CN103183997B - Automobile water-based dissolubility bottom coating composition and the method by its formation coating - Google Patents
Automobile water-based dissolubility bottom coating composition and the method by its formation coating Download PDFInfo
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- CN103183997B CN103183997B CN201210236069.5A CN201210236069A CN103183997B CN 103183997 B CN103183997 B CN 103183997B CN 201210236069 A CN201210236069 A CN 201210236069A CN 103183997 B CN103183997 B CN 103183997B
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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Abstract
A kind of water-soluble coating composition, based on the total amount of this coating composition, it comprises: 20 ~ 50 % by weight by use urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin manufactured by emulsifying agent, 3 ~ 10 % by weight curing agent mixture, the vibrin of 2 ~ 10 % by weight and the water of surplus.Based on the total amount of curing agent mixture, described curing agent mixture comprises: the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, 5 ~ 15 % by weight METHYLPYRROLIDONE, the wetting ability melamine resin of 25 ~ 35 % by weight, hydrophobicity melamine resin and 2 ~ 5 % by weight of 15 ~ 25 % by weight nonionogenic tenside.This coating composition has the good character comprising outward appearance, water tolerance, adhesivity etc.
Description
Technical field
The present invention relates to automobile water-based dissolubility bottom coating composition and use said composition to form the method for coating.More specifically, the present invention relates to and there is good appearance and good mechanical properties and the good water-soluble bottom coating composition relating to the coating waste water of flowing and stain and use said composition to form the method for coating, described outward appearance comprises glossiness and image definition, and described mechanical properties comprises the adhesiveproperties that water tolerance, adhesivity, shock resistance, elasticity and overbaking coating are coated with again.
Background technology
In the automotive industry, coating process is the axis in the manufacturing processed of engine manufacturing processed and steering gear part.Because the regulation of the volatile organic compounds (VOC) for discharge implements the several years, thus relevant with automobile coating process there has been wide variation.Particularly, the use to restriction volatile organic compounds of European countries and developed country is extremely paid close attention to and is limited the use of volatile organic compounds energetically and apply to sanction to comprising the product using volatile organic compounds.
In general, volatile organic compounds can easily volatilization and to be naturally diffused in air with gaseous phase thus to become main topsoil factor.In addition, volatile organic compounds can have bio-toxicity and chemical reactivity, and becomes a factor damaging the ozone layer thus cause Greenhouse effect and produce unpleasant odor.
In view of the restrictive policy of discharging volatile organic compounds, to the protection of environment and the improvement of Working environment, the amount reducing volatile organic compounds in automotive coating composition becomes very important theme.In order to reduce the amount of volatile organic compounds in automotive coating composition, dealer have developed various method.Such as, prepared and there is highly filled oil-based coating compositions thus shorten the time of implementing needed for oil-based coating compositions coating process, and prepared water-soluble coating composition.The most effectual way of amount reducing volatile organic compounds comprise to make in coating composition comprise volatile organic compounds amount minimize.In addition, oil-based coating compositions is replaced by water-soluble coating composition gradually.Especially effectively, the oil base primary coating composition replacing comprising about organic solvent of 50 ~ 70 % by weight with water-soluble primary coating composition can be required.Therefore, dealer has carried out the development research to water-soluble primary coating composition energetically.Top coating composition can comprise primary coating composition and clear coating composition.
In general, oil-based coating compositions can comprise acrylic resin, melamine resin, vibrin, polyurethane resin, organic solvent etc.Oil-based coating compositions can have good image definition and good mechanical properties (as adhesivity, shock resistance, resistance to bending etc.).Alternately, water-soluble coating composition can comprise water soluble acrylic resin, water-soluble microgel resin or ACRYLIC EMULSION etc. as Primary resins and assisted resin (as vibrin and polyurethane dispersion) together with wetting ability melamine resin.Water-soluble coating composition also can comprise Primary resins, assisted resin and hydrophobicity trimeric cyanamide aqueous dispersant.When compared with oil-based coating compositions, water-soluble coating composition has poor comprising and is flowing in interior workability and poor water tolerance.
Widely used water-soluble coating composition can comprise: acrylic resin and transoid and core/shell type microgel resin, also have for improving chipping resistance and the direction-sense assisted resin of luminous pigment (as urethane dispersion and vibrin).
Especially, when preparing hydrophobicity trimeric cyanamide aqueous dispersant, acrylic resin can be used as reacting resin.But, owing to using anionic reactive emulsifying agent in microgel resin, thus use have the coating composition of above-mentioned composition form coating water tolerance can reduce.
As the solidifying agent used in water soluble paint for automobile composition, aminoresin, block isocyanate compound, nitrogen heterocycle propane compound, epoxy compounds etc. can be enumerated.The aminoresin that may be used as solidifying agent can comprise wetting ability melamine resin and hydrophobicity melamine resin.Wetting ability melamine resin can directly join in water-soluble coating composition.But, in order to promote the physical properties (comprising adhesivity) of composition, hydrophobicity melamine resin can be used as melamine resin aqueous dispersant.
By making specific acrylic resin and hydrophobicity melamine resin react, and obtain hydrophobicity trimeric cyanamide aqueous dispersant.Therefore, the turnout by using hydrophobicity melamine resin to reduce water-soluble coating composition.
When only comprising wetting ability melamine resin, the adhesivity coated again by clear coating composition in the overbaking coating of primary coating composition can be deteriorated.
Summary of the invention
Some embodiments provide the new type water-solubility coating composition with good appearance (comprising glossiness and image definition) and good mechanical properties (comprising the adhesiveproperties that water tolerance, sticking property, shock resistance, resistance to bending and overbaking coating are coated with again).
Some other embodiments provide the method using described water-soluble coating composition to form coating.
According to some embodiments, the total amount of coating based composition, water-soluble coating composition comprises: 20 ~ 50 % by weight by using urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin manufactured by emulsifying agent, the curing agent mixture of 3 ~ 10 % by weight is (based on the total amount of curing agent mixture, comprise the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, the METHYLPYRROLIDONE of 5 ~ 15 % by weight, the wetting ability melamine resin of 25 ~ 35 % by weight, the hydrophobicity melamine resin of 15 ~ 25 % by weight, with 2 ~ 5 % by weight nonionogenic tenside), the vibrin of 2 ~ 10 % by weight, and the water of surplus.
