CN103183997A - Water-soluble basecoat paint composition for automobiles and method of forming paint layer using the same - Google Patents
Water-soluble basecoat paint composition for automobiles and method of forming paint layer using the same Download PDFInfo
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- CN103183997A CN103183997A CN2012102360695A CN201210236069A CN103183997A CN 103183997 A CN103183997 A CN 103183997A CN 2012102360695 A CN2012102360695 A CN 2012102360695A CN 201210236069 A CN201210236069 A CN 201210236069A CN 103183997 A CN103183997 A CN 103183997A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
- C09D5/16—Antifouling paints; Underwater paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
A water-soluble coating composition, based on the total amount of the coating composition, comprises: 20 to 50 by weight of shell resin-alkaline expandable core manufactured by using a urethane aqueous dispersing agent as an emulsifier, 3 to 10% by weight of a curing agent mixture, 2 to 10% by weight of a polyester resin, and the balance water. Based on the total amount of the curing agent mixture, the curing agent mixture comprises: 10 to 30% by weight of butyl cellosolve, 10 to 30% by weight of isopropanol, from 5 to 15% by weight of N-methyl-2 - pyrrolidone, 25 to 35% by weight of a hydrophilic melamine resin, 15 to 25 % by weight of a hydrophobic melamine resin, and 2 to 5% by weight of a nonionic surfactant. The coating composition has inner natures of a good appearance, water resistance, adhesion, 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 have that good appearance and good mechanical properties and good relating to are flowed and the water-soluble bottom coating composition of the coating processibility of 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 is coated with again on water tolerance, adhesivity, shock resistance, elasticity and the overbaking coating.
Background technology
In automotive industry, coating process is the axis in the manufacturing processed of engine manufacturing processed and steering gear part.Because the rules at the volatile organic compounds (VOC) that discharges have been implemented the several years, thereby the coating process relevant with automobile had wide variation.Particularly, European countries and developed country extremely pay close attention to and limit energetically the use of volatile organic compounds and use the product of volatile organic compounds to apply sanction to comprising the use of restriction volatile organic compounds.
In general, thus easily volatilization and be diffused into gaseous phase naturally and become main topsoil factor in the atmosphere of volatile organic compounds.In addition, volatile organic compounds can have bio-toxicity and chemical reactivity, thereby and becomes a factor that damages the ozone layer and cause Greenhouse effect and produce unpleasant odor.
In view of the restrictive policy that volatile organic compounds is discharged, to the protection of environment and the improvement of Working environment, the amount that reduces volatile organic compounds in the automotive coating composition becomes very important theme.In order to reduce the amount of volatile organic compounds in the automotive coating composition, the dealer has developed the whole bag of tricks.For example, have the highly filled oil-based paint composition shortening enforcement oil-based paint composition required time of coating process thereby prepared, and prepared water-soluble coating composition.The most effectual way that reduces the amount of volatile organic compounds comprises minimizes the amount that comprises volatile organic compounds in the coating composition.In addition, the oil-based paint composition is replaced by water-soluble coating composition gradually.Especially effectively, can require to replace comprising with water-soluble bottom coating composition the oil base bottom coating composition of the organic solvent of about 50～70 weight %.Therefore, the dealer has carried out the development research to water-soluble bottom coating composition energetically.The top coating composition can comprise bottom coating composition and clear coating composition.
In general, the oil-based paint composition can comprise acrylic resin, melamine resin, vibrin, polyurethane resin, organic solvent etc.The oil-based paint composition can have preferable image sharpness and favorable mechanical character (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 main resin and assisted resin (as vibrin and polyurethane dispersion) together with the wetting ability melamine resin.Water-soluble coating composition also can comprise main resin, assisted resin and hydrophobicity trimeric cyanamide aqueous dispersant.When comparing with the oil-based paint composition, water-soluble coating composition has relatively poor comprising and is flowing in interior workability and relatively poor water tolerance.
Widely used water-soluble coating composition can comprise: acrylic resin and transoid and core/shell type microgel resin, also be useful on and improve chipping resistance and the direction-sense assisted resin of luminous pigment (as urethane ester dispersion and vibrin).
Especially, when preparation hydrophobicity trimeric cyanamide aqueous dispersant, can be with acrylic resin as reacting resin.Yet, owing in microgel resin, use the anionic reactive emulsifying agent, thereby use the water tolerance of the coating that coating composition forms with above-mentioned composition to reduce.
As employed solidifying agent in the automobile water-based soluble paint composition, can enumerate aminoresin, block isocyanate compound, nitrogen heterocycle propane compound, epoxy compounds etc.The aminoresin that may be used as solidifying agent can comprise wetting ability melamine resin and hydrophobicity melamine resin.The wetting ability melamine resin can directly join in the water-soluble coating composition.Yet, for the physical properties (comprising adhesivity) that promotes composition, can be with the hydrophobicity melamine resin as the melamine resin aqueous dispersant.
Can react by making specific acrylic resin and hydrophobicity melamine resin, and obtain hydrophobicity trimeric cyanamide aqueous dispersant.Therefore, can reduce the turnout of water-soluble coating composition by using the hydrophobicity melamine resin.
When only comprising the wetting ability melamine resin, the adhesivity of clear coating composition being coated again on the overbaking coating of bottom coating composition can variation.
Summary of the invention
Some embodiments provide the new type water-solubility coating composition of have good appearance (comprising glossiness and image definition) and good mechanical properties (comprise on water tolerance, sticking property, shock resistance, resistance to bending and the overbaking coating adhesiveproperties of coating) again.
