture is heated to 80 ℃ and kept 4 hours.After reaction is finished, by adding ethylene glycol butyl ether reaction mixture is cooled off, neutralize with acetate then.
Preparation embodiment 4-6: the preparation of microgel water dispersion
The microgel water dispersion for preparing embodiment 4-6 respectively by the preparation of the mixture of ingredients shown in the following table 4-6.
The preparation component of the microgel water dispersion of table 4 preparation embodiment 4
| Composition | Weight part |
| ?YD-128 | 119.20 |
| Dihydroxyphenyl propane | 33.60 |
| The ethoxylation dihydroxyphenyl propane | 43.80 |
| Dimethylbenzene | 12.00 |
| Methyl proxitol (first) | 6.00 |
| BDMA (benzyl dimethyl amine) | 0.53 |
| Methyl proxitol (second) | 35.80 |
| Deionized water (first) | 18.00 |
| The tertiary ammonium salt of preparation embodiment 3 | 29.70 |
| Deionized water (second) | 708.00 |
| Ethylene diamine | 0.60 |
| Acetate | 3.8 |
The preparation component of the microgel water dispersion of table 5 preparation embodiment 5
| Composition | Weight part |
| ?YD-128 | 119.20 |
| Dihydroxyphenyl propane | 33.60 |
| The ethoxylation dihydroxyphenyl propane | 43.80 |
| Dimethylbenzene | 12.00 |
| Methyl proxitol (first) | 6.00 |
| BDMA (benzyl dimethyl amine) | 0.53 |
| Methyl proxitol (second) | 35.80 |
| Deionized water (first) | 18.00 |
| The tertiary ammonium salt of preparation embodiment 3 | 30.00 |
| Deionized water (second) | 707.00 |
| Ethylene diamine | 1.20 |
| Acetate | 7.6 |
The preparation component of the microgel water dispersion of table 6 preparation embodiment 6
| Composition | Weight part |
| ?YD-128 | 119.20 |
| Dihydroxyphenyl propane | 33.60 |
| The ethoxylation dihydroxyphenyl propane | 43.80 |
| Dimethylbenzene | 12.00 |
| Methyl proxitol (first) | 6.00 |
| BDMA (benzyl dimethyl amine) | 0.53 |
| Methyl proxitol (second) | 35.80 |
| Deionized water (first) | 18.00 |
| The tertiary ammonium salt of preparation embodiment 3 | 30.00 |
| Deionized water (second) | 707.00 |
| Ethylene diamine | 1.71 |
| Acetate | 10.8 |
YD-128, dihydroxyphenyl propane, ethoxylation dihydroxyphenyl propane and dimethylbenzene are added reaction vessel and is heated to 120 ℃.Under vacuum, reclaim dimethylbenzene.After adding methyl proxitol (first) and BDMA, reaction mixture is heated to 145 ℃.Note giving birth to heat, reaction mixture was remained on this temperature following 3.5 hours, be cooled to 90-100 ℃ then.Add methyl proxitol (second) and deionized water (first) then and with the temperature regulation to 50 of reaction mixture ℃.Dropwise add the tertiary ammonium salt resin of preparation embodiment 3.Keep reaction mixture following 1 hour at 50 ℃.By dropwise adding deionized water (second) reaction mixture is dispersed in the water.Add ethylene diamine, and keep this mixture following 5 hours at 45 ℃.After reaction is finished, neutralize this reaction mixture and prepare microgel water-dispersion with acetate.
Preparation embodiment 7: the preparation of pigment paste
Prepare pigment paste by the mixture of ingredients shown in the following table 7.
The preparation component of table 7 pigment paste
| Composition | Weight part |
| Be used for pigment dispersion resin (KCC Co., LS2284) | 121.6 |
| Carbon black | 3 |
| Titanium dioxide | 413.7 |
| Dibutyltin oxide is stuck with paste | 205.7 |
| Deionized water | 37.7 |
To be used for the resin, carbon black, titanium dioxide of pigment dispersion and dibutyltin oxide sticks with paste and joins container and by mixing.Deionized water is added in this mixture, stir this mixture then.By using dispersing apparatus to disperse this mixture to become the 10-12 μ m that is used for the pigment paste preparation up to the size of discrete particles.