In some embodiments, urethanum aqueous dispersant is prepared: make two functional isocyanate compounds, have 1 by following method, 500 ~ 2, the polycarbonate polyol of 500 molecular weight and the compound with at least two hydroxy functional groups and a carboxylic acid functional react, and are formed in the prepolymer that end has isocyanate functional group.Then, by this prepolymer in the aqueous solution of amine, then chain extension process can be implemented.
In some embodiments, two functional isocyanate compounds can be selected from least one in 1,6-six methylene vulcabond, isophorone diisocyanate and 4,4-vulcabond cyclohexyl-methane.
In some embodiments, the compound with at least two hydroxy functional groups and a carboxylic acid functional can be at least one in dimethylol propionic acid and dimethylolpropionic acid.
In some embodiments, alkali swellable core-shell structure copolymer resin can comprise core and the shell part around this core.By emulsifying agent and the first monomer mixture letex polymerization and obtain core.Second comonomer mixture can be used and obtain shell part.Here, the Mixing ratio by weight of the first monomer mixture and second comonomer mixture can in the scope of 65 ~ 85: 15 ~ 35; Based on the total amount of the first monomer mixture and second comonomer mixture, the amount of described emulsifying agent can be 5 ~ 30 % by weight.
In some embodiments, the first monomer mixture can comprise the cycloalkyl methacrylate with 4 ~ 12 carbon atoms of 75 ~ 90mol% and copolymerizable single alkylidene group unsaturated monomer (copolymerizablemonoalkylenicunsaturatedmonomer) of 10 ~ 25mol%; Second comonomer mixture can comprise the methacrylic acid of 20 ~ 40mol% and copolymerizable single alkylidene group unsaturated monomer of 60 ~ 80mol%.
In some embodiments, urethanum aqueous dispersant can have the acid number of 90 ~ 100mgKOH/g and the solids content of 28 ~ 34%.
In some embodiments, water-soluble coating composition also can comprise: the metallic pigment of 1 ~ 3 % by weight, the pigment-water dispersion liquid of 5 ~ 50 % by weight, 3 ~ 6 % by weight solubility promoter, 0.1 ~ 2 % by weight wetting agent, 0.1 ~ 2 % by weight dispersion agent, the defoamer of 0.1 ~ 1.5 % by weight, tackifier and 0.1 ~ 3 % by weight of 0.1 ~ 1.0 % by weight neutralizing agent.
According to some embodiments, in the method forming coating, water-soluble coating composition is coated on base material.The total amount of coating based composition, water-soluble coating composition comprises: 20 ~ 50 % by weight by using urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin manufactured by emulsifying agent, the curing agent mixture of 3 ~ 10 % by weight is (based on the total amount of curing agent mixture, comprise the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, the METHYLPYRROLIDONE of 5 ~ 15 % by weight, the wetting ability melamine resin of 25 ~ 35 % by weight, the hydrophobicity melamine resin of 15 ~ 25 % by weight, with 2 ~ 5 % by weight nonionogenic tenside), the vibrin of 2 ~ 10 % by weight, and the water of surplus.Then, the composition dries through coating is made.
In some embodiments, described coating can form the thickness of 10 ~ 25 microns, and this coating is the undercoat of vehicle top coating.
In some embodiments, a kind of method in spraying coating and electrostatic applications can be utilized to implement coating.
In some embodiments, the step coated by clear coating composition in described coating can be implemented further.
As mentioned above, when using described water-soluble primary coating composition to form coating, the flowing after being coated with and stain can be prevented.In addition, the baking water tolerance of coating and the directional property of metallic particles can be improved.In addition, the coating with good chipping resistance can be obtained when not using assisted resin.
Embodiment
To more fully describe various illustrative embodiments below, which illustrates some illustrative embodiments.But, many different forms can be adopted to implement the present invention, and do not should be understood to the illustrative embodiments that the present invention is confined to state herein.On the contrary, make this specification sheets be thoroughly and completely and scope of the present invention is fully conveyed to those skilled in the art by providing these illustrative embodiments.In the accompanying drawings, for clarity sake, the size in each layer and each region and relative size can be amplified.
Term "and/or" used herein comprises one or more arbitrary combination in relevant Listed Items and all combinations.
Although it should be understood that and term first, second, third, etc. can be used herein to describe various element and/or composition, these elements and/or composition should by the restrictions of these terms.These terms are only used for an element or composition and another element or composition to differentiate.Therefore, without deviating from the teachings, the first element described below or composition can be described as the second element or composition.
Term used herein is only not intended to limit the present invention for the purpose of concrete illustrative embodiments to illustrate.Odd number used herein " one ", " one " and " being somebody's turn to do " are intended that and also comprise plural form, unless context explicitly points out.It is also to be understood that, when use term " to comprise " herein and/or " comprising " time, specifically refer to the existence of institute's features set forth, integer, step, operation, element and/or composition, but do not get rid of one or more further feature, integer, step, operation, element, the existence of composition and/or its combination or interpolation.
Unless otherwise prescribed, all terms used herein (comprising technology and scientific terminology) have the implication identical with the implication that those skilled in the art in the invention understand usually.It is also to be understood that, the term defined in such as common dictionary should be counted as having the implication consistent with the implication in this context and association area, and by not being counted as Utopian implication or excessively formal implication, unless so defined clearly herein.
Hereinafter, described in detail to the illustrative embodiments of coating composition according to the present invention and the method that uses this coating composition to form coating.
In the exemplary embodiment, the total amount of coating based composition, described coating composition comprises: 20 ~ 50 % by weight by using urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin manufactured by emulsifying agent, the curing agent mixture of 3 ~ 10 % by weight is (based on the total amount of curing agent mixture, it comprises the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, the METHYLPYRROLIDONE of 5 ~ 15 % by weight, the wetting ability melamine resin of 25 ~ 35 % by weight, the hydrophobicity melamine resin of 15 ~ 25 % by weight, with 2 ~ 5 % by weight nonionogenic tenside), the vibrin of 2 ~ 10 % by weight, and the water of surplus.