Some other embodiments provide the method for 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 weight % pass through use urethanum aqueous dispersant as the alkali swellable nuclear-shell resin of emulsifying agent manufacturing, the curing agent mixture of 3～10 weight % (based on the total amount of curing agent mixture, comprises the ethylene glycol butyl ether of 10～30 weight %, the Virahol of 10～30 weight %, the N-N-methyl-2-2-pyrrolidone N-of 5～15 weight %, the wetting ability melamine resin of 25～35 weight %, the hydrophobicity melamine resin of 15～25 weight %, nonionogenic tenside with 2～5 weight %), the vibrin of 2～10 weight %, and the water of surplus.
In some embodiments, can prepare the urethanum aqueous dispersant by the following method: make two functional isocyanate compounds, have 1,500～2, the polycarbonate polyol of 500 molecular weight and have at least two hydroxy functional groups and the compound of a carboxylic acid functional reacts, and be formed on the prepolymer that the end has the isocyanate functional group.Then, this prepolymer can be scattered in the aqueous solution of amine, implement the chain extension process then.
In some embodiments, two functional isocyanate compounds can be to be selected from least a in 1,6-, six methylene vulcabond, isophorone diisocyanate and 4, the 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 a in dimethylol propionic acid and the dimethylolpropionic acid.
In some embodiments, alkali swellable nuclear-shell resin can comprise the shell part of examining and centering on this nuclear.Can obtain nuclear by the letex polymerization of emulsifying agent and first monomer mixture.Can use second monomer mixture and obtain the shell part.Here, the weight ratio of mixture of first monomer mixture and second monomer mixture can be 65～85: in 15～35 the scope; Based on the total amount of first monomer mixture and second monomer mixture, the amount of described emulsifying agent can be 5～30 weight %.
In some embodiments, first monomer mixture can comprise the methacrylic acid cycloalkyl ester with 4～12 carbon atoms of 75～90mol% and copolymerizable single alkylidene group unsaturated monomer of 10～25mol% (copolymerizable monoalkylenic unsaturated monomer); Second monomer mixture can comprise the methacrylic acid of 20～40mol% and copolymerizable single alkylidene group unsaturated monomer of 60～80mol%.
In some embodiments, the urethanum aqueous dispersant can have the acid number of 90～100mgKOH/g and 28～34% solids content.
In some embodiments, water-soluble coating composition also can comprise: the defoamer of the wetting agent of the pigment-water dispersion liquid of the metallic pigment of 1～3 weight %, 5～50 weight %, the solubility promoter of 3～6 weight %, 0.1～2 weight %, the dispersion agent of 0.1～2 weight %, 0.1～1.5 weight %, the tackifier of 0.1～1.0 weight % and the neutralizing agent of 0.1～3 weight %.
According to some embodiments, in the method that forms coating, water-soluble coating composition is coated on the base material.The total amount of coating based composition, water-soluble coating composition comprises: 20～50 weight % pass through use urethanum aqueous dispersant as the alkali swellable nuclear-shell resin of emulsifying agent manufacturing, the curing agent mixture of 3～10 weight % (based on the total amount of curing agent mixture, comprises the ethylene glycol butyl ether of 10～30 weight %, the Virahol of 10～30 weight %, the N-N-methyl-2-2-pyrrolidone N-of 5～15 weight %, the wetting ability melamine resin of 25～35 weight %, the hydrophobicity melamine resin of 15～25 weight %, nonionogenic tenside with 2～5 weight %), the vibrin of 2～10 weight %, and the water of surplus.Then, make through the coating composition dries.
In some embodiments, described coating can form 10～25 microns thickness, and this coating is the undercoat of automobile top coat.
In some embodiments, can utilize a kind of method in spraying coating and the electrostatic applications to implement coating.
In some embodiments, can further implement clear coating composition is coated step on the described coating.
As mentioned above, when using described water-soluble bottom coating composition to form coating, flowing and stain after can preventing from being coated with.In addition, can improve the water tolerance of baking coating and the directional property of metallic particles.In addition, can under the situation of not using assisted resin, obtain to have the coating of good chipping resistance.
Embodiment
To more fully describe various illustrative embodiments below, wherein illustrate some illustrative embodiments.Yet, can adopt many different forms to implement the present invention, and not should be understood to the illustrative embodiments that the present invention is confined to state herein.On the contrary, by providing these illustrative embodiments to make this specification sheets be thoroughly and fully convey to those skilled in the art completely and with scope of the present invention.In the accompanying drawings, for clarity sake, size and the relative size in each layer and each zone are scalable.
Term used herein " and/or " comprise one or more arbitrary combination in the relevant Listed Items and all combinations.
Although it should be understood that and can use the term first, second, third, etc. to describe various elements and/or composition herein, these elements and/or composition should not be subjected to the restriction of these terms.These terms only are used for an element or composition and another element or composition are differentiated.Therefore, under situation without departing the teaching of the invention, first element described below or composition can be described as second element or composition.
Term used herein is only to illustrate that concrete illustrative embodiments is that purpose is not intention restriction the present invention.Odd number used herein " one ", " one " and " being somebody's turn to do " are intended that and also comprise plural form, unless context spells out.What will also be understood that is, when using term " to comprise " herein and/or when " comprising ", specifically refer to the existence of institute's features set forth, integer, step, operation, element and/or composition, but do not get rid of existence or the interpolation of one or more further features, integer, step, operation, element, composition and/or its combination.
Unless otherwise prescribed, all terms used herein (comprising technology and scientific terminology) have the implication identical with the implication of those skilled in the art in the invention's common sense.What will also be understood that is, should be counted as having the implication consistent with the implication in this context and the association area such as defined term in the common dictionary, and will not be counted as Utopian implication or excessive formal implication, unless so definition clearly herein.
