CN109836989A - Aqueous double-formulation is once coated with coating composition - Google Patents
Aqueous double-formulation is once coated with coating composition Download PDFInfo
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Abstract
The present invention provides a kind of aqueous double-formulation and is once coated with coating composition, and curability at low temperatures is excellent, can form the film of the real color of hardness, finish excellent appearance.It is the acrylic resin (A) containing hydroxyl that aqueous double-formulation of the invention, which is once coated with coating composition, the polyester resin (B) of hydroxyl, the aqueous double-formulation of polyisocyanate compound (C) and coloring pigment (D) is once coated with coating composition, wherein, the acrylic resin (A) of hydroxyl is that hydroxyl value is 100~200mgKOH/g, acid value is the acrylic resin of 5~50mgKOH/g, the polyester resin (B) of hydroxyl includes alicyclic polycarboxylic acid (the including acid anhydrides) sour component of (x1) as raw material, its content is at least 30 moles of % on the basis of the total amount of sour component, it and include that the carbon atom number with branched alkylidene is at least the alcohol component of 5 glycol (x2) as raw material, its content is at least on the basis of the total amount of alcohol component 40 moles of %, and be the polyester resin that hydroxyl value is 100~200mgKOH/g, acid value is 10~30mgKOH/g.
Description
Technical field
The present invention relates to a kind of aqueous double-formulations to be once coated with coating composition, and curability at low temperatures is excellent, can be formed hard
It spends, the film of reality (solid) color of finish excellent appearance.
Background technique
Coating cation electrodeposition coating etc. is lower in automobile exterior panel portion applies coating and middle painting coating, then in its coating surface
The coating of coating reality colour system etc. and the coating process for carrying out finish, and in the lower coating that applies such as cation electrodeposition coating
Direct coating coating in coating surface and the coating process for carrying out finish has been known.Since these methods are applied using primary
Mode for cloth forms painting film, thus has the advantage that process is few and productivity is high.
In the past, as such solid coatings, organic solvent system is mainstream, but from saving resource, public hazards countermeasure
Viewpoint considers, it is intended that the upper Tu Yici paint used for coating that exploitation is aqueous.Such as a kind of water is proposed in patent document 1
Property on apply primary coating white color system coating, which is characterized in that containing (A) hydroxyl value be 120~160, acid value be 20~40 it is poly-
Ester resin, (B) aqueous melamine resin and (C) white color system coloring pigment, and show and can form that apply adhesion again excellent
Different film.
In recent years, from the viewpoint of energy attenuating, it is intended that realize the low temperature of the sintering temperature of film, in addition,
It is intended that forming upper painting film on raw materials for plastics production with a coating method, such as propose in patent document 2
The aqueous primary coating coating composition of double-formulation a kind of, contains water system acrylic resin (A), water system polyester resin
(B) and the isocyanate curing agent (C) of self emulsifying property, the hydroxyl value of aforementioned resin (A) are 50~150mgKOH/g, and number is divided equally
Son amount is 1000~5000, and the acid value of aforementioned resin (B) is 20~50mgKOH/g, and hydroxyl value is 50~150mgKOH/g, and number is divided equally
Son amount is 1000~5000, and meltability parameter is 8.5~9.7, and two containing 10~40 mass % in whole monomer components
Polyacids ingredient, and show the film of available aesthetic appearance, weatherability, good chemical resistance.
But in terms of the coating composition of patent document 2, curability at low temperatures and finish are excellent, but there are films
Hardness is insufficient, cannot be considered in terms of bad phenomenon as hardness and finish appearance.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-206439 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-152232 bulletin
Summary of the invention
The project solved is wanted in invention
It is an object of the invention to eliminate above-mentioned bad phenomenon, a kind of aqueous double-formulation is provided and is once coated with Coating material composition
Object, curability at low temperatures is excellent, can form the film of the real color of hardness, finish excellent appearance.