Described in detail to formation according to each composition of the coating composition of illustrative embodiments below.
Can be Primary resins by using urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin prepared by emulsifying agent, and prepare this alkali swellable core-shell structure copolymer resin by following method: utilize letex polymerization to form core, and formed be centered around circumnuclear wetting ability shell portion by the monomer mixture comprising hydrophilic vinylic monomer is added drop-wise to formed core.
By use described alkali swellable core-shell structure copolymer resin as Primary resins and the shell part neutralizing this core-shell structure copolymer resin with amine compound to show the extension of shell and expansion thus to obtain structural viscosity, the good workability (it comprises mobility) of coating composition can be obtained.In addition, the directional property of particle can be improved, can be formed simultaneously and there is good outward appearance and the coating of granular sensation.
Urethanum aqueous dispersant is prepared: make two functional isocyanate compounds, have 1 by following method, 500 ~ 2, the polycarbonate polyol of 500 molecular weight and the compound with at least two hydroxy functional groups and a carboxylic acid functional react, be formed in the prepolymer that end has isocyanate functional group thus, then make prepolymer in the aqueous solution of amine, then implement chain extension step.
The two functional isocyanate compounds for the preparation of urethanum aqueous dispersant can comprise: be selected from 1, at least one in 6 hexamethylene diisocyanates, isophorone diisocyanate and 4,4-vulcabond cyclohexyl-methane.
The compound with at least two hydroxy functional groups and a carboxylic acid functional for the preparation of urethanum aqueous dispersant can comprise at least one in dimethylol propionic acid and dimethylolpropionic acid.
Neutralizing agent for the water-dispersion of prepolymer can comprise triethylamine, ammonia etc.
In order to utilize urethanum aqueous dispersant to prepare alkali swellable core-shell structure copolymer resin as emulsifying agent, urethanum aqueous dispersant based on the total amount 5 ~ 30 % by weight of monomer can be used as emulsifying agent.More preferably, the urethanum aqueous dispersant of 10 ~ 20 % by weight can be used to implement letex polymerization.Urethanum aqueous dispersant can have the acid number of 90 ~ 100mgKOH/g and the solids content of 28 ~ 34%.
Alkali swellable core-shell structure copolymer resin can be the polymkeric substance by implementing prepared by least two steps.First, first monomer mixture that can be prepared as follows, it comprises other copolymerizable single alkylidene group unsaturated monomer of the cycloalkyl methacrylate comprising the cycloalkyl with 4 ~ 12 carbon atoms of 75 ~ 90mol% and 10 ~ 25mol%.In the case, the total amount of these two kinds of monomers can be 100mol%.
Then, the second comonomer mixture that can be prepared as follows, it comprises other copolymerizable single alkylidene group unsaturated monomer of the methacrylic acid of 20 ~ 40mol% and 60 ~ 80mol%.In the case, the total amount of these two monomers can be 100mol%.
Carry out copolymerization step by step by the second comonomer mixture of the first monomer mixture and 15 ~ 35 % by weight making 65 ~ 85 % by weight, described alkali swellable core-shell structure copolymer resin can be prepared.This resin can comprise the carboxylic acid group deriving from least part of Ionized methacrylic acid.
The cycloalkyl methacrylate comprising the cycloalkyl with 4 ~ 12 carbon atoms for the preparation of the first monomer mixture can comprise: butyl acrylate, butyl methacrylate, Octyl acrylate, isobornyl acrylate, 2-EHA, isobornyl methacrylate, 2-Ethylhexyl Methacrylate, dodecylacrylate, lauryl methacrylate, and composition thereof etc.Preferred compound in above-claimed cpd can comprise: butyl acrylate, butyl methacrylate and composition thereof.
Copolymerizable single alkylidene group unsaturated monomer for the preparation of the first monomer mixture can comprise: methyl methacrylate, methyl acrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, methacrylic acid 2-methoxy acrylate, methacrylic acid 2-ethoxy ethyl ester, vinylformic acid 3-methoxyl group propyl ester, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxybutyl, the own ester of vinylformic acid 6-hydroxyl, and composition thereof etc.In these compounds, preferably methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate and their mixture; Also preferably vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester and their mixture.
Copolymerizable single alkylidene group unsaturated monomer for the preparation of second comonomer mixture can comprise: vinylbenzene, Vinyl toluene, vinyl cyanide, methacrylonitrile, methyl methacrylate, methyl acrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, butyl acrylate, butyl methacrylate, 2-EHA, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2 hydroxy propyl ester, vinylformic acid 4-hydroxybutyl, the own ester of vinylformic acid 6-hydroxyl, methacrylic acid 2-methoxy acrylate, methacrylic acid 2-ethoxy ethyl ester, their mixture etc.
With regard to emulsion co-polymerization closes, the radical initiator comprising ammonium persulphate, Sodium Persulfate, Potassium Persulphate etc. can be used.In the temperature range of about 70 ~ 80 DEG C, the copolymerization of these monomer mixtures under atmospheric pressure can be implemented in the saturated atmosphere of nitrogen.By add neutralizing agent (as ammonia and amine compound) can neutralize obtain about 80 ~ 100% of carboxylic acid.Described amine compound can comprise: triethylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine etc.
Based on the total amount of water-soluble coating composition, the amount of alkali swellable core shell resin can be 20 ~ 50 % by weight.When this amount is less than 20 % by weight, the viscosity of the coating composition of so preparation can reduce and coating processability and water tolerance can reduce.When this amount is more than 50 % by weight, the sticking property of coating when can suppress to be coated with again.
