CN101583678A - A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same - Google Patents
A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same Download PDFInfo
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- CN101583678A CN101583678A CNA2008800022747A CN200880002274A CN101583678A CN 101583678 A CN101583678 A CN 101583678A CN A2008800022747 A CNA2008800022747 A CN A2008800022747A CN 200880002274 A CN200880002274 A CN 200880002274A CN 101583678 A CN101583678 A CN 101583678A
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G17/00—Connecting or other auxiliary members for forms, falsework structures, or shutterings
- E04G17/06—Tying means; Spacers ; Devices for extracting or inserting wall ties
- E04G17/065—Tying means, the tensional elements of which are threaded to enable their fastening or tensioning
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/40—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 characterised by the curing agents used
- C08G59/50—Amines
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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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G17/00—Connecting or other auxiliary members for forms, falsework structures, or shutterings
- E04G17/04—Connecting or fastening means for metallic forming or stiffening elements, e.g. for connecting metallic elements to non-metallic elements
- E04G17/047—Connecting or fastening means for metallic forming or stiffening elements, e.g. for connecting metallic elements to non-metallic elements simultaneously tying two facing forms
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Abstract
The present invention relates to a cationic pigment grinding resin and an electrodepositable coating composition comprising the same. More specifically, the present invention relates to a cationic pigment grinding resin, as a polyepoxide-amine resin, comprising (i) an acid-neutralizable amine group derived from monoepoxide- amine compound resulting from the reaction of monoepoxide and amine having 3 and more active hydrogen, and (ii) a quaternary ammonium salt group, in the middle of its chain, and an electrodepositable coating composition comprising the same.
Description
Technical field
The present invention relates to be used for the resin cation (R.C.) (being also referred to as " cationic pigment grind resin ") of pigment dispersion and comprise its electrodepositable paint (or coating) composition.More particularly, the present invention relates to cationic pigment grind resin as polyepoxide-polyimide resin, its comprise (i) but derived from monoepoxide with have the acid neutral amido of monoepoxide-amine compound that the reaction of the amine of 3 and more a plurality of active hydrogens produces and a (ii) quaternary ammonium salt base in the middle part of its chain; With the electrodepositable coating composition that comprises this pigment grind resin.
Background technology
Galvanic deposit applies and to be meant non-conductive coating film technique, and wherein electropolymer is moved to the electrode of opposite charges in direct galvanic action, and changes the polymkeric substance of emanating by the pH that is caused by electrolysis.Galvanic deposit applies the superiority that is better than non-electrophoresis method and is that electrodeposited coating shows bigger binding property and has significant preservative effect, and the environmental pollution degree of electrodeposition process is low.
The anionic electrodeposition deposition method of anodic object is served as in early stage galvanic deposit from coating.Yet the automobile of producing stands its floating coat and the adherent cationic electrodeposition of negative electrode more than 90% recently.When applying electromotive force, the surface of coating particles has positively charged ion so that the lacquer particle moves on to negative electrode by electrophoresis.Recently, most of resins of electrodepositable coating use and use in the acid and the system of polyepoxide-amine reaction product.
Be used for the pigment grind resin that the process of preparation electrodepositable paint is introduced pigment should make pigment stable so that it does not precipitate, and should be charged thus it will be in electric field electrophoresis.The resin that is mainly used in pigment grind is polyepoxide and have the adducts of the amine of the structure that is similar to the galvanic deposit base resin preferably, and preferred this resin contains hydrophobic group and makes pigment stabilization in aqueous medium so that be hydrophobic surface of pigments by encirclement in some part.
The representative instance that is used for the pigment grind resin of cationic electrodeposition is a U.S. Patent number 4,007,154 and 4,186, and the resin that contains quaternary ammonium salt base described in 124.Yet though disclosed resin has good pigment wetting properties and thermostability owing to the introducing of quaternary ammonium salt in the above-mentioned document, this resin has the shortcoming that such as the lacquering outward appearance serious coarse and film thickens difficulty.
In order to remedy these defectives, U.S. Patent number 4,230,552 disclose pigment grind resin, and this pigment grind resin has with the larger molecular weight alcohol quaternary ammonium salt of the end capped vulcabond-amine compound of aliphatic alkyl phenol for example.Yet this resin does not still solve the outward appearance problem of rough of lacquering.
Simultaneously, from phase late 1980s, disclosing the resin that preparation is used to grind, (for example U.S. Patent number 4,715, the disclosed resin that contains sulfonium salt in 898) technology wherein by make some epoxy group(ing) ends toughness reinforcing with end-blockings such as nonylphenols, neutralizes with thiodiethanol and acid then.By using above-mentioned technology, can obtain to have break voltage and can thicken the galvanic deposit system of film of height.Yet, it is reported, with containing under the lacquer situation of sulfonium salt resins, when lead in resin and the pigment or carbon black interaction, heat passage stability reduction.In addition, when the resin that contains sulfonium salt was generally used for industrial cationic electrodeposition and bathes, lacquer became to be loaded into the shearing force instability on it through recycle pump the time.The storage stability that it is also known that lead-containing compounds or sooty lacquer is poor especially.In order to remedy these defectives, attempted the mixture of sulfonium salt resin and quaternary ammonium resin, but this mixture also produces roughened appearance.
In the nineties in 20th century, in order to remedy above-mentioned defective, U.S. Patent number 5,130,004 discloses the preparation method of the lacquer that heat passage stability is improved in leaded paint, this method is following carries out: by neutral sulfide-amine mixt being added to side by side producing sulfonium salt-quaternary ammonium mixture in the toughness reinforcing Resins, epoxy of nonylphenol, but it has low hydrophobic problem.