Preparation embodiment 8-12: be used for the preparation of the water dispersed resin of electrodepositable coating
The water dispersed resin that is used for electrodepositable coating for preparing embodiment 8-12 respectively by the preparation of the mixture of ingredients shown in the following table 8-12.
The preparation component of the water dispersed resin that is used for electrodepositable coating of table 8 preparation embodiment 8
| Composition | Weight part |
| The poly epoxy resin of preparation embodiment 1 | 363.9 |
| The polyisocyanates of preparation embodiment 2 | 169 |
| Tensio-active agent (Surfynol 104, Air Products Co.) | 13.4 |
| Formic acid | 5.89 |
| Deionized water | 609 |
| The microgel water dispersion of preparation embodiment 4 | 23.2 |
The preparation component of the water dispersed resin that is used for electrodepositable coating of table 9 preparation embodiment 9
| Composition | Weight part |
| The poly epoxy resin of preparation embodiment 1 | 363.9 |
| The polyisocyanates of preparation embodiment 2 | 169 |
| Tensio-active agent (Surfynol 104, Air Products Co.) | 13.4 |
| Formic acid | 5.89 |
| Deionized water | 609 |
| The microgel water dispersion of preparation embodiment 4 | 46.4 |
The preparation component of the water dispersed resin that is used for electrodepositable coating of table 10 preparation embodiment 10
| Composition | Weight part |
| The poly epoxy resin of preparation embodiment 1 | 363.9 |
| The polyisocyanates of preparation embodiment 2 | 169 |
| Tensio-active agent (Surfynol 104, Air Products Co.) | 13.4 |
| Formic acid | 5.89 |
| Deionized water | 609 |
| The microgel water dispersion of preparation embodiment 5 | 23.2 |
The preparation component of the water dispersed resin that is used for electrodepositable coating of table 11 preparation embodiment 11
| Composition | Weight part |
| The poly epoxy resin of preparation embodiment 1 | 363.9 |
| The polyisocyanates of preparation embodiment 2 | 169 |
| Tensio-active agent (Surfynol 104, Air Products Co.) | 13.4 |
| Formic acid | 5.89 |
| Deionized water | 609 |
| The microgel water dispersion of preparation embodiment 5 | 46.4 |
The preparation component of the water dispersed resin that is used for electrodepositable coating of table 12 preparation embodiment 12
| Composition | Weight part |
| The poly epoxy resin of preparation embodiment 1 | 363.9 |
| The polyisocyanates of preparation embodiment 2 | 169 |
| Tensio-active agent (Surfynol 104, Air Products Co.) | 13.4 |
| Formic acid | 5.89 |
| Deionized water | 609 |
| The microgel water dispersion | - |
The poly epoxy resin of preparation embodiment 1 and the blocked polyisocyanates of preparation embodiment 2 are joined container and be heated to 90 ℃.Keeping mixture to be in this temperature after 30 minutes, sealed vessel, and under vacuum, reclaim solvent in the mixture.Add tensio-active agent and formic acid, and in 2 hours, dropwise add deionized water.At last, add each microgel water dispersion for preparing embodiment (except that preparation embodiment 12) is used for electrodepositable coating with preparation every kind of water dispersed resin.
Embodiment 1-4 and comparative example
Composition below mixing respectively prepares cationic electrodeposition solution.
Table 13 embodiment 1-4 and comparative example's preparation component
Water dispersed resin, 1503 parts by weight of deionized water and the 3 weight part acetate of each preparation embodiment of 1197 weight parts are added at room temperature the bath, and stir.Stirring this bath solution simultaneously, adding 297 weight parts and prepare the pigment paste of embodiment 7 to prepare every kind of cationic electrodepositable bath solution.
The pH value of the bath solution of preparation is 5.8-6.2.To in this electrodeposition bath, under 28 ℃, apply 2 minutes with the pretreated steel plate of zinc phosphate in 240 volts (voltage) following electropaining.In baking oven 170 ℃ of following cured coating films 25 minutes.
Experimental example
Table 14 test-results
1.Erichsen trier: the spheroid with radius 1.5cm is suppressed the sample that applies.Peel off when filming or when coming off, measure depth of groove.(unit: mm)
2. ◎: very good, zero: good, *: poor
3. measure levelling by the Surtronic 3+ that uses Taylor-Hobson Co..