Hereinafter, will be to being described in detail according to the illustrative embodiments of coating composition of the present invention and the method for using this coating composition to form coating.
In the exemplary embodiment, the total amount of coating based composition, described coating composition comprises: 20～50 weight % pass through use urethanum aqueous dispersant as the alkali swellable nuclear-shell resin of emulsifying agent manufacturing, (based on the total amount of curing agent mixture, it comprises the ethylene glycol butyl ether of 10～30 weight % to the curing agent mixture of 3～10 weight %, the Virahol of 10～30 weight %, the N-N-methyl-2-2-pyrrolidone N-of 5～15 weight %, the wetting ability melamine resin of 25～35 weight %, the hydrophobicity melamine resin of 15～25 weight %, nonionogenic tenside with 2～5 weight %), the vibrin of 2～10 weight %, and the water of surplus.
To be described in detail formation each composition according to the coating composition of illustrative embodiments below.
Can be main resin by using the urethanum aqueous dispersant as the prepared alkali swellable nuclear-shell resin of emulsifying agent, and can prepare this alkali swellable nuclear-shell resin by the following method: utilize letex polymerization to form nuclear, and be added drop-wise to institute by the monomer mixture that will comprise hydrophilic ethylene base monomer and form to examine and form the circumnuclear wetting ability shell portion that is centered around.
Thereby by using described alkali swellable nuclear-shell resin as main resin and with neutralize extension and the expansion acquisition structural viscosity of shell part to show shell of this nuclear-shell resin of amine compound, can obtain the good workability (it comprises flowability) of coating composition.In addition, the directional property of particle can be improved, the coating with good surface appearance and granular sensation can be formed simultaneously.
Can prepare the urethanum aqueous dispersant by the following method: make two functional isocyanate compounds, have 1,500～2, the polycarbonate polyol of 500 molecular weight and have at least two hydroxy functional groups and the compound of a carboxylic acid functional reacts, be formed on the prepolymer that the end has the isocyanate functional group thus, prepolymer is scattered in the aqueous solution of amine, implements the chain extension step then.
Two functional isocyanate compounds for the preparation of the urethanum aqueous dispersant can comprise: be selected from least a in 1,6 hexamethylene diisocyanate, isophorone diisocyanate and 4, the 4-vulcabond cyclohexyl-methane.
Can comprise at least a in dimethylol propionic acid and the dimethylolpropionic acid for the preparation of the compound with at least two hydroxy functional groups and a carboxylic acid functional of urethanum aqueous dispersant.
The neutralizing agent that is used for the water-dispersion of prepolymer can comprise triethylamine, ammonia etc.
In order to utilize the urethanum aqueous dispersant to prepare alkali swellable nuclear-shell resin as emulsifying agent,, can use urethanum aqueous dispersant based on total amount 5～30 weight % of monomer as emulsifying agent.More preferably, can use the urethanum aqueous dispersant of 10～20 weight % to implement letex polymerization.The urethanum aqueous dispersant can have the acid number of 90～100mgKOH/g and 28～34% solids content.
Alkali swellable nuclear-shell resin can be by implementing at least two polymkeric substance that step is prepared.At first, first monomer mixture that can be prepared as follows, it comprises other copolymerizable single alkylidene group unsaturated monomer of the methacrylic acid cycloalkyl ester of the cycloalkyl that has 4～12 carbon atoms comprising of 75～90mol% and 10～25mol%.In the case, the total amount of these two kinds of monomers can be 100mol%.
Then, second monomer 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%.
First monomer mixture by making 65～85 weight % and second monomer mixture of 15～35 weight % carry out copolymerization step by step, can prepare described alkali swellable nuclear-shell resin.This resin can comprise the carboxylic acid group who derives from least part of Ionized methacrylic acid.
The methacrylic acid cycloalkyl ester that has the cycloalkyl of 4～12 carbon atoms for the preparation of comprising of first monomer mixture can comprise: butyl acrylate, butyl methacrylate, Octyl acrylate, isobornyl acrylate, 2-EHA, isobornyl methacrylate, methacrylic acid 2-ethylhexyl, dodecylacrylate, lauryl methacrylate, and composition thereof etc.Preferred compound in the above-claimed cpd can comprise: butyl acrylate, butyl methacrylate and composition thereof.
Copolymerizable single alkylidene group unsaturated monomer for the preparation of first monomer mixture can comprise: methyl methacrylate, methyl acrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, isopropyl acrylate, methacrylic acid 2-methoxyl group ethyl ester, 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-hydroxyl butyl ester, the own ester of vinylformic acid 6-hydroxyl, and composition thereof etc.In these compounds, preferably methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, 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 monomer mixture can comprise: vinylbenzene, Vinyl toluene, vinyl cyanide, methacrylonitrile, methyl methacrylate, methyl acrylate, ethyl propenoate, Jia Jibingxisuanyizhi, 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 esters, vinylformic acid 4-hydroxyl butyl ester, the own ester of vinylformic acid 6-hydroxyl, methacrylic acid 2-methoxyl group ethyl ester, methacrylic acid 2-ethoxy ethyl ester, their mixture etc.
With regard to the emulsification copolymerization, can use the radical initiator that comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate etc.Can in the saturated atmosphere of nitrogen, in about 70～80 ℃ temperature range, under atmospheric pressure implement the copolymerization of these monomer mixtures.By add neutralizing agent (as ammonia and amine compound) can neutralize the acquisition carboxylic acid about 80～100%.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 nucleocapsid resin can be 20～50 weight %.When this measured less than 20 weight %, the viscosity of the coating composition of preparation like this can reduce and be coated with workability and water tolerance can reduce.When this amount surpasses 50 weight %, the sticking property of coating in the time of can suppressing to be coated with again.