Solution for solving the problem
That is, the present invention relates to a kind of aqueous double-formulations to be once coated with coating composition, which is characterized in that it is containing containing hydroxyl
The acrylic resin (A) of base, the polyester resin (B) of hydroxyl, polyisocyanate compound (C) and coloring pigment (D)
Aqueous double-formulation is once coated with coating composition, wherein the acrylic resin (A) of hydroxyl be hydroxyl value be 100~
200mgKOH/g, the acrylic resin that acid value is 5~50mgKOH/g, the polyester resin (B) of hydroxyl include alicyclic polynary
Carboxylic acid (the include acid anhydrides) sour component of (x1) as raw material, content are at least 30 to rub on the basis of the total amount of sour component
Your %, and include that the carbon atom number with branched alkylidene is at least the alcohol component of 5 glycol (x2) as raw material, content with
Be at least 40 moles of % on the basis of the total amount of alcohol component, and be hydroxyl value be 100~200mgKOH/g, acid value be 10~
The polyester resin of 30mgKOH/g.
The effect of invention
Aqueous double-formulation according to the present invention is once coated with coating composition, and curability at low temperatures is excellent, can form hardness, essence
Adorn the film of excellent appearance.
Specific embodiment
Aqueous double-formulation of the invention, which is once coated with coating composition, to be the acrylic resin (A) containing hydroxyl, contains
The aqueous double-formulation of the polyester resin (B) of hydroxyl, polyisocyanate compound (C) and coloring pigment (D) is once coated with coating
Composition.
The acrylic resin (A) of above-mentioned hydroxyl be hydroxyl value be 100~200mgKOH/g, acid value is 5~50mgKOH/g
Acrylic resin, in general, can be by by the polymerism unsaturated monomer of hydroxyl and can be with the polymerism of the hydroxyl
Other polymerism unsaturated monomers that unsaturated monomer is copolymerized, for example in organic solvent using method known to its own
Solution polymerization process, the methods of emulsion polymerization in water, be copolymerized manufacturing.
Especially in the present invention, the propylene from the viewpoint of the hardness and finish for forming film, about hydroxyl
Acid resin (A), preferably through in presence of organic solvent by the polymerism unsaturated monomer of mutually different composition at
Graduation is polymerize and obtains acrylic resin with being divided into the multistage, and the acrylic resin is carried out water dispersion to obtain
, the polymerism unsaturated monomer ingredient (I) as one of them preferably comprises the polymerism unsaturated monomer containing epoxy group
(a1), the polymerism unsaturated monomer (a2) of hydroxyl and other polymerism unsaturated monomers (a3), it is other at least one
Polymerism unsaturated monomer ingredient (II) used in the polymerization in stage preferably comprises carboxylic polymerism unsaturated monomer
(b1), the polymerism unsaturated monomer (b2) of hydroxyl and other polymerism unsaturated monomers (b3).
Polymerism unsaturated monomer (a1) containing epoxy group is: in order to aftermentioned polymerism unsaturated monomer ingredient (II)
Contained in carboxyl reacted, in order to will be based on copolymer obtained from polymerism unsaturated monomer ingredient (I) with based on poly-
Copolymer obtained from conjunction property unsaturated monomer ingredient (II) is grafted, in order to more improve the water of acrylic resin emulsion
The monomer that dispersion stabilization thus uses；Such as enumerate: (methyl) glycidyl acrylate, Beta-methyl glycidyl (first
Base) acrylate, 3,4- epoxycyclohexyl-methyl (methyl) acrylate, 3,4- epoxycyclohexylethyl (methyl) acrylic acid
Ester, 3,4- epoxycyclohexyl propyl (methyl) acrylate, allyl glycidyl ether etc., they can be used alone or
It combines two or more and uses.
The polymerism unsaturated monomer (a2) of hydroxyl is: in order to be used for and aftermentioned polyisocyanate compound (C)
The hydroxyl reacted is directed in the monomer in the acrylic resin (A) of hydroxyl thus being copolymerized, such as can enumerate:
(methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 4-
The monoesters compound of (methyl) acrylic acid such as hydroxy butyl ester and the dihydric alcohol of carbon atom number 2~8；It should (methyl) acrylic acid and carbon atom number
The 6-caprolactone modified body of the monoesters compound of 2~8 dihydric alcohol；Allyl alcohol etc., they can be used alone or combine 2 kinds with
Above use.