When the alkali swellable core-shell structure copolymer resin utilized prepared by above-mentioned steps is used as the water-soluble bottom coating composition of automobile top coating composition, the while of the thixotropy of water-soluble primary coating composition can being controlled and realize good workability, do not produce flowing and stain.This coating composition can show good outward appearance, adhesivity, shock resistance and buckling.Particularly, the water tolerance that may reduce because of emulsifying agent can be improved.In addition, the directional property of metallic pigment can improve.Particularly, when this coating composition is mixed with Polyester Resin Water Soluble, can further improve described directional property.Because urethanum aqueous dispersant can be used as emulsifying agent, so the coating with good chipping resistance can be obtained when not adding independently for improving the urethanum dispersion agent of chipping resistance.
Hereinafter, curing agent mixture is described in detail.
When wetting ability melamine resin is directly added in water-soluble coating composition, cohesive force can be produced hardly.But, when hydrophobicity melamine resin is directly added in water-soluble coating composition, can cohesive force be produced.The generation of cohesive force can make the outward appearance of coating and physical properties and poor adhesion.
According to illustrative embodiments, the curing agent mixture comprising hydrophilic resin, hydrophobic resin and nonionogenic tenside can be used for the compatibility optimized with alkali swellable core-shell structure copolymer resin and water.Therefore, the adhesivity of described coating and overbaking coating when being coated with again is good.
Solvent for the preparation of described curing agent mixture can comprise: ethylene glycol butyl ether, Virahol, N N-methyl-2-2-pyrrolidone N-etc.Based on the total amount of curing agent mixture, curing agent mixture can comprise: the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, 5 ~ 15 % by weight METHYLPYRROLIDONE, the wetting ability melamine resin of 25 ~ 35 % by weight, hydrophobicity cymel and 2 ~ 5 % by weight of 15 ~ 25 % by weight tensio-active agent.
When the amount of ethylene glycol butyl ether is less than 10 % by weight, melamine resin can not fully dissolve and the outward appearance of coating and physical properties can be deteriorated.When the amount of ethylene glycol butyl ether is more than 30 % by weight, the thixotropy index (TI) of the coating composition of so preparation can reduce and coating processability can reduce.Therefore, based on the total amount of curing agent mixture, the preferred amounts of ethylene glycol butyl ether can in the scope of 10 ~ 30 % by weight.
Based on the total amount of curing agent mixture, the amount of Virahol can be 10 ~ 30 % by weight.When this amount is less than 10 % by weight, the storage quality of coating composition can reduce, and when making coating dry, pin-hole phenomena and cracking (cutting) phenomenon can occur when this amount is more than 30 % by weight.
METHYLPYRROLIDONE can increase the solubleness of melamine resin and improve the storage quality of coating composition.Based on the total amount of solidifying agent, the amount of METHYLPYRROLIDONE can in the scope of 5 ~ 15 % by weight.When the amount of METHYLPYRROLIDONE is less than 5 % by weight, the raising degree of coating composition storage quality can reduce, when the amount of METHYLPYRROLIDONE is more than 15 % by weight, the TI of coating composition can reduce, and can produce mobile defect and occur owing to solidifying the coating cracking defect caused when implementing coating process.
Wetting ability melamine resin can comprise: purchased from the Lubipal-052 of Cytec company Cymel-202, Cymel-325, Cymel-327, Cymel-370, Cymel-385 and Cymel-254 and available from BASF.
Hydrophobicity melamine resin can comprise: purchased from M3-1280 and M3-1286 of NorooPaint company, purchased from Setamine-146 and Setamine-138 of Nuplex company, purchased from Cymel-683, Cymel-1158 and Cymel-1156 of Cytec company.
The Mixing ratio by weight of wetting ability melamine resin and hydrophobicity melamine resin can in the scope of 50: 50 ~ 70: 30.When being coated with when the amount of wetting ability melamine resin exceedes this given range, the adhesiveproperties of coating can reduce again, and when the amount of hydrophobicity melamine resin exceedes this given range, the exterior quality of water-soluble bottom coating composition can reduce.
As the tensio-active agent for the preparation of curing agent mixture, nonionogenic tenside can be used.Based on the total amount of curing agent mixture, the amount of tensio-active agent can in the scope of 2 ~ 5 % by weight.When the amount of tensio-active agent is less than 2 % by weight, the compatibility of curing agent mixture and water-soluble coating composition can be deteriorated.When the amount of tensio-active agent is more than 5 % by weight, the total cost of coating composition can be increased and water tolerance can reduce.In addition, the surface tension of water-soluble bottom coating composition can decline and cratering phenomenon can occur.Tensio-active agent can comprise Surfynol-420, Surfynol-440, Surfynol-465 etc. purchased from AirProducts company.
Hereinafter, using being illustrated the vibrin as assisted resin comprised in coating composition according to illustrative embodiments.
Described vibrin has the dispersion type resin being about 50nm particle diameter.The total amount of coating based composition, the amount of vibrin can in the scope of 2 ~ 10 % by weight.When vibrin be less than 2 % by weight time, the adhesivity of particle and directional property can reduce.When the amount of vibrin is more than 10 % by weight, physical properties (comprising shock resistance, resistance to bending etc.) can be deteriorated.Vibrin can comprise the Norooster8210 purchased from Norooholdings company.
The metallic pigment comprised in water soluble paint for automobile composition can have the mean diameter (D50) being about 5 ~ 40 microns.This pigment is changed over by processing surface of pigments the type being applicable to water-soluble coating composition.Particularly, this pigment can comprise non-staining or painted metal or metal oxide, comprises aluminium and aluminum oxide.Particularly, aluminum paste can be enumerated.Described metallic pigment can comprise the aluminum paste product of the Hydran series purchased from Eckardt company.The total amount of coating based composition, can suitably control in the scope of 1 ~ 3 % by weight by the amount of this pigment.
Mineral dye and pigment dyestuff can be comprised as pigment according to the pigment dispersing solution comprised in the water-soluble coating composition of illustrative embodiments.The total amount of coating based composition, the amount of pigment can in the scope of 5 ~ 50 % by weight.When the amount of pigment is less than 5 % by weight, the shield effectiveness of primer coating can reduce, and when the amount of pigment is more than 50 % by weight, the storage quality of described coating composition and the disperse properties of pigment can be deteriorated.