When utilizing the prepared alkali swellable nuclear-shell resin of above-mentioned steps, can control the thixotropy of water-soluble bottom coating composition and realize that good workability does not produce mobile and stain simultaneously during with the water-soluble bottom coating composition of top coating composition as automobile.This coating composition can show good surface appearance, adhesivity, shock resistance and anti-twist property.Particularly, can improve the water tolerance that may reduce because of emulsifying agent.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 can be with the urethanum aqueous dispersant as emulsifying agent, so can under the situation that does not add the urethanum dispersion agent that is used for the raising chipping resistance independently, obtain to have the coating of good chipping resistance.
Hereinafter, curing agent mixture is described in detail.
When directly adding in the water-soluble coating composition, can produce cohesive force hardly to the wetting ability melamine resin.Yet, when directly adding in the water-soluble coating composition, can produce cohesive force to the hydrophobicity melamine resin.The generation of cohesive force can make outward appearance and physical properties and the adhesivity variation of coating.
According to illustrative embodiments, the curing agent mixture that comprises hydrophilic resin, hydrophobic resin and nonionogenic tenside can be used for optimizing the compatibility with alkali swellable nuclear-shell resin and water.Therefore, the adhesivity of described coating and the overbaking coating when being coated with again is for 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 N-N-methyl-2-2-pyrrolidone N-of the Virahol of the ethylene glycol butyl ether of 10～30 weight %, 10～30 weight %, 5～15 weight %, the wetting ability melamine resin of 25～35 weight %, the hydrophobicity cymel of 15～25 weight % and the tensio-active agent of 2～5 weight %.
When the amount of ethylene glycol butyl ether during less than 10 weight %, melamine resin can not fully dissolve and outward appearance and the physical properties of coating can variation.When the amount of ethylene glycol butyl ether surpassed 30 weight %, so the thixotropy index (TI) of the coating composition of preparation meeting reduction and coating workability can reduce.Therefore, based on the total amount of curing agent mixture, the preferred amounts of ethylene glycol butyl ether can be in the scope of 10～30 weight %.
Based on the total amount of curing agent mixture, the amount of Virahol can be 10～30 weight %.When this amount during less than 10 weight % the storage quality of coating composition can reduce, when this amount surpasses 30 weight % when making coating dry pin hole phenomenon and cracking (cutting) phenomenon can take place.
The N-N-methyl-2-2-pyrrolidone N-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 N-N-methyl-2-2-pyrrolidone N-can be in the scope of 5～15 weight %.When the raising degree of the amount of N-N-methyl-2-2-pyrrolidone N-coating composition storage quality during less than 5 weight % can reduce, the TI of coating composition can reduce when the amount of N-N-methyl-2-2-pyrrolidone N-surpasses 15 weight %, the coating cracking defective that can produce mobile defect and take place to cause owing to solidifying when implementing coating process.
The wetting ability melamine resin can comprise: available from the Cymel-202 of Cytec company, Cymel-325, Cymel-327, Cymel-370, Cymel-385 and Cymel-254 and available from the Lubipal-052 of BASF AG.
The hydrophobicity melamine resin can comprise: available from M3-1280 and the M3-1286 of Noroo Paint company, available from Setamine-146 and the Setamine-138 of Nuplex company, available from Cymel-683, Cymel-1158 and the Cymel-1156 of Cytec company.
The weight ratio of mixture of wetting ability melamine resin and hydrophobicity melamine resin can be in 50: 50～70: 30 scope.The adhesiveproperties of coating can reduce when being coated with when the amount of wetting ability melamine resin surpasses this given range again, and the exterior quality of water-soluble bottom coating composition can reduce when the amount of hydrophobicity melamine resin surpasses this given range.
As the tensio-active agent for the preparation of curing agent mixture, can use nonionogenic tenside.Based on the total amount of curing agent mixture, the amount of tensio-active agent can be in the scope of 2～5 weight %.When the amount of tensio-active agent during less than 2 weight %, the compatibility of curing agent mixture and water-soluble coating composition can variation.When the amount of tensio-active agent surpassed 5 weight %, total cost and the water tolerance that can increase coating composition can reduce.In addition, the surface tension of water-soluble bottom coating composition can descend and the cratering phenomenon can take place.Tensio-active agent can comprise available from the Surfynol-420 of Air Products company, Surfynol-440, Surfynol-465 etc.
Hereinafter, will be illustrated according to the vibrin as assisted resin to comprising in the coating composition of illustrative embodiments.
Described vibrin is to have the dispersion type resin that is about the 50nm particle diameter.The total amount of coating based composition, the amount of vibrin can be in the scope of 2～10 weight %.When vibrin less than 2 weight % the time, the adhesivity of particle and directional property can reduce.When the amount of vibrin surpassed 10 weight %, physical properties (comprising shock resistance, resistance to bending etc.) can variation.Vibrin can comprise the Norooster 8210 available from Noroo holdings company.
The metallic pigment that comprise in the automobile water-based soluble paint composition can have the mean diameter (D50) that is about 5～40 microns.Can be by surface of pigments is handled this pigment be changed over the type that is 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, can enumerate aluminum paste.Described metallic pigment can comprise the aluminum paste product available from the Hydran series of Eckardt company.The total amount of coating based composition can suitably be controlled the amount of this pigment in the scope of 1～3 weight %.