It is the polymerization other than above-mentioned monomer (a1) and monomer (a2) about other polymerism unsaturated monomers (a3)
Property unsaturated monomer, such as enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl,
(methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,
(methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) nonylphenol acrylate
Ester, (methyl) acrylic acid tridecane ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, isostearyl acrylate
(trade name, the manufacture of Osaka organic chemistry company), (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (first
Base) (methyl) third such as t-butylcyclohexyl ester, (methyl) acrylic acid cyclododecane ester, (methyl) acrylic acid tricyclodecyl ester
Olefin(e) acid alkyl or cycloalkyl ester；(methyl) isobornyl acrylate etc. has the polymerism unsaturated monomer of isobornyl；(first
Base) the polymerism unsaturated monomer with adamantyl such as acrylic acid Buddha's warrior attendant alkyl ester；The tool such as (methyl) acrylic acid tricyclodecenyl esters
There is the polymerism unsaturated monomer of tricyclic decenyl；(methyl) benzyl acrylate, styrene, α-methylstyrene, vinyl first
The polymerism unsaturated monomer containing aromatic rings such as benzene；Vinyltrimethoxysilane, vinyl methyl dimethoxysilane, second
Alkenyl triethoxysilane, vinyl methyl diethoxy silane, vinyl three (2- methoxy ethoxy) silane, vinyl three
Isopropoxy silane, γ-(methyl) acryloyloxypropyltrimethoxysilane, γ-(methyl) acryloxypropyl
Dimethoxysilane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl
Diethoxy silane, three positive propoxy silane of γ-(methyl) acryloxypropyl, γ-(methyl) acryloxypropyl three
Isopropoxy silane, vinyltriacetoxy silane, β-(methyl) acryloyl-oxyethyl trimethoxy silane etc. have water
The polymerism unsaturated monomer of solution property silicyl；(methyl) perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl octyl
Ethyl ester etc. (methyl) perfluoroalkyl acrylate；Fluoroolefins etc. has the polymerism unsaturated monomer of fluoro-alkyl；N- vinyl
The vinyl compounds such as pyrrolidones, ethylene, butadiene, chlorobutadiene, vinyl propionate, vinyl acetate；2- acryloyl-oxy
Base ethyl acid phosphate, 2- methacryloxyethyl phosphate ester acid, 2- acryloxypropyl phosphate ester acid, 2-
The polymerism unsaturated monomer of the phosphorous acidic group such as methacryloxypropyl phosphate ester acid；(methyl) acrylic acid, maleic acid,
The carboxylic polymerism unsaturated monomer such as crotonic acid, P-carboxy ethyl acrylates；(methyl) acrylonitrile, (methyl) acryloyl
Amine, di-2-ethylhexylphosphine oxide (methyl) acrylamide, bis- (methyl) acrylamides of ethylene, 2- (methylacryloyl oxygroup) ethyl-trimethyl
The nitrogenous polymerism unsaturated monomer such as the addition product of ammonium chloride, (methyl) glycidyl acrylate and amine；(methyl) propylene
Allyl propionate, two (methyl) acrylic acid 1,6- hexylene glycol ester etc. are poly- at least two polymerism unsaturated group in 1 molecule
Conjunction property unsaturated monomer；2- acrylamido -2- methyl propane sulfonic acid, (methyl) acrylic acid 2- sulphur ethyl ester, allyl sulphonic acid, 4-
Styrene sulfonic acid etc.；Sodium salt and ammonium salt of these sulfonic acid etc. have sulfonic polymerism unsaturated monomer；Maleic anhydride, clothing
Health acid anhydrides, citraconic anhydride etc. have anhydride group polymerism unsaturated monomer etc., they can be used alone or combine 2 kinds with
Above use.
As carboxylic polymerism unsaturated monomer (b1), also in the acrylic resin (A) to hydroxyl
Water dispersion base is imported, while in order to import and be based on institute in copolymer obtained from above-mentioned polymerism unsaturated monomer ingredient (I)
The monomer that functional group that the epoxy group contained is reacted thus uses, specifically enumerate (methyl) acrylic acid, maleic acid, crotonic acid,
P-carboxy ethyl acrylates etc., they can be used alone or combine two or more and use.
As in the polymerism unsaturated monomer (b2) of hydroxyl, with the polymerism unsaturated monomer (a2) of above-mentioned hydroxyl
The compound being set out is likewise, can be used alone among them or combine two or more and use.