Simultaneously, disclose contain primary, the resin of the second month in a season and tertiary ammonium salt is as the grinding resin.Though they make the galvanic deposit lacquering level and smooth, this resin has low stability and gratifying pigment grind is not provided after the medium-term and long-term storage of electrodeposition bath solution.It is believed that because above-mentioned amine salt is the salt that contains proton, so in pigment grind and memory period generation proton-exchange reaction, so that storage stability is prolonging storage back step-down.
Yet the hydrophilic group that is fit to is incorporated into can improve pigment grind and the resin stability at memory period in these amine salt.Specifically, because hydrophilic group provides the stefic stabilization effect for grinding with resin, so can improve pigment grind and storage stability.Therefore, problem becomes during the preparation of pigment grind resin which kind of hydrophilic group to be introduced to grind and uses resin.For example, austrian patent numbers 365,214 and 380,264 discloses the epoxy resin that is used for pigment grind of Han oxazolidinyl.Oxazolidinyl in this resin does not still solve the problem of storage difference in bathing solution, but is using owing to its good pigment grind always.
The above-mentioned needs that show produce good appearance, have good pigment grind and even after prolonging storage stabilized resins still.
Summary of the invention
In order to solve the aforementioned problems in the prior, the present invention seeks to prepare the pH and the adjustable cationic pigment grind resin of wetting ability of various pigment in the electrodepositable coating composition, this resin produces good surface appearance, has good pigment grind and even still stable and comprise the electrodepositable coating composition of this resin cation (R.C.) after prolonging storage.
According to an aspect of the present invention, cationic pigment grind resin as polyepoxide-polyimide resin is provided, its comprise (i) but acid neutral amido, it is derived from monoepoxide with have monoepoxide-amine compound that the reaction of the amine of 3 or more a plurality of active hydrogens produces and (ii) at the quaternary ammonium salt base at its chain middle part.
According to another aspect of the present invention, provide the pigment paste that contains cationic pigment grind resin of the present invention.
According to a further aspect of the invention, provide the electrodepositable coating composition that contains cationic pigment grind resin of the present invention.
Detailed Description Of The Invention
Describe the present invention below in detail.
Cationic pigment grind resin of the present invention is polyepoxide-polyimide resin basically.Polyepoxide in described polyepoxide-polyimide resin has 180-2 usually, and 000 epoxy equivalent (weight) weight also preferably has 2 or more a plurality of 1, the 2-epoxide group.The example of preferred poly-epoxide resin is for example polyglycidyl ether of bisphenol-A of the polyglycidyl ether of polyphenol or aromatic polyol.By aromatic polyol and epihalohydrin for example Epicholorohydrin or dichlorohydrin, or the ether prepared in reaction poly-epoxide resin of two epihalohydrins in the presence of alkali.Other example of above-mentioned poly-epoxide resin is the modified poly-epoxy resin derived from novolac resin, polyphenol resin etc.Simultaneously, the polyglycidyl ether that the molecular weight of the polyglycidyl ether of poly-hydroxy material can be by making aromatic diol with can improve with the polyol reaction of epoxide group reaction.The examples of polyhydric alcohols that is applicable to above-mentioned reaction is ethylene glycol, Diethylene Glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol and bisphenol-A etc.
Can be used for monoepoxide of the present invention for example is, below the monoepoxide of formula 1.
[formula 1]
In above-mentioned formula 1, R
1Be hydrogen or methyl; R
2Be hydrogen, the alkyl that comprises cycloalkyl (preferred C
1-C
18Alkyl), aryl (preferred C
6-C
18Aryl) or not hinder the alkyl or aryl of the replacement of the reaction between monoepoxide and the amine.The example of alkyl or aryl of replacement that does not hinder the reaction between monoepoxide and the amine is as follows:
--CH
2OR
3.
[R wherein
3Be alkyl (the preferred C that comprises cycloalkyl
1-C
18Alkyl) or C
6-C
18Aryl]
The suitable example of monoepoxide of the present invention is the Racemic glycidol yl acetate, and it is glycidyl esters, glycidyl butyric ester, glycidyl cetylate, the glycidyl laurate of single acid and can be used as CARDURA E
TMThe glycidyl esters that is purchased; Butylglycidyl ether, it is the glycidyl esters, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether of alcohol or phenol and to (tertiary butyl) phenyl glycidyl ether etc.
For with the amine with 3 or more a plurality of active hydrogens of above-mentioned monoepoxide reaction, can use diamines, triamine or tetramine compound alone or in combination.More preferably use diamines or triamine.The example of preferred amine is ethylene diamine, hexamethylene-diamine, four (pentamethylene) diamines, five methylene diamine, 2-methyl pentamethylene diamine, polyoxy alkylidene diamines, diethylenetriamine, amino ethyl ethanolamine, Triethylenetetramine (TETA) or their mixture.
By making in monoepoxide and the amine prepared in reaction monoepoxide-amine compound with 3 or more a plurality of active hydrogens, the combination ratio by the conditioned reaction thing is retained in monoepoxide-amine compound 2 or more a plurality of (preferred 2) active hydrogen.When the monoepoxide-amine compound that contains 2 or more a plurality of active hydrogens by use prepares pigment grind resin, during preparation process, form polyepoxide-amine with poly-epoxide resin with the amido that is positioned at the chain middle part by chain extending reaction, can regulate the molecular weight of pigment grind resin thus, and wetting ability is enhanced.In addition, be positioned at monoepoxide on the side chain and not only give resin with hydrophobicity but also give pigment paste, produce excellent pigment-dispersing and stability with steric hindrance.In addition, the monoepoxide that is positioned on the side chain is given pigment grind resin with flexible, thereby produces the lacquering of smooth surface.
In addition, can strengthen wetting ability with amido by in the preparation of pigment paste, adding in the additional acid also.The advantage that also has is the pH regulator of pigment paste can be arrived the level that is fit to.