The colo(u)rant dispersion solution that comprises in the water-soluble coating composition according to illustrative embodiments can comprise that mineral dye and pigment dyestuff are as pigment.The total amount of coating based composition, the amount of pigment can be in the scope of 5～50 weight %.When the amount of pigment during less than 5 weight % the shield effectiveness of primer coating can reduce, the storage quality of described coating composition and dispersing of pigments character can variation when the amount of pigment surpasses 50 weight %.
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 be in the scope of 3～6 weight %.When the planarization of the amount of solubility promoter coating during less than 3 weight % can variation, thereby the planarization of coating can improve but the amount of volatile organic compounds can increase atmosphere pollution when the amount of solubility promoter surpasses 6 weight %.Can separate with the solvent that comprises in the curing agent mixture and use solubility promoter.
The wetting agent that comprises in the water-soluble coating composition can be polyether siloxane copolymers type wetting agent, nonionic organic surface active agent type wetting agent etc.The total amount of coating based composition, the amount of wetting agent can be in the scope of 0.1～2 weight %.When the amount of wetting agent during less than 0.1 weight %, the wettability during coating can descend.When the amount of wetting agent surpassed 2 weight %, the water tolerance of coating and anti-cratering can variation.Wetting agent can comprise: available from TEGO Wet-260, the TEGO Wet-265 of TEGO company, TEGO Wet-270, TEGOWet-280, TEGO Wet-500 etc.
The dispersion agent that comprises in the water-soluble coating composition can comprise: have the segmented copolymer of acidic-group pure amine salt, comprise to above-mentioned pigment have good affinity polymkeric substance segmented copolymer or comprise the solution of this segmented copolymer.By using this dispersion agent, disperse to form pigment-water dispersion liquid thereby can make granules of pigments stablize mixing ground.In addition, can prevent the interior cohesion again of surface treated metallic pigment.This dispersion agent can comprise: available from DISPERBYK-180, the DISPERBYK-182 of BYK company, DISPERBYK-190, DISPERBYK-192, DISPERBYK-2012 etc.
The total amount of coating based composition, the amount of described dispersion agent can be in the scope of 0.1～2 weight %.When the amount of dispersion agent during less than 0.1 weight %, the particle diameter of dispersing material can be that the storage quality of inhomogeneous and dispersing material can variation.When the amount of dispersion agent surpassed 2 weight %, the water tolerance of coating can reduce.
The pin hole phenomenon that takes place when the foam generation in the defoamer meeting limit combination that comprises in the coating composition according to illustrative embodiments and inhibition baking coating.Can when the preparation coating composition, add all defoamers of amount.Alternately, can at first a part of defoamer be added in the pigment-water dispersion liquid foam that is produced when preparing pigment-water dispersion liquid to remove.
The total amount of coating based composition, the amount of defoamer can be in the scope of 0.1～1.5 weight %.When the amount of defoamer during less than 0.1 weight %, the defoaming of coating composition can be more weak and the pin hole phenomenon of coating can be taken place.When the amount of defoamer surpassed 1.5 weight %, water tolerance can reduce.Defoamer can comprise available from the DF-110D of Air Product company, available from the SN-DEFORMER 1320 of Sannopco company, available from the BYK-028 of BYK company.
Water-soluble coating composition according to illustrative embodiments can comprise tackifier.This coating composition can make shell expand by neutralizing with amine compound and enlarge display structure viscosity thus.Yet it can be not enough utilizing said structure viscosity to control viscosity.In order to replenish viscosity, can use tackifier.Can give good thixotropy and obtain molecule based on acrylic acid alkaline viscosity increase type emulsion and based on urethane-modified polyester based association type tackifier by common use, thereby improve the directional property of particle.Can obtain the good appearance of coating.Particularly, can obtain based on the thixotropy viscosity of acrylic acid alkaline viscosity increase type solution and realize good coating workability.Tackifier can comprise available from the NOPALL-642 of Sannopco company, NOPALL UT-666, SN-THICKENER 617, SN-THICKENER AM-1, NOPALL700N etc.
The total amount of coating based composition, the amount of tackifier can be in the scope of 0.1～1.0 weight %.When this amount during less than 0.1 weight %, can in having the spray booth of high humidity, produce and comprise the work defective of coating composition in being flowing in.When this amount surpassed 1.0 weight %, the decline of coating composition storage quality, the defective that forms fine particle, albinism etc. can take place.
Neutralizing agent can be used for according to the water-soluble coating composition of the illustrative embodiments pH value with the control combination thing.The total amount of coating based composition, the amount of neutralizing agent can be in the scope of 0.1～3 weight %.When the amount of neutralizing agent during less than 0.1 weight %, thereby the directional property of particle can reduce and the storage quality of coating composition can reduce cohesion again or the precipitation that pigment takes place.When the amount of neutralizing agent surpassed 3 weight %, solvent resistance particularly alkali resistance can variation.The pH value of coating composition can remain on about 7.5～8.5.Neutralizing agent can comprise amine compound, for example is 2-dimethylaminoethanol, ammonia, triethylamine of AMIETOL M21 etc. available from the common name of TAMINCO company.
The water that comprises in the automobile water-based soluble paint composition according to illustrative embodiments can be primary solvent.But water replace organic solvent and can prepare eco-friendly water-soluble coating composition.Water can be any kind, comprises deionized water, pure water etc.
Can utilize the automobile water-based soluble paint composition according to illustrative embodiments to form coating.
Can utilize methods such as aerial spraying, electrostatic applications to implement coating process.When described coating composition was used as the bottom coating composition that forms the automobile top coat, based on cured coating, the preferred thickness of coating can be about 10～25 microns.The top is coated with and can comprises undercoat and Clear coating.