It is the polymerization other than above-mentioned monomer (b1) and monomer (b2) about other polymerism unsaturated monomers (b3)
Property unsaturated monomer, such as enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl,
(methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,
(methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid nonyl
Ester, (methyl) acrylic acid tridecane ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) acrylic acid are different
Stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (first
Base) (methyl) acrylic acid alkyl or the cycloalkyl ester such as acrylic acid cyclododecane ester, (methyl) acrylic acid tricyclodecyl ester；(methyl)
Isobornyl acrylate etc. has the polymerism unsaturated monomer of isobornyl；(methyl) acrylic acid Buddha's warrior attendant alkyl ester etc. has Buddha's warrior attendant
The polymerism unsaturated monomer of alkyl；(methyl) acrylic acid tricyclodecenyl esters etc. have the polymerism of tricyclic decenyl unsaturated single
Body；The polymerism insatiable hunger of (methyl) benzyl acrylate, styrene, α-methylstyrene, vinyltoluene etc. containing aromatic rings
And monomer；2- acryloyl-oxyethyl phosphate ester acid, 2- methacryloxyethyl phosphate ester acid, 2- acryloxy
The polymerism unsaturated monomer of the phosphorous acidic groups such as propyl phosphate ester acid, 2- methacryloxypropyl phosphate ester acid；2-
Acrylamido -2- methyl propane sulfonic acid, (methyl) acrylic acid 2- sulphur ethyl ester, allyl sulphonic acid, 4- styrene sulfonic acid etc.；These
Sodium salt and ammonium salt of sulfonic acid etc. have sulfonic polymerism unsaturated monomer；Maleic anhydride, itaconic anhydride, citraconic anhydride etc.
Polymerism unsaturated monomer with anhydride group etc.；Vinyltrimethoxysilane, vinyl methyl dimethoxysilane, ethylene
Ethyl triethoxy silicane alkane, vinyl methyl diethoxy silane, vinyl three (2- methoxy ethoxy) silane, vinyl three are different
Npropoxysilane, γ-(methyl) acryloyloxypropyltrimethoxysilane, γ-(methyl) acryloxypropyl two
Methoxy silane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl two
Ethoxysilane, three positive propoxy silane of γ-(methyl) acryloxypropyl, γ-(methyl) acryloxypropyl three are different
Npropoxysilane, vinyltriacetoxy silane, β-(methyl) acryloyl-oxyethyl trimethoxy silane etc. have hydrolysis
The polymerism unsaturated monomer of property silicyl；(methyl) perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl octyl second
Ester etc. (methyl) perfluoroalkyl acrylate；Fluoroolefins etc. has the polymerism unsaturated monomer of fluoro-alkyl；N- vinylpyridine
The vinyl compounds such as pyrrolidone, ethylene, butadiene, chlorobutadiene, vinyl propionate, vinyl acetate；(methyl) acrylonitrile,
(methyl) acrylamide, di-2-ethylhexylphosphine oxide (methyl) acrylamide, bis- (methyl) acrylamides of ethylene, 2- (methylacryloyl oxygen
Base) ethyl-trimethyl salmiac, (methyl) glycidyl acrylate and amine the nitrogenous polymerism such as addition product it is unsaturated single
Body；(methyl) allyl acrylate, two (methyl) acrylic acid 1,6- hexylene glycol ester etc. have at least two polymerism in 1 molecule
Polymerism unsaturated monomer of unsaturated group etc., they can be used alone or combine two or more and use.
In the acrylic resin (A) of hydroxyl, about the monomer in above-mentioned polymerism unsaturated monomer ingredient (I)
(a1)~(a3) use ratio, can appropriate adjustment as long as being within the scope of the invention, it is however generally that, it can be following
In range:
Monomer (a1) be 0.1~40 mass %, preferably 0.5~25 mass %,
Monomer (a2) be 15~54.9 mass %, preferably 20~44.5 mass %,
Monomer (a3) is 45~84.9 mass %, preferably 55~79.5 mass %.