Be incorporated into the following formation of quaternary ammonium salt base at the chain middle part of pigment grind resin of the present invention:, be incorporated into the middle part of chain then by chain extending reaction even the epoxide group of above-mentioned polyepoxide-amine and tertiary ammonium salt react.
Above-mentioned tertiary ammonium salt is by the hydroxyl of dialkyl group alkanolamine and the amino-formate bond of vulcabond, and obtain with the acid neutralization.Dialkyl group alkanolamine be can use, dimethylethanolamine, dimethyl propanol amine, diethylethanolamine, diethylpropanolamine and their mixture are preferably selected from by following formula 2 expressions.
[formula 2]
R wherein
1Be aliphatic hydrocrbon with 2-4 carbon atom, R
2It is aliphatic hydrocrbon with 2-6 carbon atom.
The vulcabond that forms amino-formate bond with the hydroxyl of above-mentioned dialkyl group alkanolamine can be methylenediphenyl diisocyanates, tolylene diisocyanate or isophorone diisocyanate, more preferably methylenediphenyl diisocyanates.
To the type of the acid that is used to form quaternary ammonium salt without limits.Organic carboxyl acid is preferred, and one or more carboxylic acids that are selected from lactic acid, acetate, propionic acid, butyric acid, neopentanoic acid, acid dimethyl, formic acid and oxyacetic acid are preferred.
Preferred above-mentioned dialkyl group alkanolamine and vulcabond are pressed 1: 2 molar ratio reaction respectively.Make the tertiary ammonium salt that the reaction by dialkyl group alkanolamine and vulcabond forms and the epoxide reaction of described polyepoxide-amine form quaternary ammonium salt, and make the molecular weight of chain extension with this reaction simultaneously with the raising chain.As a result, quaternary ammonium salt is positioned at the middle part of pigment grind resin chain.
Be not limited to specified proportion with sour neutral amido (i) and the quaternary ammonium salt base ratio (ii) that in resin of the present invention, contains.Yet, consider that the molecular weight of polymkeric substance disperses or hydrophilicity, every 1g pigment grind resin, the 0.25-1.4 milliequivalent (ii) is suitable with sour neutral amido (i) and quaternary ammonium salt base.When with sour neutral amido (i) and quaternary ammonium salt base content (ii) during less than the content of advising above, the wetting properties variation of pigment.When their content during greater than the content of advising above, owing to form extremely water miscible carrier, the wetting properties variation of pigment.For the stability of the slickness of gained lacquering and pigment paste and electrodepositable coating composition, every 1g pigment grind resin, the 0.01-1.3 milliequivalent (ii) is suitable with sour neutral amido (i) and the above-mentioned quaternary ammonium salt base of 0.01-1.2 milliequivalent.
Aforesaidly can and be positioned at the quaternary ammonium salt base unique structural characteristics (ii) at chain middle part because have with sour neutral amido (i), pigment grind resin of the present invention has excellent dispersiveness, simultaneously, make that the electrodepositable coating composition and the pigment paste that contain this pigment grind resin are highly stable.
By being ground, various pigment component and pigment grind resin of the present invention prepare pigment paste of the present invention.Conventional electrodepositable paint causes that usually pigment shifts instable problem.Pigment grind resin of the present invention helps to make to shift to be stablized.
Use the pigment component of preparation pigment paste can comprise titanium dioxide, weisspiessglanz, zinc oxide, barium carbonate, lime carbonate, pure aluminium silicate, silicon oxide, magnesiumcarbonate and/or Magnesium Silicate q-agent.Can also use tinting pigment, for example cadmium yellow, cadmium red, carbon black, phthalocyanine blue, chrome yellow, toluidine red and hydrous iron oxide.Especially, carbon black shows poor thermostability owing to its little particle size and strong hydrophobicity usually in when storage.Pigment grind resin of the present invention can help to make carbon black stable under the heat storage.Pigment paste can also comprise optional component for example wetting Agent for Printing Inks, tensio-active agent and defoamer except above-mentioned pigment component and pigment grind resin component.
Usually grind up to pigment and be reduced to desired size, preferably by using ball mill, sand mill and continuous mill to grind up to pigment wetting or dispersion by grinding carrier.Usually, the particle size of pigment is 10 microns or littler based on Hai Geman rule (Hegman gauge) after grinding, preferred 6-8, more preferably 7-8.
Usually, in the aqueous liquid dispersion of carrier, carry out the grinding of pigment component.Since in the aqueous liquid dispersion amount of water should be enough forming external phase, so electrodepositable paint comprises the 30-70wt% solid usually.If there is water very little, then the phenomenon that viscosity increases continuously can take place.On the contrary, if use too much water, the effective capacity of grinding will be crossed low the reduction owing to mixing medium viscosity.In grinding steps, the solid weight ratio in pigment component and the pigment grind resin keeps about 1.5 usually: 1-10: 1, preferred 3: 1-6: 1.
Usually, when cationic electrodepositable resin that will be used for cationic electrodeposition (it is a resin known in the art) and pigment paste of the present invention combination, obtain electrodepositable coating composition of the present invention.In most of the cases, final electrodepositable coating composition has the pigment ratio of about 0.1-0.5.The bath that will contain 5-25wt% pigment and resin solid usually is used for electrodeposition process, and therefore, final electrodepositable coating composition can also further comprise secondary resin, solvent, antioxidant, tensio-active agent etc. except pigment paste and electrodepositable master resin.The described water-based electrodepositable coating composition of lay then, is being counted volts DS and the 0.25-15A/ft of V to hundreds of V to contact with anode with electric negative electrode
2Current density under carry out galvanic deposit.After finishing galvanic deposit, use water washing process and curing process and produce final lacquering.Usually under 150-200 ℃ temperature, be cured process 15-60 minute.