When described coating composition is used as the bottom coating composition of automobile, can be coated with the water-soluble coating composition according to illustrative embodiments, toasted about 2～5 minutes down at about 80 ℃ then.Then, can under about 140～150 ℃, carry out the coating of about 20～40 minutes transparent coating composition, thereby make this two coating generation bridge joints and oven dry simultaneously.Can prevent from flowing and the generation of stain and can improving through the water tolerance of baking coating and the directional property of metallic particles.In addition, can form have good appearance (comprising image definition), the coating of good mechanical properties (comprise adhesivity, shock resistance, resistance to bending, chipping resistance and coat adhesiveproperties on the overbaking coating again).
Wait to describe in detail the present invention below with reference to synthesis example, embodiment, comparative example.
Synthesis example 1
The preparation of alkali swellable nuclear-shell resin
Be that 2,000 polycarbonate polyol, the dimethylol propionic acid of 64 weight parts, the N-Methyl pyrrolidone of 190 weight parts and the dibutyl tin laurate of 0.3 weight part join in the reaction vessel with the molecular weight of 23 weight parts.Temperature is elevated to 65 ℃.Then, 4, the 4 isocyanate group cyclohexyl-methanes that slowly add 220 weight parts.Temperature is elevated to 80 ℃ and keep this temperature, makes the NCO equivalent reach 970, prepare prepolymer thus.Under 25～35 ℃ temperature, the ion exchanged water of 400 weight parts and the triethylamine of 50 weight parts are mixed and stirring fast.Add prepolymer with 20 fens clock times, thus the preparation aqueous dispersant.Then, add the mixture of 40 weight part ion exchanged waters and 9.0 weight parts, 80% hydrazine hydrate so that chain extension.Having the acid number of 95mgKOH/g and the self-emulsifying type urethanum aqueous dispersant of 31% solids content is prepared.
The urethanum aqueous dispersant that 10g is so prepared joins the temperature control of 170g in 80 ℃ ion exchanged water.Stir and add 23g methyl methacrylate, 20g n-BMA, 22g n-butyl acrylate, 4g vinylformic acid 2-hydroxy methacrylate and 1g methacrylic acid down.Prepare the pre-emulsification of monomer thus.The pre-emulsification of this monomer of 43g is joined in the flask.After 10 minutes, add 10% ammonium persulfate solution that is dissolved in the deionized water, stir then.After 10 minutes, with the pre-emulsification of 4 hour time dropping monomer, dripped the mixture of 17g methyl methacrylate, 5g methacrylic acid and 10g vinylformic acid 2-hydroxy methacrylate then with 3 hour time, in 40～50 ℃ of 10% dimethylethanolamines with 60g this product that neutralizes, preparation has the alkali swellable nuclear-shell resin of the median size of 24.6% solid content, 6.5 pH value and 150nm thus after 2 hours.
Synthesis example 2
The preparation of curing agent mixture 1
244g ethylene glycol butyl ether, 127g Virahol and 114g N-N-methyl-2-2-pyrrolidone N-are dropped in the container, stir then.Stir and add 220g wetting ability melamine resin Cymel 327 down.Stir after 10 minutes, under 25～30 ℃ temperature, add 220g hydrophobicity melamine resin Setamine-146 and stirred 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 114g N-N-methyl-2-2-pyrrolidone N-are dropped in the container, stir then.Stir down, add 176g wetting ability melamine resin Cymel 327.Stir after 10 minutes, under 25～30 ℃ temperature, add 246g hydrophobicity melamine resin Setamine-146 and stirred 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 114g N-N-methyl-2-2-pyrrolidone N-are dropped in the container, stir then.Stir down, add 352g wetting ability melamine resin Cymel 327.Stir after 10 minutes, under 25～30 ℃ temperature, add 88g hydrophobicity melamine resin Setamine-146 and stirred 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 the blue pigments aqueous dispersions, in 380g deionized water, the DISPERBYK-2012 and 10g DF-110 input container as defoamer of 100g as dispersion agent, stir then.Add 300g as the G-314 of blue pigments, carry out about 1 hour pre-the stirring then.Then, utilize sand mill to make reactant be dispersed into particle diameter less than about 5 microns.Add 18g 10% dimethylethanolaminesolution solution and 72g deionized water, prepare the blue pigments aqueous dispersions thus.
Embodiment 1
Alkali swellable nuclear-shell resin and the 10g deionized water of preparation in the 35g synthesis example 1 are dropped in the container-1, stir then.Slowly add the curing agent mixture 1 of preparation in the 7g synthesis example 2, stirred then 20 minutes.Observe particle diameter less than about 5 microns.Add 6g as the Norooster-8210 (Noroo holdings company) of vibrin, stirred then 20 minutes.
One by one the pigment-water dispersion liquid, 4g of preparation in 3g metallic pigment (STAPA IL Hydrolan 9157), the 6g synthesis example 5 are put in the container-2 as the TEGO Wet 500 of wetting agent as the DISPERBYK-192 of dispersion agent and 0.9g as the 2-Rutgers 612 of solubility promoter 2,1.1g as the 2-Ethylhexyl Alcohol of solubility promoter 1,1g, then this mixture was stirred 10 minutes.
Mixture in the container-2 is dropped in the container-1, stirred then 10 minutes.One by one add 0.2g tackifier 1 (NOPALL 642), 0.4g tackifier 2 (NOPALL UT-666) and 2g as 10% dimethylethanolaminesolution solution of neutralizing agent, stirred then 20 minutes.The final viscosity of the product that so obtains is adjusted to 55 seconds (No. 4 Ford cup), prepare the automobile water-based soluble paint composition according to illustrative embodiments thus.