In addition, about these monomer (b1)~(b3) use ratios in above-mentioned polymerism unsaturated monomer ingredient (II)
Example, can appropriate adjustment as long as being within the scope of the invention, it is however generally that, it can be in following range:
Monomer (b1) be 5~60 mass %, preferably 10~50 mass %,
Monomer (b2) be 20~75 mass %, preferably 25~65 mass %,
Monomer (b3) is 20~75 mass %, preferably 25~65 mass %.
In addition, in terms of these polymerism unsaturated monomer ingredients (I) and (II), according to relative to polymerism unsaturation
The amount of carboxyl contained in polymerism unsaturated monomer ingredient (II) contained in monomer component (I) for 1 mole of epoxy group
It is adjusted as 3~30 moles, particularly as the mode in the range of 6~20 moles, this acrylic compounds from hydroxyl
It is also suitable from the viewpoint of the storage stability of resin (A) and the finish of film obtained.
In the present invention, about above-mentioned polymerism unsaturated monomer ingredient (I) and the use ratio of (II), according to monomer
Ingredient (I)/monomer component (II) mass ratio and in the range of 60/40~95/5, be especially in 70/30~90/10
In the range of, this sight from the dispersion stability of the acrylic resin (A) of hydroxyl and the finish of film obtained
Point considers to be suitable.
The polymerization of above-mentioned polymerism unsaturated monomer ingredient (I) and (II) are not particularly limited, for example, on one side organic
It is heated in the presence of solvent and polymerism unsaturated monomer ingredient (I) is added dropwise and is polymerize on one side, to based on polymerism unsaturation
In the copolymer solution that monomer component (I) obtains, polymerism unsaturated monomer ingredient (II) is added dropwise and is polymerize, this tends to make
Water dispersible, the superior storage stability of the acrylic resin (A) of hydroxyl obtained are obtained, and is preferred.
In addition, can also as needed and be suitable for it is additional based in addition to above-mentioned polymerism unsaturated monomer ingredient (I) and
(II) polymerism unsaturated monomer ingredient other than and the polymerization carried out.
Reaction temperature when monomer (I) and (II) are polymerize is typically about 60~about 200 DEG C of range, preferably
It is about 70~about 160 DEG C of range, and the reaction time was typically about 10 hours hereinafter, preferably from about 0.5~about 6 hour.
It is preferably suitable for adding polymerization initiator in terms of above-mentioned reaction.As such polymerization initiator, such as arrange
Lift: benzoyl peroxide, decoyl peroxide, lauroyl peroxide, stearyl peroxide, cumene hydroperoxide,
Tert-butyl peroxide, two t-amyl peroxy compounds, peroxide -2-ethyl hexanoic acid tert-butyl, the peroxylauric acid tert-butyl ester, mistake
Aoxidize the organic peroxides such as isopropyl t-butyl carbonate, peroxide acetic acid butyl ester, diisopropylbenzene (DIPB) hydroperoxides；Azo two
Isobutyronitrile, azo bis- (2,4- methyl pentane nitriles), azo bis- (2- methyl propionitrile), azo bis- (2- methylbutyronitriles), 4,4 '-azos
Bis- (4- cyano butyric acids), dimethyl azo bis- (2 Methylpropionic acid esters), azo bis- [2- methyl-N- (2- ethoxy)-propionamides],
The azo-compounds such as azo bis- { 2- methyl-N- [2- (1- hydroxybutyl)]-propionamides }；Potassium peroxydisulfate, ammonium persulfate, persulfuric acid
Persulfates such as sodium etc..
These polymerization catalysts can be used alone or can also be used in combination of two or more.In addition, polymerism unsaturated monomer at
When dividing the polymerization of (I) and polymerism unsaturated monomer ingredient (II), it is different even if the type of polymerization initiator and amount
It does not have any problems.
About the compounding amount of polymerization initiator, stablize from the water dispersion of the acrylic resin (A) of hydroxyl obtained
Property from the viewpoint of, based on 100 mass parts of polymerism unsaturated monomer, preferably 0.01~20 mass used at this stage
Part range, the particularly preferably range of 0.1~15 mass parts, the further particularly preferably range of 0.3~10 mass parts.