Electrodepositable coating composition of the present invention comprises end capped isocyanic ester as solidifying agent.Above-mentioned end capped isocyanic ester is an organic multiple isocyanate, and can be such polyisocyanates, i.e. its isocyanate group and end-caps reaction so that end capped isocyanate group at room temperature keep stable to active hydrogen but high temperature down and reactive with active hydrogen.
Aliphatic series (comprising cyclic aliphatic) or aromatic polyisocyanate can be used for preparing above-mentioned end capped polyisocyanate curing agent.Representative instance is 2,4-or 2,6-tolylene diisocyanate or their mixture, to phenylene vulcabond, tetramethylene or hexamethylene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, isophorone diisocyanate, ditan-4,4 '-vulcabond and polymethylene polyphenyl isocyanate.In addition, can use for example triisocyanate of more senior polyisocyanates.Differently, can use triphenyl methane-4,4 ', 4 " triisocyanates.In addition, can use for example for example neopentyl glycol and TriMethylolPropane(TMP) of polyisocyanates and polyvalent alcohol of NCO-prepolymer, or with the polymer polyatomic alcohol reaction product of polycaprolactone glycol and triol for example.
Simultaneously, can use end capped polyisocyanate curing agent by dual mode.At first, can use and wherein do not have the remaining complete end capped form of free isocyanate.In this form, it is via existing as 2-component resin system with the blend of Resins, epoxy main chain.Secondly, behind the end-blocking that merotomizes, make the reactive with active hydrogen in end capped polyisocyanate curing agent and the epoxy polymer skeleton and prepare the 1-component resin.Consider the stability of resin, it is more stable that wherein Resins, epoxy main chain and carbamate solidifying agent form the latter event of the chemical bond cause water-dispersion stability.Yet, because the strong reactivity of end capped solidifying agent that merotomizes,, therefore, have the in-problem shortcoming in production stability aspect so the end capped curing agent component that is difficult to keep merotomizing is stable between extending storage period.Simultaneously, curing catalysts, for example tin catalyst is present in the hardener component usually.Described hardening catalyst for example can be, dibutyl tin laurate and dibutyltin oxide.The preferred amounts of tin component is about 0.05-1wt% of resin solid gross weight.
To explain the present invention in more detail by following examples, but the present invention is not limited by these embodiment.
Preparation embodiment 1: the preparation of monoepoxide-amine compound
Prepare monoepoxide-amine compound by the composition shown in the following table 1.
The preparation component of table 1 monocycle hydride-amine compound
| Composition | Weight part |
| CARDURA E10 | 724.6 |
| The 2-methyl pentamethylene diamine | 175.4 |
| Butoxy ethanol | 100.0 |
[CARDURA E10: the monocycle epoxy resins that can be purchased from Shell Chemical Co.]
2-methyl pentamethylene diamine and butoxy ethanol are added in the reactor, and under slowly stirring, be heated to 70 ℃.Maintaining under 70-80 ℃ the temperature, add monoepoxide lentamente.After interpolation is finished, with reaction mixture be heated to 100 ℃ and stir 2 hours with the preparation monoepoxide-amine compound.
Preparation embodiment 2: the preparation of monoepoxide-amine compound
Prepare monoepoxide-amine compound by the composition shown in the following table 2.
The preparation component of table 2 monoepoxide-amine compound
| Composition | Weight part |
| 2-ethylhexyl glycidyl ether | 759.8 |
| Diethylenetriamine | 140.2 |
| Butoxy ethanol | 100.0 |
Diethylenetriamine and butoxy ethanol are added in the reactor, and under slowly stirring, be heated to 70 ℃.Maintaining under 70-80 ℃ the temperature, add 2-ethylhexyl glycidyl ether lentamente.After interpolation is finished, with reaction mixture be heated to 100 ℃ and stir 2 hours with the preparation monoepoxide-amine compound.
Preparation embodiment 3: the preparation of quaternizing agent
By the tertiary ammonium salt of the preparation of the composition in the following table 3 as quaternizing agent.
The preparation component of table 3 quaternizing agent
| Composition | Weight part |
| PAPI2940 | 300.5 |
| Methyl iso-butyl ketone (MIBK) | 136.5 |
| Dimethylethanolamine | 228.0 |
| Butoxy ethanol | 164.5 |
| Acetate | 160.2 |
[PAPI2940: the polymkeric substance methylenediphenyl diisocyanates that can be purchased from Dow Chemical Co.]
PAPI2940 and methyl iso-butyl ketone (MIBK) are added reaction vessel, and add dimethylethanolamine.At that time, thermopositive reaction takes place.Reaction mixture is heated to 80 ℃.Keeping temperature to be under 80 ℃ the situation stirred reaction mixture 3 hours.Then reaction mixture is cooled to 60 ℃ and add butoxy ethanol.Add acetate then, and stir about 1 hour of this mixture and the synthesis of quaternary ammonium agent down at 65 ℃.
Embodiment 1: the preparation of pigment grind resin
Prepare pigment grind resin by the composition shown in the following table 4.
The preparation component of table 4 pigment grind resin
| Composition | The weight part of solution | The solid weight part |
| N8010 | 465.6 | 465.6 |
| Butoxy ethanol (first) | 134.2 | - |
| Monoepoxide-amine compound of preparation embodiment 1 | 142.1 | 127.9 |
| Butoxy ethanol (second) | 303.5 | - |
| Deionized water | 50.9 | - |
| The quaternizing agent of preparation embodiment 3 | 145.6 | 101.9 |
| Butoxy ethanol (the 3rd) | 30.0 | - |
[N8010 :] by the diglycidylether of the dihydroxyphenyl propane with epoxy equivalent (weight) weight of 480 of KCC Co. preparation
N8010 and butoxy ethanol (first) are added in the reaction vessel, under agitation be heated to 90 ℃ then.Add monocycle epoxy resins-amine compound of preparation embodiment 1 lentamente.At this moment, produce some heat.Temperature of reaction is brought up to 120 ℃ and kept 2 hours.Keep reaction to reach 1,200 epoxy equivalent (weight).When epoxy equivalent (weight) reaches at 1,200 o'clock, add butoxy ethanol (second).After reaction mixture is cooled to 85-90 ℃, add the quaternizing agent that deionized water then adds preparation embodiment 3.Reach about 1 up to acid number, the temperature that keeps reaction mixture is added butoxy ethanol (the 3rd) and the preparation pigment grind resin then at 80-90 ℃.