Embodiment 2～3
By implementing the step identical with step described in the embodiment 1 and adopt the composition shown in the table 1 and amount thereof, and prepare automobile water-based soluble paint composition.
Comparative example 1～4
By implementing the step identical with step described in the embodiment 1 and adopt composition shown in the table 1 and amount thereof, and prepare automobile water-based soluble paint composition.
Table 1
In the table 1,1) represent Polyester Resin Water Soluble available from Noroo holdings company and Norooster-8210; 2) representative is used for the metallic pigment of water-soluble color compositions and available from the STAPA IL Hydrolan 9157 of ECKART company; 3) represent 2-Ethylhexyl Alcohol; 4) represent 2-ethylhexyl glycol; 5) representative pigment is had affinity polymkeric substance segmented copolymer and available from the DISPERBYK-192 of BYK company; 6) represent nonionic organic surface active agent type wetting agent and available from the TEGO Wet 500 of TEGO company; 7) represent nonionic non-silicon type tensio-active agent and available from the DF-110D of Air Product company; 8) represent acrylic alkalescence and viscosity increase type emulsion and available from the NOPALL 642 of Sannopco company; 9) representative is based on urethane-modified polyester based association type tackifier with available from the NOPALL UT-666 of Sannopco company; 10) represent 10% dimethylethanolaminesolution solution.
Experiment for assessment of physical properties
The water-soluble coating composition that preparation is obtained by embodiment 1～3 and comparative example 1～4.For evaluation of physical properties, form prime coat, surfacer layer and top coat seriatim.
Cation electroplating paint composition is coated on for the exemplar of testing automobile with coating composition, thereby forms prime coat.Coating is carried out about 25 minutes curing then available from the KED-2000Gray of Noroo holdings company in about 70% relative humidity under about 150 ℃.Then, will be coated on available from the WP-3000 of Norooholdings company on the primer coating of formation like this, under about 140 ℃, under about 70% relative humidity, carry out about 30 minutes curing then, form the surfacer layer thus.
Then, form top coat.At first, the water-soluble coating composition with preparation in embodiment 1～3 and the comparative example 1～4 is coated on the surfacer coating as undercoat.Implement about 3 minutes solidification process down in about 80 ℃.After solidifying end, coating is as the DSC-3000 available from Noroo holdings company of clear coating composition.Form top coat at the surfacer layer.
In order to assess, the surfacer layer is formed be about 30～40 microns thickness, undercoat is formed be about 10～25 microns thickness, Clear coating is formed be about 30～50 microns thickness.
The evaluation result of various character is shown in table 2.
Table 2
In table 2, obtain each character by following experiment and appraisal procedure.
Stability: described coating composition was preserved 5 days down in 40 ℃.Utilize No. 4 Ford Cup to assess the concentration difference of preserving front and back.Whether the assessment differences in viscosity is in scope approximately-20%～+ 20%.
Mobile: as when the described composition of coating, to observe mobility status by the staff.
Stain: when the described composition of coating and after being solidified to form coating, the generation degree of being observed stain by the staff.
Glossiness: whether the glossiness of observing each coating from 60 ° angle is more than 90.
Outward appearance (sharpness of image): utilize the structure spectrum of the coatingsurface of wave front aberration DOI to analyze, show crooked size and appearance character with assessment.
Grain orientation: the direction mutation status of being observed metallic pigment in the coating by the staff.
Water tolerance: exemplar was soaked 10 days in about 40～50 ℃ of warm water and observe coating by the staff.
Adhesivity: form about 100 grids with about 2mm * 2mm size, adhesive tape is sticked on the coating that comprises grid.Then, with tape stripping and observed the separate stage of coating by the staff.
Shock resistance: use the counterweight of about 300g and the Apparatus for Impacting at low-temp of use DuPont company, assess the shock resistance degree by applying from the impact of about 40cm height.
Resistance to bend(ing): make this sample along having the circular steel bending that is about 3/16 inch circumference, and the coating of observing this sample is to check crack and the generation that separates.
Chipping resistance: exemplar was kept 4 hours down in-40 ℃, under the pressure of 4 bar, this sample is applied impact with Honda stone then.Observe have the separated part that is about 1～2mm length in the coating quantity whether less than 10 and quantity with the separated part that is about the above length of 2mm whether less than 1.
Coat the adhesivity on the overbaking coating again: after coating water-soluble bottom coating composition and transparent composition on the floating coat, implement to solidify normally, this coating is carried out 1 hour overbaking under about 150 ℃.Then, under normal operation bottom coating composition and transparent composition are coated with again and solidify.The test of enforcement adhesivity determines that adhesivity is about more than 90/100.
For the symbol of appointment, the ◎ representative is outstanding, and zero representative is good, and the △ representative is general, and * representative is poor.
As shown in table 2, show good and outstanding character according to the major part in the water-soluble coating composition of illustrative embodiments.When each composition according to illustrative embodiments is compared, can utilize the amount of alkali swellable nuclear-shell resin to change the physical properties that comprises outward appearance, storage quality, coating workability, grain orientation, water tolerance etc.
As mentioned above, by using the urethanum aqueous dispersant as emulsifying agent, can make described water-soluble coating composition comprise alkali swellable nuclear-shell resin and can prevent the reduction of water tolerance.Described water-soluble composition also can have good coating workability, and this is because because structural viscosity can limit the generation of flowing when being coated with stain.During utilization is carried out with neutralizing agent (as amine compound) and the time nuclear-shell resin expand and enlargement phenomenon, can obtain structural viscosity.In addition, can have the preferable image sharpness according to the coating composition of illustrative embodiments and to the had good adhesion of overbaking coating when being coated with again.