Above-mentioned polymerization usually carries out in presence of organic solvent.It, can be by considering to polymerize about the selection of organic solvent
Temperature, aqueous dispersion manufacture when processing easness and aqueous dispersion obtained long-term storage stability and be suitable for into
Row.
In addition, organic solvent can also be added even if in the case where acrylic resin to be dispersed in water.
As above-mentioned organic solvent, preferably alcohol series solvent, cellosolve (cellosolve) series solvent, carbitol series solvent
Deng.Specifically, for example, the alcohol series solvents such as n-butanol can be enumerated；Ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol
Monomethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Dan Zhengding
The cellosolves series solvent such as ether；Carbitols series solvent such as diethylene glycol monobutyl ether, diethylene glycol monoethyl ether etc..
In addition, can also be caused in the dispersion stability not to the acrylic resin of hydroxyl (A) about organic solvent
The range of obstruction is using the nonactive organic solvent not mixed with water in addition to the foregoing, as such organic solvent, such as
It can enumerate: the aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, the ester series solvents such as ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone
Etc. ketone series solvents etc..
The acrylic resin (A) of the hydroxyl obtained about as described above operate, weight average molecular weight are in 5,000
It in the range of~100,000, is especially in the range of 10,000~50,000, is more particularly in 10,000~30,000
In the range of, this sees from the dispersion stability of the acrylic resin (A) of hydroxyl and finish, the flatness of film etc.
Point considers to be suitable.
In the present specification, about weight average molecular weight and number-average molecular weight, (trade name, the east " HLC-8120GPC " can be used
The manufacture of Cao Co., Ltd.) it is used as gel permeation chromatograph device, 1 " TSKgel G4000HXL ", 2 " TSKgel can be used
G3000HXL " and 1 " TSKgel G2000HXL " (trade name, any one is all TOSOH Co., Ltd's manufacture) 4 total
As chromatographic column, it can be used differential refractometer as detector, it can be in mobile phase: tetrahydrofuran, measuring temperature: 40 DEG C, flow velocity:
It is measured under conditions of 1mL/min.
It, can be contained in acrylic resin (A) of the alkali compounds by above-mentioned hydroxyl as the technology of water dispersion
Some or all neutralized in the anionic groups such as carboxyl and be dispersed in water, or can also be by the acrylic compounds
Resin makes an addition in the aqueous medium containing alkali compounds and disperses.
As the alkali compounds for neutralization, for example, ammonia, diethylamine, ehtylethanolamine, diethanol amine, three can be enumerated
Ethanol amine, monoethanolamine, single Propanolamine, isopropanolamine, ethylamino ethamine, aminoethyle alcohol, triethylamine, tri-n-butylamine, dimethyl second
The organic amines such as hydramine, diethylenetriamines；Or alkali metal hydroxides such as caustic soda, caustic potash etc., relative to acrylic compounds
Using 0.1~1.5 equivalent, it is preferable to use 0.5~1.2 equivalent, this is appropriate for carboxyl in resin.
The acrylic resin (A) of the hydroxyl of operation and acquisition can be core-shell-type acrylic compounds cream as described above
Liquid will be made about the core-shell-type acrylic emulsions based on copolymer obtained from polymerism unsaturated monomer ingredient (I)
Core, will be made shell based on copolymer obtained from polymerism unsaturated monomer ingredient (II), and average grain diameter can be made into 0.05~
It 1.0 μm, preferably can be made into the range of 0.08~0.8 μm.
In the present specification, average grain diameter is set as following value, that is, using submicron particles analyzer N4 (trade name,
Beckman Coulter K.K. manufacture, particle size distribution device), sample is diluted to suitable for measurement using deionized water
Concentration is measured the value obtained from room temperature (20 DEG C or so).
In addition, the acrylic resin (A) about above-mentioned hydroxyl, from storage stability, the finish of the film of formation
From the viewpoint of, the hydroxyl value of the solid content of unit is in the range of 100~200mgKOH/g, especially in 100~130mgKOH/
In the range of g, further especially in the range of 100~120mgKOH/g, the acid value of the solid content of unit 5~
In the range of 50mgKOH/g, especially in the range of 10~35mgKOH/g, further especially 20~30mgKOH/g's
In range.