Embodiment 2: the preparation of pigment grind resin
Prepare pigment grind resin by the composition shown in the following table 5.
The preparation component of table 5 pigment grind resin
| Composition | The weight part of solution | The solid weight part |
| N8010 | 465.6 | 465.6 |
| Butoxy ethanol (first) | 137.5 | - |
| Monoepoxide-amine compound of preparation embodiment 2 | 168.0 | 151.2 |
| Butoxy ethanol (second) | 314.1 | - |
| Deionized water | 48.9 | - |
| The quaternizing agent of preparation embodiment 3 | 138.2 | 96.7 |
| Butoxy ethanol (the 3rd) | 31.0 | - |
N8010 and butoxy ethanol (first) are added in the reaction vessel, under agitation be heated to 90 ℃ then.Add monocycle epoxy resins-amine compound of preparation embodiment 2 lentamente.At this moment, produce some heat.Temperature of reaction is brought up to 120 ℃ and kept 2 hours.Keep reaction to reach 1,300 epoxy equivalent (weight).When epoxy equivalent (weight) reaches at 1,300 o'clock, add butoxy ethanol (second).Reaction mixture is cooled to 85-90 ℃ and add the quaternizing agent that deionized water then adds preparation embodiment 3.Reach about 1 up to acid number, the temperature that keeps reaction mixture is added butoxy ethanol (the 3rd) and the preparation pigment grind resin then at 80-85 ℃.
Comparative preparation embodiment 1: the preparation of quaternizing agent
Prepare quaternizing agent by the composition shown in the following table 6.
The preparation component of table 6 quaternizing agent
| Composition | The weight part of solution | The solid weight part |
| 2-Ethylhexyl Alcohol half end capped tolylene diisocyanate (in methyl iso-butyl ketone (MIBK)) | 320.0 | 304.0 |
| Dimethylethanolamine | 87.2 | 87.2 |
| Lactic acid aqueous solution | 117.6 | 88.2 |
| Butoxy ethanol | 39.2 | - |
Tolylene diisocyanate is added in the reaction vessel, and this tolylene diisocyanate is present in the solvent of methyl iso-butyl ketone (MIBK) and by 2-Ethylhexyl Alcohol half end-blocking.At that time, thermopositive reaction takes place.80 ℃ of following stirred reaction mixtures 1 hour, add lactic acid aqueous solution and butoxy ethanol then successively.65 ℃ of following stirred reaction mixtures 1 hour and the synthesis of quaternary ammonium agent.
The comparative example 1: the preparation of pigment grind resin
Prepare pigment grind resin by the composition shown in the following table 7.
The preparation component of table 7 pigment grind resin
| Composition | The weight part of solution | The solid weight part |
| EPON 829 | 710.0 | 682.0 |
| Dihydroxyphenyl propane | 289.6 | 289.6 |
| 2-Ethylhexyl Alcohol half end capped tolylene diisocyanate (in methyl iso-butyl ketone (MIBK)) | 406.0 | 386.1 |
| The quaternizing agent of comparative preparation embodiment 1 | 496.3 | 421.9 |
| Deionized water | 71.2 | - |
| Butoxy ethanol | 1290.0 | - |
[EPON 829: the diglycidylether of the dihydroxyphenyl propane with epoxy equivalent (weight) weight of 188 that can be purchased from Shell Chemical Co.]
Add EPON829 and dihydroxyphenyl propane in nitrogen atmosphere reaction vessel, and be heated to 150-160 ℃ to cause thermopositive reaction.Under 150-160 ℃, reacted 1 hour.Reaction mixture is cooled to 120 ℃ then, and adds 2-Ethylhexyl Alcohol half end capped tolylene diisocyanate in methyl isobutyl ketone solvent.The temperature that keeps reaction mixture is added butoxy ethanol then between 110-120 ℃.After reaction mixture is cooled to 85-90 ℃, adds deionized water and then add quaternizing agent.Reach about 1 up to acid number, the temperature of reaction mixture is remained on 80-85 ℃.
Preparation embodiment 4: the preparation that dibutyltin oxide is stuck with paste
Preparing dibutyltin oxide by the composition shown in the following table 8 sticks with paste.
The preparation component that table 8 dibutyltin oxide is stuck with paste
| Composition | Weight part |
| The pigment grind resin of preparation among the embodiment 1 | 757.5 |
| Dibutyltin oxide | 481.3 |
| Deionized water (first) | 421.4 |
| Deionized water (second) | 839.8 |
In stirring embodiment 1, in the pigment grind resin of preparation, add dibutyltin oxide.When viscosity uprises owing to the increase of pigment powder, add deionized water (first) and stir this mixture fully up to the pigment powder homogenizing.At last, dilute this mixture with deionized water (second).By SL-703 shredder (BYK) said mixture is dispersed to Hegman numbers 8.
Preparation embodiment 5 and comparative preparation embodiment 2: the preparation that dibutyltin oxide is stuck with paste
By the same procedure of preparation embodiment 4, use embodiment 2 and comparative example's 1 resin to stick with paste respectively as every kind of dibutyltin oxide of pigment grind resin preparation preparation embodiment 5 and comparative preparation embodiment 2.
Embodiment 3: the preparation of pigment paste
Prepare pigment paste by the composition shown in the following table 9.