Solubility promoter can comprise: 2-Ethylhexyl Alcohol, 2-Rutgers 612, butyl carbitol, Virahol, butanols etc.The total amount of coating based composition, the amount of solubility promoter can in the scope of 3 ~ 6 % by weight.When the amount of solubility promoter is less than 3 % by weight, the planarization of coating can be deteriorated, and when the amount of solubility promoter is more than 6 % by weight, the planarization of coating can improve but the amount of volatile organic compounds can increase thus atmosphere pollution.Can separate with the solvent that comprises in curing agent mixture and use solubility promoter.
The wetting agent comprised in water-soluble coating composition can be polyether siloxane copolymers type wetting agent, nonionic organic surfactant type wetting agent etc.The total amount of coating based composition, the amount of wetting agent can in the scope of 0.1 ~ 2 % by weight.When the amount of wetting agent is less than 0.1 % by weight, wettability during coating can decline.When the amount of wetting agent is more than 2 % by weight, water tolerance and the anti-cratering of coating can be deteriorated.Wetting agent can comprise: purchased from TEGOWet-260, TEGOWet-265, TEGOWet-270, TEGOWet-280, TEGOWet-500 etc. of TEGO company.
The dispersion agent comprised in water-soluble coating composition can comprise: have the alcohol amine salt of the segmented copolymer of acidic-group, comprise and have the segmented copolymer of the polymkeric substance of good affinity to above-mentioned pigment or comprise the solution of this segmented copolymer.By using this dispersion agent, disperseing thus forming pigment-water dispersion liquid while the stable mixing of granules of pigments can be made.In addition, the interior again cohesion of surface treated metallic pigment can be prevented.This dispersion agent can comprise: purchased from DISPERBYK-180, DISPERBYK-182, DISPERBYK-190, DISPERBYK-192, DISPERBYK-2012 etc. of BYK company.
The total amount of coating based composition, the amount of described dispersion agent can in the scope of 0.1 ~ 2 % by weight.When the amount of dispersion agent is less than 0.1 % by weight, the particle diameter of dispersing material can be uneven and the storage quality of dispersing material can be deteriorated.When the amount of dispersion agent is more than 2 % by weight, the water tolerance of coating can reduce.
Can produce and suppress the pin-hole phenomena that occurs during baking coating by foam in limit combination according to the defoamer that comprises in the coating composition of illustrative embodiments.The defoamer of whole amount can be added when preparing coating composition.Alternately, can first a part of defoamer be added in pigment-water dispersion liquid, the foam produced when preparing pigment-water dispersion liquid to remove.
The total amount of coating based composition, the amount of defoamer can in the scope of 0.1 ~ 1.5 % by weight.When the amount of defoamer is less than 0.1 % by weight, the defoaming of coating composition can be more weak and the pin-hole phenomena of coating can occur.When the amount of defoamer is more than 1.5 % by weight, water tolerance can reduce.Defoamer can comprise the DF-110D purchased from AirProduct company, the SN-DEFORMER1320 purchased from Sannopco company, BYK-028 purchased from BYK company.
Water-soluble coating composition according to illustrative embodiments can comprise tackifier.This coating composition makes shell expand and expand display structure viscosity thus by carrying out neutralizing with amine compound.But, utilize said structure viscosity can be inadequate to control viscosity.In order to supplementary viscosity, tackifier can be used.By jointly using based on acrylic acid alkaline viscosity increase type emulsion and giving good thixotropy based on urethane-modified polyester based association type tackifier and obtain molecule, thus improve the directional property of particle.The good appearance of coating can be obtained.Particularly, the thixotropy viscosity based on acrylic acid alkaline viscosity increase type solution can be obtained and realize good coating processability.Tackifier can comprise NOPALL-642, NOPALLUT-666, SN-THICKENER617, SN-THICKENERAM-1, NOPALL700N etc. purchased from Sannopco company.
The total amount of coating based composition, the amount of tackifier can in the scope of 0.1 ~ 1.0 % by weight.When this amount is less than 0.1 % by weight, the work defect comprising coating composition flow can be produced in the spray booth with high humidity.When this amount is more than 1.0 % by weight, defect, albinism etc. that coating composition storage quality declines, forms fine particle can be there is.
Neutralizing agent can be used in the water-soluble coating composition according to illustrative embodiments with the pH value of control composition.The total amount of coating based composition, the amount of neutralizing agent can in the scope of 0.1 ~ 3 % by weight.When the amount of neutralizing agent is less than 0.1 % by weight, the directional property of particle can reduce and the storage quality of coating composition can reduce thus re-uniting or precipitating of pigment occurs.When the amount of neutralizing agent is more than 3 % by weight, solvent resistance particularly alkali resistance can be deteriorated.The pH value of coating composition can remain on about 7.5 ~ 8.5.Neutralizing agent can comprise amine compound, such as, be the DMAE, ammonia, triethylamine etc. of AMIETOLM21 purchased from the common name of TAMINCO company.
Can be primary solvent according to the water comprised in the water soluble paint for automobile composition of illustrative embodiments.Water can replace organic solvent and can prepare eco-friendly water-soluble coating composition.Water can be any type, comprises deionized water, pure water etc.
Can utilize and form coating according to the water soluble paint for automobile composition of illustrative embodiments.
The method such as aerial spraying, electrostatic applications can be utilized to implement coating process.When described coating composition is used as the bottom coating composition forming vehicle top coating, based on the coating of solidification, the preferred thickness of coating can be about 10 ~ 25 microns.Top painting can comprise undercoat and Clear coating.
When described coating composition is used as the bottom coating composition of automobile, the water-soluble coating composition according to illustrative embodiments can be coated with, then at about 80 DEG C, toasts about 2 ~ 5 minutes.Then, the coating of the transparent coating composition of about 20 ~ 40 minutes can be carried out at about 140 ~ 150 DEG C, thus make this two coating generation bridge joints and oven dry simultaneously.The generation of flowing and stain can be prevented and can improve through the baking water tolerance of coating and the directional property of metallic particles.In addition, the coating with good appearance (comprising image definition), good mechanical properties (adhesiveproperties comprising adhesivity, shock resistance, resistance to bending, chipping resistance and coat in overbaking coating again) can be formed.