It is once coated with coating composition about aqueous double-formulation of the invention, with 100 mass of resin solid content in coating
It, can be in the range of 20~70 mass parts, preferably to contain above-mentioned hydroxyl in the range of 20~65 mass parts on the basis of part
Acrylic resin (A).
About the polyester resin (B) of above-mentioned hydroxyl, be obtained and using sour component with reacting for alcohol component, and
It is that hydroxyl value is 100~200mgKOH/g, is preferably 105~195mgKOH/g, and acid value is 10~30mgKOH/g, is preferably
The polyester resin of 10~25mgKOH/g.
It include alicyclic polycarboxylic acid from the viewpoint of ensuring hardness of film about the polyester resin (B) of hydroxyl
(the including acid anhydrides) sour component of (x1) as raw material, content is at least 30 moles of % on the basis of the total amount of sour component,
And include that the carbon atom number with branched alkylidene is at least the alcohol component of 5 glycol (x2) as raw material, content with alcohol at
It is at least 40 moles of % on the basis of the total amount divided.
In terms of alicyclic polycarboxylic acid (including acid anhydrides) (x1), being included in 1 molecule has at least one ester ring type structure
(preferably 4~6 ring structures) and the compound of at least two carboxyl and the acid anhydrides of the compound, specifically, for example enumerating
1,2- cyclohexane cyclohexanedimethanodibasic, 1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride, 1,3- cyclohexane cyclohexanedimethanodibasic, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 4- hexamethylene
Alkene -1,2- dioctyl phthalate, 4- cyclohexene -1,2- dicarboxylic acid anhydride, 3- methyl-1,2- cyclohexane cyclohexanedimethanodibasic, 3- methyl-1,2- hexamethylene
Dicarboxylic acid anhydride, 4- methyl-1,2- cyclohexane cyclohexanedimethanodibasic, 4- methyl-1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride, 1,2,4- hexamethylene front threes
Acid, 1,2,4- hexamethylene tricarboxylic acid -1,2- acid anhydrides, HET acid (HET acid) etc., wherein preferably use 1,2- hexamethylene two
Formic acid, 1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride.Above-mentioned alicyclic polycarboxylic acid (including acid anhydrides) (x1) can be used alone respectively or
It combines two or more and uses.
It can be not particularly limited with other sour components of aforementioned alicyclic polycarboxylic acid (including acid anhydrides) (x1), it can be same
Sour component usually used when manufacturing polyester resin is used to sample, such as can be enumerated: succinic acid, glutaric acid, adipic acid, heptan
Diacid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid (brassylic acid), ten
The aliphatic polycarboxylic acids such as eight docosandioic acids, citric acid, maleic acid, fumaric acid, itaconic acid and their acid anhydrides (include acid
Acid anhydride)；Phthalic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimellitic anhydride, equal benzene four
The aromatic polycarboxylic acids such as acid, pyromellitic dianhydride, naphthalenedicarboxylic acid (including acid anhydrides)；It is coco-nut oil fatty acid, cottonseed oil fatty acid, big
Flaxseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, Linseed oil fat
The fat such as acid, tung oil fatty acid, rapeseed oil fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid
Acid；Benzoic acid, 4- p t butylbenzoic acid etc..
As aforementioned alcohol component, preferably using the polyalcohol in 1 molecule at least two hydroxyl, specifically, example
It such as enumerates: ethylene glycol, propylene glycol, diethylene glycol, trimethylene, triethylene glycol, tetraethylene glycol, dipropylene glycol, Isosorbide-5-Nitrae-fourth
Glycol, 1,3-BDO, 2,3-butanediol, 1,2- butanediol, 3- methyl-1,2- butanediol, 2,2- diethyl -1,3- the third two
Alcohol, 2- butyl -2- ethyl -1,3-PD, 1,2- pentanediol, 1,5-PD, Isosorbide-5-Nitrae-pentanediol, 2,4- pentanediol, 2,3-
Dimethyltrimethylene glycol, tetramethylene glycol, 3- methyl -4,3- pentanediol, 3- methyl-1,5- pentanediol, 2,2,4- tri-
Methyl-1,3- pentanediol, 1,6- hexylene glycol, 1,5- hexylene glycol, Isosorbide-5-Nitrae-hexylene glycol, 2,5- hexylene glycol, neopentyl glycol, hydroxyl spy penta
The dihydric alcohols such as sour neopentyl glycol ester；By the lactones such as 6-caprolactone addition polylactone diol obtained from these dihydric alcohols；It is double
The esterdiols classes such as (ethoxy) terephthalate；The alkylene oxide addition product of bisphenol-A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol
Etc. polyetherdiol class；Glycerol, trimethylolpropane, trimethylolethane, diglycerol, triglycerin, 1,2,6- hexanetriols, Ji Wusi
3 yuan of alcohol, dipentaerythritol, sorbierite, mannitol etc. or more of alcohol；By the addition of the lactones such as 6-caprolactone in these 3 yuan or more
Alcohol obtained from poly-lactone polyol class；1,3-CHDM, 1,4-CHDM, Tricyclodecane Dimethanol,
Alicyclic polyols such as hydrogenated bisphenol A, hydrogenated bisphenol F etc..