4. the pretreated coated sample of zinc phosphate 960 hours are used in test in the salt-fog test machine, use the zona pellucida release coated film then.The length that measurement is peeled off.
5. electropaining is covered with the sample of circumference and quadrangle perforation, tests 240 hours in the salt-fog test machine then.After test, use the zona pellucida peel sample, the state of release surface to perforation compares then.
Industrial applicability
According to the present invention, when being applied to electrodepositable coating, obtain the cationic microgel that is used for electrodepositable coating with very good mechanical properties.The electrodepositable coating composition that comprises this cationic microgel applies excellent to the edge and suppresses arc crater by controlling the flowable during the curing of coating fully effectively and forms filming of good smooth is provided.
Claims (8)
1. be used for the preparation method of the cationic microgel of electrodepositable coating, may further comprise the steps:
(1) by making tertiary amine with hydroxyl and di-isocyanate reaction then with preparing the tertiary ammonium salt resin with the mixture of gained in the acid; With
(2) make middle tertiary ammonium salt resin that obtains of above-mentioned steps (1) and poly epoxy resin reaction and preparation contain the poly epoxy resin of quaternary ammonium salt, the poly epoxy resin that contains quaternary ammonium salt for preparing be dispersed in the dispersion medium, and in the presence of diamines, react,
Wherein said tertiary amine with hydroxyl is the alkanolamine of following formula 1:
Wherein, R
1Be alkylidene group with 1-4 carbon atom, R
2And R
3Be alkyl, aryl, have the ether of 1-10 carbon atom or have the ester group of 1-10 carbon atom with 5-18 carbon atom with 1-10 carbon atom.
2. according to the process of claim 1 wherein that described vulcabond is selected from isophorone diisocyanate, hexamethylene diisocyanate, isocyanuric acid ester, tolylene diisocyanate, methane diphenyl vulcabond, polymkeric substance methane diphenyl vulcabond, hydrogenation methane diphenyl vulcabond, Xylene Diisocyanate, tetramethylxylene diisocyanate and their mixture.
3. according to the process of claim 1 wherein that described poly epoxy resin is the polymerisate of polyvalent alcohol and polyepoxide.
4. according to the process of claim 1 wherein the tertiary ammonium salt resin that uses preparation in the step (1) by the amount that with respect to epoxide group in the poly epoxy resin of 100% equivalent weight is the 15-90% equivalent weight.
5. according to the process of claim 1 wherein that described diamines is selected from ethylene diamine, hexamethylene-diamine, five methylene diamine, tetramethylene-diamine, 2-methyl pentamethylene diamine and their mixture.
6. be that the amount of 10-99% equivalent weight is used described diamines according to the process of claim 1 wherein by residual epoxide group in the main chain with respect to 100% equivalent weight.
7. according to the process of claim 1 wherein with in the acid and the reaction mixture that in step (2), obtains obtaining.
8. electrodepositable coating composition, it comprises by the water dispersion according to the cationic microgel of each method preparation among the claim 1-7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070007109 | 2007-01-23 | ||
| KR10-2007-0007109 | 2007-01-23 | ||
| KR1020070007109A KR100929040B1 (en) | 2007-01-23 | 2007-01-23 | Electrodeposit coating composition comprising a method for producing a cationic microgel for electrodeposition paint and a microgel manufactured therefrom |
| PCT/KR2008/000354 WO2008091082A1 (en) | 2007-01-23 | 2008-01-21 | A method for preparing cationic microgel for electrodepositable coating and an electrodepositable coating composition comprising cationic microgel prepared from the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101583681A CN101583681A (en) | 2009-11-18 |
| CN101583681B true CN101583681B (en) | 2011-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800022573A Active CN101583681B (en) | 2007-01-23 | 2008-01-21 | A method for preparing cationic microgel for electrodepositable coating and an electrodepositable coating composition comprising cationic microgel prepared from the same |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR100929040B1 (en) |