The present invention is described in detail below with reference to synthesis example, embodiment, comparative example etc.
synthesis example 1
the preparation of alkali swellable core-shell structure copolymer resin
Be that the dibutyl tin laurate of the polycarbonate polyol of 2,000, the dimethylol propionic acid of 64 weight parts, the N-Methyl pyrrolidone of 190 weight parts and 0.3 weight part joins in reaction vessel by the molecular weight of 23 weight parts.Temperature is elevated to 65 DEG C.Then, slowly add 4 of 220 weight parts, 4 isocyanate group cyclohexyl-methanes.Temperature be elevated to 80 DEG C and keep this temperature, making NCO equivalent reach 970, prepare prepolymer thus.At the temperature of 25 ~ 35 DEG C, the triethylamine of the ion exchanged water of 400 weight parts and 50 weight parts is mixed and rapid stirring.Add prepolymer with 20 minutes, thus prepare aqueous dispersant.Then, the mixture of 40 weight part ion exchanged waters and 9.0 weight part 80% hydrazine hydrates is added to make chain extension.Prepared by the self-emulsifying type urethanum aqueous dispersant with the acid number of 95mgKOH/g and the solids content of 31%.
The temperature that the urethanum aqueous dispersant so prepared by 10g joins 170g controls in the ion exchanged water of 80 DEG C.23g methyl methacrylate, 20g n-BMA, 22g n-butyl acrylate, 4g vinylformic acid 2-hydroxy methacrylate and 1g methacrylic acid is added under stirring.Prepare monomer pre-emulsification thing thus.This monomer pre-emulsification thing of 43g is joined in flask.After 10 minutes, add 10% ammonium persulfate solution be dissolved in deionized water, then stir.After 10 minutes, monomer pre-emulsification thing is dripped with 4 hours, then the mixture of 17g methyl methacrylate, 5g methacrylic acid and 10g vinylformic acid 2-hydroxy methacrylate is dripped with 3 hours, neutralize this product in 40 ~ 50 DEG C with 10% dimethylethanolamine of 60g after 2 hours, preparation has the alkali swellable core-shell structure copolymer resin of the median size of the solid content of 24.6%, the pH value of 6.5 and 150nm thus.
synthesis example 2
the preparation of curing agent mixture 1
244g ethylene glycol butyl ether, 127g Virahol and 114gN-N-methyl-2-2-pyrrolidone N-are dropped in container, then stirs.220g wetting ability melamine resin Cymel327 is added under stirring.Stir after 10 minutes, at the temperature of 25 ~ 30 DEG C, add 220g hydrophobicity melamine resin Setamine-146 and stir 20 minutes.Add 36.9g tensio-active agent Surfynol-440, prepare curing agent mixture 1 thus.
synthesis example 3
the preparation of curing agent mixture 2
244g ethylene glycol butyl ether, 127g Virahol and 114gN-N-methyl-2-2-pyrrolidone N-are dropped in container, then stirs.Under stirring, add 176g wetting ability melamine resin Cymel327.Stir after 10 minutes, at the temperature of 25 ~ 30 DEG C, add 246g hydrophobicity melamine resin Setamine-146 and stir 20 minutes.Add 36.9g tensio-active agent Surfynol-440, prepare curing agent mixture 2 thus.
synthesis example 4
the preparation of curing agent mixture 3
244g ethylene glycol butyl ether, 127g Virahol and 114gN-N-methyl-2-2-pyrrolidone N-are dropped in container, then stirs.Under stirring, add 352g wetting ability melamine resin Cymel327.Stir after 10 minutes, at the temperature of 25 ~ 30 DEG C, add 88g hydrophobicity melamine resin Setamine-146 and stir 20 minutes.Add 36.9g tensio-active agent Surfynol-440, prepare curing agent mixture 3 thus.
synthesis example 5
the preparation of pigment-water dispersion liquid
In order to prepare blue pigments aqueous dispersions, 380g deionized water, 100g being dropped in container as the DF-110 of defoamer as DISPERBYK-2012 and 10g of dispersion agent, then stirs.Add the G-314 of 300g as blue pigments, then carry out stirring in advance for about 1 hour.Then, utilize sand mill to make reactant be dispersed into particle diameter and be less than about 5 microns.Add 18g10% dimethylethanolaminesolution solution and 72g deionized water, prepare blue pigments aqueous dispersions thus.
embodiment 1
The alkali swellable core-shell structure copolymer resin of preparation in 35g synthesis example 1 and 10g deionized water are dropped in container-1, then stirs.Slowly add the curing agent mixture 1 of preparation in 7g synthesis example 2, then stir 20 minutes.Observe particle diameter and be less than about 5 microns.Add the Norooster-8210 (Norooholdings company) of 6g as vibrin, then stir 20 minutes.
One by one the pigment-water dispersion liquid of preparation in 3g metallic pigment (STAPAILHydrolan9157), 6g synthesis example 5,4g are put in container-2 as DISPERBYK-192 and 0.9g of dispersion agent as the TEGOWet500 of wetting agent as the 2-Rutgers 612 of solubility promoter 2,1.1g as the 2-Ethylhexyl Alcohol of solubility promoter 1,1g, then this mixture is stirred 10 minutes.