The preparation component of table 9 pigment paste
| Composition | Weight part |
| The pigment grind resin of embodiment 1 | 397.0 |
| The dibutyltin oxide of preparation embodiment 4 is stuck with paste | 237.8 |
| Carbon black | 10.1 |
| Deionized water (first) | 613.8 |
| ASP200 | 93.0 |
| Titanium dioxide | 1013.5 |
| Surfynol 104 | 12.5 |
| Deionized water (second) | 110.8 |
[ASP 200: the pure aluminium silicate that can be purchased from Engelhard Co..
Surfynol 104: the hexin glycol-based wetting Agent for Printing Inks that can be purchased from Air Products]
In adding embodiment 1, behind the pigment grind resin of preparation, under agitation add mentioned component successively.When viscosity uprises owing to the increase of pigment powder, add deionized water (first) and stir this mixture fully up to the pigment powder homogenizing.At last, dilute this mixture with deionized water (second).(BYK) is dispersed to Hegman number+6 with said mixture by the SL-703 shredder.
Embodiment 4: the preparation of pigment paste
Same procedure by embodiment 3 prepares pigment paste, and difference is to use the pigment grind resin of embodiment 2 and the dibutyltin oxide of preparation embodiment 5 to stick with paste.
The comparative example 2: the preparation of pigment paste
Same procedure by embodiment 3 prepares pigment paste, and difference is to use comparative example 1 pigment grind resin and the dibutyltin oxide of comparative preparation embodiment 2 to stick with paste.
Preparation embodiment 6: the preparation of carbamate solidifying agent
The carbamate solidifying agent that is used for the cationic electrodepositable resin by the preparation of the composition shown in the following table 10.
The preparation component of table 10 carbamate solidifying agent
| Composition | Weight part |
| PAPI 2940 | 1320.0 |
| Methyl iso-butyl ketone (MIBK) | 687.5 |
| Dibutyl tin laurate | 1.0 |
| 2-(2-butoxy oxyethyl group) ethanol (first) | 997.5 |
| TriMethylolPropane(TMP) | 134.2 |
| 2-(2-butoxy oxyethyl group) ethanol (second) | 138.1 |
PAPI 2940, methyl iso-butyl ketone (MIBK) and dibutyl tin laurate are dropped into reaction flask and be heated to 30 ℃ under nitrogen atmosphere.Add 2-(2-butoxy oxyethyl group) ethanol (first) lentamente, maintain the temperature at simultaneously between 60-65 ℃.After interpolation is finished, keep reaction mixture following 90 minutes at 65 ℃.Then add TriMethylolPropane(TMP) and with mixture heating up to 110 ℃ and remained on this temperature following 3 hours.Add 2-(2-butoxy oxyethyl group) ethanol (second) then.Maintain the temperature at continuously under 110 ℃ up to not detecting non-reacted NCO by UV detection.
Preparation embodiment 7: the preparation of cationic electrodeposition master resin dispersion
Prepare cationic electrodeposition master resin dispersion by the composition shown in the following table 11.
The preparation component of table 11 cationic electrodeposition master resin dispersion
| Composition | Weight part |
| EPON 828 | 680.9 |
| Dihydroxyphenyl propane-ethylene oxide adduct (1: 6 mol ratio) | 249.9 |
| Dihydroxyphenyl propane | 199.2 |
| Methyl iso-butyl ketone (MIBK) | 59.1 |
| Benzyldimethylamine (first) | 1.0 |
| Benzyldimethylamine (second) | 2.7 |
| The carbamate solidifying agent of preparation embodiment 6 | 1194.8 |
| KT-22 | 75.5 |
| The N-Mono Methyl Ethanol Amine | 65.7 |
| 85% formic acid | 64.0 |
| Deionized water (first) | 1407.3 |
| Deionized water (second) | 1866.7 |
| Deionized water (the 3rd) | 244.5 |
[EPON 828: the diglycidylether of the dihydroxyphenyl propane with epoxy equivalent (weight) weight of 188 that can be purchased from Shell Chemical Co.
The product of KT-22:Air Products Co.; Two ketoimines (diketimine), it is the end capped diethylenetriamine of methyl iso-butyl ketone (MIBK), 73% solution in methyl iso-butyl ketone (MIBK)]
EPON828, dihydroxyphenyl propane-ethylene oxide adduct, dihydroxyphenyl propane and methyl iso-butyl ketone (MIBK) are added reaction vessel and be heated to 30 ℃ under nitrogen atmosphere.Add benzyldimethylamine (first), and make the reaction mixture temperature rise to about 185 ℃.Remove the water of existence then by the backflow azeotropic.Reaction mixture is cooled to 160 ℃ and remained on this temperature following 30 minutes.Further this mixture is cooled to 145 ℃, adds benzyldimethylamine (second) then.Maintain the temperature at 145 ℃ and reach 1,100-1,140 up to epoxy equivalent (weight) weight.In case epoxy equivalent (weight) weight reaches desirable value, just add carbamate solidifying agent, KT22 and the N-Mono Methyl Ethanol Amine of preparation embodiment 6 successively.Reaction mixture is cooled to 125 ℃ after the mixture temperature rise making.Remaining on 125 ℃ after following 2 hours, lentamente reaction mixture is added in the mixture that comprises formic acid and deionized water (first), fully stir to disperse.Then, add deionized water (second) and deionized water (the 3rd) lentamente, but and carry by vacuum gas and to remove organic solvent to prepare solids content be 36% cationic electrodepositable water dispersion resin with further dilution.
Embodiment 5-6 and comparative example 3: be the preparation of the electrodepositable coating composition of electrodeposition bath form
Stirring 3, but 318 weight parts are by the above-mentioned method synthetic water dispersion resin and 3 for preparing embodiment 7, in the time of the mixture of 638 parts by weight of deionized water, add in the pigment paste of preparation among 536 weight part embodiment 3, embodiment 4 and the comparative example 2 each and be 20% cationic electrodepositable coatings composition with the solids content for preparing embodiment 5-6 and comparative example 3 respectively.