| CN (1) | CN101583681B (en) |
| RU (1) | RU2428446C2 (en) |
| TR (2) | TR200905554T1 (en) |
| WO (1) | WO2008091082A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101940377B1 (en) * | 2016-08-18 | 2019-01-18 | 주식회사 케이씨씨 | Electrodeposition Paint Composition |
| CN106905664B (en) * | 2017-04-10 | 2020-03-17 | 立邦涂料（中国）有限公司 | Functional polyamine modified microgel, preparation method and application thereof |
| KR102042239B1 (en) * | 2017-08-08 | 2019-11-08 | 주식회사 케이씨씨 | Cationic urethane curing agent and electro-deposition paint composition comprising the same |
| CN113710754B (en) * | 2019-04-25 | 2022-08-02 | 关西涂料株式会社 | Cationic electrodeposition coating composition |
| CN111393683B (en) * | 2020-04-20 | 2023-05-23 | 广东科德环保科技股份有限公司 | Modified cationic microgel and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171764A (en) * | 1990-02-16 | 1992-12-15 | Kansai Paint Co., Ltd. | Resin composition for cationically electrodepositable paint containing finely divided gelled polymer based on radically polymerizable hydrolyzable silane monomers |
| US5288770A (en) * | 1990-01-20 | 1994-02-22 | Kansai Paint Co., Ltd. | Resin composition for cationically electrodepositable paint comprising alicyclic epoxy resins and emulsion polymerized, finely divided gelled polymers |
| CN1167497A (en) * | 1994-11-04 | 1997-12-10 | Ppg工业公司 | Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition |
| CN1551907A (en) * | 2001-02-05 | 2004-12-01 | Ppg工业俄亥俄公司 | Photodegradation-resistant electrodepositable coating compositions and processes related thereto |
| US6998040B2 (en) * | 2001-01-24 | 2006-02-14 | University Of South Florida | Sol-gel open tubular ODS columns with charged inner surface for capillary electrochromatography |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407976A (en) | 1993-10-27 | 1995-04-18 | E. I. Du Pont De Nemours And Company | Isocyanate crosslinked microgel for cathodic electrocoating compositions |
| KR100974766B1 (en) * | 2003-02-14 | 2010-08-06 | 주식회사 케이씨씨 | Cationic microgel, preparing method thereof, and electro-deposition paint composition containing the same |
| KR20050069729A (en) * | 2003-12-31 | 2005-07-05 | 주식회사 케이씨씨 | Cationic microgel for electro-deposition paint, preparing method thereof, and composition for electro-deposition paint containing the same |
-
2007
- 2007-01-23 KR KR1020070007109A patent/KR100929040B1/en active IP Right Grant
-
2008
- 2008-01-21 TR TR2009/05554T patent/TR200905554T1/en unknown
- 2008-01-21 WO PCT/KR2008/000354 patent/WO2008091082A1/en active Application Filing
- 2008-01-21 TR TR2011/04839T patent/TR201104839T1/en unknown
- 2008-01-21 RU RU2009131731/05A patent/RU2428446C2/en active
- 2008-01-21 CN CN2008800022573A patent/CN101583681B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288770A (en) * | 1990-01-20 | 1994-02-22 | Kansai Paint Co., Ltd. | Resin composition for cationically electrodepositable paint comprising alicyclic epoxy resins and emulsion polymerized, finely divided gelled polymers |
| US5171764A (en) * | 1990-02-16 | 1992-12-15 | Kansai Paint Co., Ltd. | Resin composition for cationically electrodepositable paint containing finely divided gelled polymer based on radically polymerizable hydrolyzable silane monomers |
| CN1167497A (en) * | 1994-11-04 | 1997-12-10 | Ppg工业公司 | Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition |
| US6998040B2 (en) * | 2001-01-24 | 2006-02-14 | University Of South Florida | Sol-gel open tubular ODS columns with charged inner surface for capillary electrochromatography |
| CN1551907A (en) * | 2001-02-05 | 2004-12-01 | Ppg工业俄亥俄公司 | Photodegradation-resistant electrodepositable coating compositions and processes related thereto |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008091082A1 (en) | 2008-07-31 |
| KR20080069419A (en) | 2008-07-28 |
| TR201104839T1 (en) | 2012-09-21 |
| KR100929040B1 (en) | 2009-11-26 |
| RU2428446C2 (en) | 2011-09-10 |
| CN101583681A (en) | 2009-11-18 |
| TR200905554T1 (en) | 2010-05-21 |
| RU2009131731A (en) | 2011-03-10 |
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