Mixture in container-2 is dropped in container-1, then stir 10 minutes.One by one add 0.2g tackifier 1 (NOPALL642), 0.4g tackifier 2 (NOPALLUT-666) and 2g 10% dimethylethanolaminesolution solution as neutralizing agent, then stir 20 minutes.The final viscosity of the product so obtained is adjusted to 55 seconds (No. 4 Ford cup), prepare the water soluble paint for automobile composition according to illustrative embodiments thus.
embodiment 2 ~ 3
By implementing the step identical with step described in embodiment 1 and adopting the composition shown in table 1 and amount thereof, and prepare water soluble paint for automobile composition.
comparative example 1 ~ 4
By implementing the step identical with step described in embodiment 1 and adopting composition shown in table 1 and amount thereof, and prepare water soluble paint for automobile composition.
table 1
In table 1,1) represent Polyester Resin Water Soluble purchased from Norooholdings company and Norooster-8210; 2) representative is used for the metallic pigment of watersoluble pigment composition and the STAPAILHydrolan9157 purchased from ECKART company; 3) 2-Ethylhexyl Alcohol is represented; 4) 2-ethylhexyl glycol is represented; 5) representative has the segmented copolymer of the polymkeric substance of affinity and the DISPERBYK-192 purchased from BYK company to pigment; 6) nonionic organic surfactant type wetting agent and the TEGOWet500 purchased from TEGO company is represented; 7) nonionic non-silicon type tensio-active agent and the DF-110D purchased from AirProduct company is represented; 8) acrylic alkalescence and viscosity increase type emulsion and the NOPALL642 purchased from Sannopco company is represented; 9) representative is based on urethane-modified polyester based association type tackifier and the NOPALLUT-666 purchased from Sannopco company; 10) dimethylethanolaminesolution solution of 10% is represented.
for assessment of the experiment of physical properties
Prepare the water-soluble coating composition obtained by embodiment 1 ~ 3 and comparative example 1 ~ 4.In order to evaluation of physical properties, form prime coat, surfacer layer and top coat seriatim.
Cation electroplating paint composition is coated on the exemplar for testing automobile coating composition, thus forms prime coat.Be coated with the KED-2000Gray purchased from Norooholdings company, at about 150 DEG C, in the relative humidity of about 70%, then carry out the solidification of about 25 minutes.Then, the WP-3000 purchased from Norooholdings company is coated on the primer coating of so formation, at about 140 DEG C, under the relative humidity of about 70%, then carries out the solidification of about 30 minutes, form surfacer layer thus.
Then, top coat is formed.First, the water-soluble coating composition of preparation in embodiment 1 ~ 3 and comparative example 1 ~ 4 is coated in surfacer coating as undercoat.The solidification process of about 3 minutes is implemented at about 80 DEG C.After solidification terminates, be coated with the DSC-3000 purchased from Norooholdings company as clear coating composition.Surfacer layer forms top coat.
In order to assess, make surfacer layer form the thickness being about 30 ~ 40 microns, make undercoat form the thickness being about 10 ~ 25 microns, make Clear coating form the thickness being about 30 ~ 50 microns.
The evaluation result of various character is shown in table 2.
Table 2
In table 2, each character is obtained by following experiment and appraisal procedure.
Stability: described coating composition is preserved 5 days at 40 DEG C.No. 4 FordCup are utilized to assess the concentration difference before and after preserving.Assessment differences in viscosity whether approximately-20% ~+20% scope in.
Mobility: when being coated with described composition, observe mobility status by staff.
Stain: when being coated with described composition and after being solidified to form coating, observed the generation degree of stain by staff.
Glossiness: whether be more than 90 from the glossiness of each coating of the angle views of 60 °.
Outward appearance (sharpness of image): utilize the structure spectrum of wave front aberration DOI to coatingsurface to analyze, to assess the size and appearance character showing to bend.
Grain orientation: the direction mutation status being observed metallic pigment in coating by staff.
Water tolerance: exemplar is soaked 10 days in about 40 ~ 50 DEG C of warm water and observes coating by staff.
Adhesivity: form about 100 grids with about 2mm × 2mm size, by tape adhesion in the coating comprising grid.Then, tape stripping is observed the separate stage of coating by staff.
Shock resistance: use the counterweight of about 300g and use the Apparatus for Impacting at low-temp of DuPont company, assesses shock resistance degree by the impact applied from about 40cm height.
Resistance to bend(ing): this sample is bent along having the circular steel being about 3/16 inch circular long, and the coating of observing this sample is to check crack and the generation be separated.
Chipping resistance: kept 4 hours at-40 DEG C by exemplar, then applies to impact to this sample under the pressure of 4 bar with Honda stone.Observe in coating the quantity with the separated part being about 1 ~ 2mm length and whether be less than 10 and whether the quantity with the separated part being about more than 2mm length is less than 1.
Coat the adhesivity in overbaking coating again: after coating on floating coat by water-soluble bottom coating composition and transparent composition, implement to solidify normally, this coating is carried out 1 hour overbaking at about 150 DEG C.Then, under normal operation bottom coating composition and transparent composition are coated with and are solidified.Enforcement adhesivity is tested, and determines that adhesivity is about more than 90/100.
For the symbol of specifying, ◎ represents outstanding, and zero representative is good, and △ representative is general, and × representative is poor.
As shown in table 2, the character good and outstanding according to the major part display in the water-soluble coating composition of illustrative embodiments.When to when comparing according to each composition of illustrative embodiments, the amount of the inflatable core-shell structure copolymer resin of utility alkali changes the physical properties comprising outward appearance, storage quality, coating processability, grain orientation, water tolerance etc.
As mentioned above, by using urethanum aqueous dispersant as emulsifying agent, described water-soluble coating composition can be made to comprise alkali swellable core-shell structure copolymer resin and the reduction of water tolerance can be prevented.Described water-soluble composition also can have good coating processability, this is because due to the generation of flowing and stain when structural viscosity can limit coating.To utilize in carrying out with neutralizing agent (as amine compound) and time core-shell structure copolymer resin expand and enlargement phenomenon, can structural viscosity be obtained.In addition, good image definition can be had according to the coating composition of illustrative embodiments and to the had good adhesion of overbaking coating when being coated with again.
Automobile water-based dissolubility primary coating composition is can be used as according to the coating composition of illustrative embodiments.Said composition can comprise transoid core/shell microgel resin and urethane dispersion, and can be used as comprising by making acrylic resin and hydrophobicity melamine resin react the automobile water-based dissolubility primary coating composition of prepared trimeric cyanamide aqueous dispersant.