Coating composition according to illustrative embodiments can be used as automobile water-based dissolubility bottom coating composition.Said composition can comprise transoid nuclear/shell microgel resin and urethane ester dispersion, and can be used as and comprise by making the react automobile water-based dissolubility bottom coating composition of prepared trimeric cyanamide aqueous dispersant of acrylic resin and hydrophobicity melamine resin.
Above-mentionedly be the illustration of illustrative embodiments and be not understood as that its restriction.Although described some illustrative embodiments, those skilled in the art will easily understand under the situation that does not deviate from new instruction of the present invention and advantage in fact can make many modifications in the exemplary embodiment.Therefore, all this modifications are intended that in being included in the scope of the invention that limits as claim.In the claims, the functional specification clause is intended that when carrying out institute's recited function contains described structure herein, and not only contains structural equivalents but also contain equivalent structure.Therefore, should understand and above-mentionedly be the illustration of various illustrative embodiments and do not should be understood to and be confined to concrete illustrative embodiments disclosed herein, the modification of illustrative embodiments disclosed herein and other illustrative embodiments are intended that comprise within the scope of the appended claims.
Claims (12)
1. water-soluble coating composition, based on the total amount of described coating composition, it comprises:
20～50 weight % pass through use urethanum aqueous dispersant as the alkali swellable nuclear-shell resin of emulsifying agent manufacturing;
The curing agent mixture of 3～10 weight %, based on the total amount of described curing agent mixture, described curing agent mixture comprises: the N-N-methyl-2-2-pyrrolidone N-of the Virahol of the ethylene glycol butyl ether of 10～30 weight %, 10～30 weight %, 5～15 weight %, the wetting ability melamine resin of 25～35 weight %, the hydrophobicity melamine resin of 15～25 weight % and the nonionogenic tenside of 2～5 weight %;
The vibrin of 2～10 weight %; And
The water of surplus.
2. coating composition according to claim 1, wherein said urethanum aqueous dispersant prepares by the following method:
Make two functional isocyanate compounds, have 1,500～2, the polycarbonate polyol of 500 molecular weight and have at least two hydroxy functional groups and the compound of a carboxylic acid functional reacts forms prepolymer thus, has the isocyanate functional group in the end of this prepolymer; And
Described prepolymer is scattered in the amine aqueous solution, implements the chain extension process then.
3. coating composition according to claim 2, wherein said two functional isocyanate compounds are to be selected from least a in 1,6 hexamethylene diisocyanate, isophorone diisocyanate and 4, the 4-vulcabond cyclohexyl-methane.
4. coating composition according to claim 2, wherein said compound with at least two hydroxy functional groups and a carboxylic acid functional are at least a in dimethylol propionic acid and the dimethylolpropionic acid.
5. coating composition according to claim 1, wherein said alkali swellable nuclear-shell resin comprises that nuclear reaches in described circumnuclear shell part, described nuclear is to obtain by making described emulsifying agent and first monomer mixture carry out letex polymerization, described shell partly utilizes second monomer mixture to form
The weight ratio of mixture of wherein said first monomer mixture and described second monomer mixture is 65～85: in 15～35 the scope, based on the total amount of described first monomer mixture and second monomer mixture, the amount of described emulsifying agent is 5～30 weight %.
6. coating composition according to claim 5, but wherein said first monomer mixture comprises the methacrylic acid cycloalkyl ester with 4～12 carbon atoms of 75～90mol% and the single alkylidene group unsaturated monomer of copolymerization of 10～25mol%, and described second monomer mixture comprises the methacrylic acid of 20～40mol% and copolymerizable single alkylidene group unsaturated monomer of 60～80mol%.
7. coating composition according to claim 1, wherein said urethanum aqueous dispersant has the acid number of 90～100mgKOH/g and 28～34% solids content.
8. coating composition according to claim 1 also comprises: the defoamer of the wetting agent of the pigment-water dispersion liquid of the metallic pigment of 1～3 weight %, 5～50 weight %, the solubility promoter of 3～6 weight %, 0.1～2 weight %, the dispersion agent of 0.1～2 weight %, 0.1～1.5 weight %, the tackifier of 0.1～1.0 weight % and the neutralizing agent of 0.1～3 weight %.
9. method that forms coating comprises:
To be coated on according to the water-soluble coating composition of claim 1 on the base material; And
Make described through the applied coating composition drying.
10. it is the undercoat of automobile top coat that method according to claim 9, wherein said coating form 10～25 microns thickness and described coating.
11. method according to claim 9, wherein said coating are to utilize a kind of method in spraying coating and the electrostatic applications and implement.
12. method according to claim 9 is further implemented:
Clear coating composition is coated on the described coating; And
Described clear coating composition through coating is solidified.
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| KR1020110143043A KR101277446B1 (en) | 2011-12-27 | 2011-12-27 | Water-soluble basecoat paint composition for automobiles and method of forming paint layer using the same |
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| CN110651013A (en) * | 2017-05-25 | 2020-01-03 | Ｋｃｃ公司 | Water-soluble paint box for automobile |
| CN114174439A (en) * | 2019-08-02 | 2022-03-11 | 关西涂料株式会社 | Aqueous coating composition |
| CN115698201A (en) * | 2020-06-02 | 2023-02-03 | 株式会社Kcc | Oil-based coating composition for automotive intermediate coating |
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Effective date of registration: 20161205 Address after: Gyeonggi Do, South Korea Patentee after: NOROO PAINT & COATINGS CO., LTD. Address before: South Korea Gyeonggi Do Anyang Wanan Borda hole 615 times Patentee before: Noroo Holdings Co., Ltd. |