Allow the electrodepositable coating composition for preparing above arrive 20% of its original volume, make the exchange of this ultrafiltrated and deionized water then by ultra-fine filter.After under whipped state, keeping one day, under 28 ℃, carrying out galvanic deposit coating 2 minutes under the volts DS of 210-270V.The steel plate that use is handled with phosphoric acid is as test sample.Applied this sample 2 minutes and made and solidified 30 minutes down at 170 ℃.The various performance numbers of measurement lacquering also are shown in the following table 12.
The measuring result of the performance of table 12 lacquering
[roughness: use Taylor-Hobson Surtronic 3+ measurement (cutoff: 0.8mm)]
According to disclosed method among the Korean Patent Publication No. 92-931, in order to estimate the pigment dispersibility and the storage stability of the pigment grind resin of preparation among the foregoing description 1-2 and the comparative example 1, test to top embodiment 3-4 and comparative example's 2 pigment paste or to embodiment 5-6 and comparative example's 3 cationic electrodepositable coatings composition.Test-results is shown in the following table 13.
The test-results of table 13 pigment paste
| The test item | Embodiment 3 | Embodiment 4 | The comparative example 2 |
| Hegman 6+ passes through the time in the pigment grind | 15 minutes | 18 minutes | 25 minutes |
| Hot storage stability | 19 days | 20 days | 15 days |
| 400 screenings are passed through | ○ | ◎ | △ |
| By the inspection (vertical component) of naked eyes to the solidified paint coating | ◎ | ◎ | △ |
| By the inspection (horizontal component) of naked eyes to the solidified paint coating | ◎ | ○ | × |
Hegman 6+ passes through the time in the-pigment grind: disperse the 3kg pigment paste by Dispermat SL-703 (BYKCo.).
-Re storage stability: by pigment paste being stored in 60 ℃ of baking ovens and measuring the expending time in of gelation with assess thermal stability.
-400 mesh sieve gating mistakes: after 1 month, allowing lacquer solution (amounting to 2kg) filter by 400 order wire cloth (800cm from the lacquer preparation
2Surface-area).Dry gained resistates is 3 hours under 110 ℃, and weighing.(◎ 1g or still less; Zero 1-4g; △ 4-10g; * 10g or more)
-by the inspection of naked eyes to the solidified paint coating:, after 1 month base material vertically or flatly is being dipped in the lacquer solution from the lacquer preparation.As described abovely carry out galvanic deposit and apply, by naked eyes every 100cm is counted in the inspection of solidified paint coating then
2Pinprick and agglomerative number.(◎ 1 or still less; Zero 1-5; △ 5-20; * 20 or more)
From table 12 and table 13 as can be seen, pigment grind resin prepared in accordance with the present invention has good pigment dispersibility, and pigment grind resin and with the pigment paste of its preparation and coating compositions even after prolonging storage, still keep stable itself, anti-pin hole and arc crater form, and produce slick outward appearance.
Industrial applicability
As can be seen from the above, according to the present invention, can prepare the generation good appearance, have good pigment dispersibility and provide the cationic pigment grind resin of good storage stability to various pigment, and comprise its pigment paste and electrodepositable coating composition.
Claims (12)
1. as the cationic pigment grind resin of polyepoxide-polyimide resin, its comprise (i) but acid neutral amido, but described acid neutral amido is derived from monoepoxide with have monoepoxide-amine compound that the reaction of the amine of 3 or more a plurality of active hydrogens produces and (ii) at the quaternary ammonium salt base at its chain middle part.
2. according to the cationic pigment grind resin of claim 1, wherein the polyepoxide in polyepoxide-polyimide resin is the polyglycidyl ether of polyphenol, the polyglycidyl ether of aromatic polyol or the poly-epoxide resin of modification.
3. according to the cationic pigment grind resin of claim 1, wherein monoepoxide is the monoepoxide of following formula 1:
R wherein
1Be hydrogen or methyl; R
2Be hydrogen, replacement or unsubstituted alkyl or cycloalkyl, or replacement or unsubstituted aryl.
4. according to the cationic pigment grind resin of claim 1, the amine that wherein has 3 or more a plurality of active hydrogens is selected from ethylene diamine, hexamethylene-diamine, four (pentamethylene) diamines, five methylene diamine, 2-methyl pentamethylene diamine, polyoxy alkylidene diamines, diethylenetriamine, amino ethyl ethanolamine, Triethylenetetramine (TETA) and their mixture.
5. according to the cationic pigment grind resin of claim 1, wherein with monoepoxide with have monoepoxide-amine compound that the reaction of the amine of 3 or more a plurality of active hydrogens produces and have 2 or more a plurality of active hydrogen, but and the acid neutral amido that forms of the chain extending reaction by monoepoxide-amine compound and poly-epoxide resin be positioned at the middle part of chain.
6. according to the cationic pigment grind resin of claim 1, wherein quaternary ammonium salt base is to form by epoxide group and the tertiary ammonium salt reaction that makes polyepoxide-amine compound.
7. according to the cationic pigment grind resin of claim 6, wherein tertiary ammonium salt is by the hydroxyl of dialkyl group alkanolamine and the amino-formate bond of vulcabond, and obtain with the acid neutralization.
8. according to the cationic pigment grind resin of claim 7, wherein acid is one or more organic carboxyl acids that are selected from lactic acid, acetate, propionic acid, butyric acid, neopentanoic acid, acid dimethyl, formic acid and oxyacetic acid.
9. according to the cationic pigment grind resin of claim 1, but wherein 1g cationic pigment grind resin contains 0.01-1.3 milliequivalent acid neutral amido (i) and the described quaternary ammonium salt base of 0.01-1.2 milliequivalent (ii).