Above-mentioned be illustrative embodiments illustration and be not understood as that to its restriction.Although described some illustrative embodiments, those skilled in the art can make many amendments by easily understanding in the exemplary embodiment when not deviating from fact new instruction of the present invention and advantage.Therefore, all this amendments are intended that being included in as defined by the appended claims in the scope of the invention.In the claims, functional specification clause is intended that contains described structure herein when performing institute's recited function, and not only contains structural equivalents but also contain equivalent structure.Therefore, should understand and be above-mentionedly the illustration of various illustrative embodiments and do not should be understood to and be confined to concrete illustrative embodiments disclosed herein, the amendment of illustrative embodiments disclosed herein and other illustrative embodiments are intended that and comprise within the scope of the appended claims.
Claims (9)
1. a water-soluble coating composition, based on the total amount of described coating composition, it comprises:
20 ~ 50 % by weight by using urethanum aqueous dispersant as the alkali swellable core-shell structure copolymer resin manufactured by emulsifying agent, wherein said alkali swellable core-shell structure copolymer resin comprises core and in described circumnuclear shell part, described core is by making described emulsifying agent and the first monomer mixture carry out letex polymerization and obtain, described shell part utilizes second comonomer mixture to be formed, the Mixing ratio by weight of wherein said first monomer mixture and described second comonomer mixture is in the scope of 65 ~ 85: 15 ~ 35, based on the total amount of described first monomer mixture and second comonomer mixture, the amount of described emulsifying agent is 5 ~ 30 % by weight, what wherein said first monomer mixture comprised the cycloalkyl methacrylate with 4 ~ 12 carbon atoms of 75 ~ 90mol% and 10 ~ 25mol% can copolymerization list alkylidene group unsaturated monomer, described second comonomer mixture comprises the methacrylic acid of 20 ~ 40mol% and copolymerizable single alkylidene group unsaturated monomer of 60 ~ 80mol%,
The curing agent mixture of 3 ~ 10 % by weight, based on the total amount of described curing agent mixture, described curing agent mixture comprises: the ethylene glycol butyl ether of 10 ~ 30 % by weight, the Virahol of 10 ~ 30 % by weight, 5 ~ 15 % by weight METHYLPYRROLIDONE, the wetting ability melamine resin of 25 ~ 35 % by weight, hydrophobicity melamine resin and 2 ~ 5 % by weight of 15 ~ 25 % by weight nonionogenic tenside;
The vibrin of 2 ~ 10 % by weight; And
The water of surplus,
Wherein said urethanum aqueous dispersant is prepared by the following method:
Make two functional isocyanate compounds, have 1,500 ~ 2, the polycarbonate polyol of the molecular weight of 500 and the compound with at least two hydroxy functional groups and a carboxylic acid functional react, and form prepolymer thus, have isocyanate functional group in the end of this prepolymer; And
By described prepolymer in amine aqueous solution, then implement chain extension process.
2. coating composition according to claim 1, wherein said two functional isocyanate compounds are selected from least one in 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4-vulcabond cyclohexyl-methane.
3. coating composition according to claim 1, the wherein said compound with at least two hydroxy functional groups and a carboxylic acid functional is at least one in dimethylol propionic acid and dimethylolpropionic acid.
4. coating composition according to claim 1, wherein said urethanum aqueous dispersant has the acid number of 90 ~ 100mgKOH/g and the solids content of 28 ~ 34%.
5. coating composition according to claim 1, also comprises: the metallic pigment of 1 ~ 3 % by weight, the pigment-water dispersion liquid of 5 ~ 50 % by weight, 3 ~ 6 % by weight solubility promoter, 0.1 ~ 2 % by weight wetting agent, 0.1 ~ 2 % by weight dispersion agent, the defoamer of 0.1 ~ 1.5 % by weight, tackifier and 0.1 ~ 3 % by weight of 0.1 ~ 1.0 % by weight neutralizing agent.
6. form a method for coating, comprising:
Water-soluble coating composition according to claim 1 is coated on base material; And
Make the described coating composition through coating dry.
7. method according to claim 6, wherein said coating formation is the thickness of 10 ~ 25 microns and described coating is the undercoat of vehicle top coating.
8. method according to claim 6, wherein said coating utilizes a kind of method in spraying coating and electrostatic applications and implements.
9. method according to claim 6, implement further:
Clear coating composition is coated in described coating; And
Make the solidification of the described clear coating composition through coating.
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| CN1145084A (en) * | 1994-04-07 | 1997-03-12 | 维诺瓦合成树脂公司 | Process for preparing water-dilutable, air-drying varnish binders and use thereof |
| CN101550308A (en) * | 2008-04-02 | 2009-10-07 | 关西涂料株式会社 | Aqueous coating composition |
| CN101636457A (en) * | 2007-03-22 | 2010-01-27 | 关西涂料株式会社 | Water-based paint compositions and multilayer coating film forming method |
| US20100273930A1 (en) * | 2008-05-26 | 2010-10-28 | Dic Corporation | Coating agent and method for production thereof |
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| KR100457010B1 (en) | 1995-12-30 | 2005-04-19 | 고려화학 주식회사 | Compositions of water-dispersed resins for automobile repair and water-soluble paints containing them |
| KR101057532B1 (en) * | 2003-12-31 | 2011-08-17 | 주식회사 케이씨씨 | Manufacturing method of water-soluble topcoat for automobile |
| KR101018955B1 (en) * | 2003-12-31 | 2011-03-02 | 주식회사 케이씨씨 | Preparing method for water dispersable silicon-acryl-urethane resin and aqueous coating composition for automobile containing said water dispersable silicon-acryl-urethane resin |
| KR101054510B1 (en) | 2004-12-31 | 2011-08-05 | 주식회사 케이씨씨 | Water-based paints that do not require emulsion resins and volatile solvents and cryoprotectants |
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| CN1145084A (en) * | 1994-04-07 | 1997-03-12 | 维诺瓦合成树脂公司 | Process for preparing water-dilutable, air-drying varnish binders and use thereof |
| CN101636457A (en) * | 2007-03-22 | 2010-01-27 | 关西涂料株式会社 | Water-based paint compositions and multilayer coating film forming method |
| CN101550308A (en) * | 2008-04-02 | 2009-10-07 | 关西涂料株式会社 | Aqueous coating composition |
| US20100273930A1 (en) * | 2008-05-26 | 2010-10-28 | Dic Corporation | Coating agent and method for production thereof |
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