10. comprise pigment paste according to each cationic pigment grind resin among the claim 1-9.
11. according to the pigment paste of claim 10, wherein the solid weight ratio of pigment component and pigment grind resin is 1.5: 1-10: 1.
12. electrodepositable coating composition, it comprises according to each cationic pigment grind resin among the claim 1-9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070004865 | 2007-01-16 | ||
| KR1020070004865A KR100891156B1 (en) | 2007-01-16 | 2007-01-16 | A cationic pigment grinding resin and an electrodepositable coating composition comprising the same |
| KR10-2007-0004865 | 2007-01-16 | ||
| PCT/KR2008/000213 WO2008088151A1 (en) | 2007-01-16 | 2008-01-14 | A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same |
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| CN101583678A true CN101583678A (en) | 2009-11-18 |
| CN101583678B CN101583678B (en) | 2013-07-17 |
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| CN2008800022747A Active CN101583678B (en) | 2007-01-16 | 2008-01-14 | A cationic resin for pigment dispersion and an electrodepositable paint composition comprising the same |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR100891156B1 (en) |
| CN (1) | CN101583678B (en) |
| RU (1) | RU2428444C2 (en) |
| TR (1) | TR200905327T1 (en) |
| WO (1) | WO2008088151A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105874014A (en) * | 2013-12-20 | 2016-08-17 | 巴斯夫涂料有限公司 | Method for producing a pigment paste, aqueous electrocoat, its use, method for cataphoretic electrocoating and article coated |
| CN109312175A (en) * | 2016-08-18 | 2019-02-05 | Ｋｃｃ公司 | Electrodeposition coating composition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5653310B2 (en) * | 2011-07-13 | 2015-01-14 | 日産自動車株式会社 | Coating composition and coating film forming method using the same |
| RU2486220C2 (en) * | 2011-09-07 | 2013-06-27 | Закрытое акционерное общество "ОНТК-94" | High diffusion power cathodic electrodeposition composition for obtaining high hardness and wear resistant coatings |
| KR101857296B1 (en) * | 2011-12-27 | 2018-06-20 | 주식회사 케이씨씨 | Modified polyepoxide-amine resin for thin electroplating coating with improved appearance, method for preparing the same and electroplating coating composition comprising the same |
| KR102341535B1 (en) * | 2017-03-10 | 2021-12-22 | 주식회사 케이씨씨 | Coating composition for cationic electrodeposition |
| CN112457721B (en) * | 2020-12-03 | 2023-02-03 | 上海瑞君电泳涂料有限公司 | Color paste for epoxy electrophoretic coating, electrophoretic coating and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4007154A (en) * | 1975-08-01 | 1977-02-08 | Ppg Industries, Inc. | Novel pigment paste for cationic electrodeposition |
| US4186124A (en) * | 1975-08-01 | 1980-01-29 | Ppg Industries, Inc. | Novel pigment grinding vehicle |
| US4715898A (en) * | 1986-06-30 | 1987-12-29 | Ppg Industries, Inc. | Sulfonium resins useful as pigment grinding vehicles in cationic electrodeposition |
| US4913968A (en) * | 1986-09-12 | 1990-04-03 | Minnesota Mining And Manufacturing Company | Water-compatible coating resin |
| ZA891937B (en) * | 1988-04-04 | 1990-11-28 | Ppg Industries Inc | Pigment grinding vehicles containing quaternary ammonium and ternary sulfonium groups |
| KR950014243A (en) * | 1993-11-02 | 1995-06-15 | 후지이 히로시 | Cationic Electrodeposition Coating Composition |
| US5820987A (en) * | 1996-08-21 | 1998-10-13 | Ppg Industries, Inc. | Cationic electrocoating compositions, method of making, and use |
| CN1112412C (en) * | 2000-09-01 | 2003-06-25 | 清华大学 | Diazo coupling process of polymer to synthesize high molecular epoxy resin dye |
| DE10109483A1 (en) * | 2001-02-28 | 2002-09-05 | Clariant Gmbh | Oxalkylation products made from epoxides and amines and their use in pigment preparations |
| US6756129B1 (en) * | 2002-12-20 | 2004-06-29 | Meadwestvaco Corporation | Polymer blend compositions |
| CN1218000C (en) * | 2003-09-10 | 2005-09-07 | 江苏鸿业涂料科技产业有限公司 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
-
2007
- 2007-01-16 KR KR1020070004865A patent/KR100891156B1/en active IP Right Grant
-
2008
- 2008-01-14 TR TR2009/05327T patent/TR200905327T1/en unknown
- 2008-01-14 WO PCT/KR2008/000213 patent/WO2008088151A1/en active Application Filing
- 2008-01-14 RU RU2009131047/05A patent/RU2428444C2/en active
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105874014A (en) * | 2013-12-20 | 2016-08-17 | 巴斯夫涂料有限公司 | Method for producing a pigment paste, aqueous electrocoat, its use, method for cataphoretic electrocoating and article coated |
| CN105874014B (en) * | 2013-12-20 | 2018-05-25 | 巴斯夫涂料有限公司 | Prepare method, water soluble electrocoating, its purposes, cataphoresis painting method and the coated product of pigment paste |
| CN109312175A (en) * | 2016-08-18 | 2019-02-05 | Ｋｃｃ公司 | Electrodeposition coating composition |
| CN109312175B (en) * | 2016-08-18 | 2021-03-09 | Ｋｃｃ公司 | Electrophoretic coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080067491A (en) | 2008-07-21 |
| TR200905327T1 (en) | 2009-09-23 |
| WO2008088151A1 (en) | 2008-07-24 |
| KR100891156B1 (en) | 2009-04-06 |
| RU2428444C2 (en) | 2011-09-10 |
| CN101583678B (en) | 2013-07-17 |
| RU2009131047A (en) | 2011-02-27 |
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