It is at least 5 glycol (x2) as the carbon atom number with branched alkylidene, can enumerates among above-mentioned dihydric alcohol
3- methyl-1,2- butanediol, 2,2- diethyl -1,3-PD, 2- butyl -2- ethyl -1,3-PD, 2,3- dimethyl three
Methylene glycol, 3- methyl -4,3- pentanediol, 3- methyl-1,5- pentanediol, 2,2,4- trimethyl -1,3- pentanediols, new penta 2
Alcohol.
The synthetic method of the polyester resin (B) of hydroxyl is not particularly limited, and can carry out according to usual way.For example,
It can be heated 5~10 hours or so by by aforementioned sour component and alcohol component, in stream of nitrogen gas at about 150~about 250 DEG C, into
The esterification of row hydroxyl and carboxyl is to synthesize.
When making above-mentioned sour component and alcohol component carries out esterification, they can disposably be added, it can also
It is divided into for several times and adds.In addition, the polyester resin of hydroxyl can also be synthesized first, then acid anhydrides is made to be reacted and be carried out
It is half-esterification.
About the polyester resin (B) of hydroxyl, from the viewpoint of the flatness of film obtained and film performance,
It is preferred that the number in the range of having usually 300~50000, particularly 500~20000, more particularly 800~10000 is divided equally
Son amount.In addition, the polyester resin (B) about hydroxyl, in order to keep mixing with water and dispersion transfiguration easy, thus preferably by
Neutralizer and neutralized.
It is once coated with coating composition about aqueous double-formulation of the invention, with 100 mass of resin solid content in coating
It, can be in the range of 10~50 mass parts, preferably to contain above-mentioned hydroxyl in the range of 10~45 mass parts on the basis of part
Polyester resin (B).
Above-mentioned polyisocyanate compound (C) is the isocyanate group with the not no sealing end of at least two in 1 molecule
Compound, for example, aliphatic polyisocyante, alicyclic polyisocyanates, aromatic-aliphatic polyisocyanates, fragrance can be enumerated
Race's polyisocyanates, derivative of the polyisocyanates etc..
It about above-mentioned aliphatic polyisocyante, such as can enumerate: trimethylene diisocyanate, two isocyanide of tetramethylene
Acid esters, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanate, 1,2- butylidene two
Isocyanates, 2,3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, 2,4,4- or 2,2,4- trimethyl, six methylene
Group diisocyanate, 2,6- diisocyanate root close the aliphatic diisocyanates such as methylhexanoic acid ester；Lysine ester triisocyanate,
Isosorbide-5-Nitrae, tri- isocyanato- octane of 8-, 1,6,11- tri- isocyanato- hendecanes, 1,8- diisocyanate root conjunction -4- isocyano
Close methyloctane, 1,3,6- tri- isocyanato- hexanes, 2,5,7- trimethyl -1,8- diisocyanate root conjunction -5- isocyanato-s
Aliphatic triisocyanate such as methyloctane etc..
It about aforementioned alicyclic polyisocyanates, such as can enumerate: 1,3- cyclopentene diisocyanate, Isosorbide-5-Nitrae-hexamethylene two
Isocyanates, 1,3- cyclohexane diisocyanate, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate are (used
With name: isophorone diisocyanate), methyl -2,4- cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanate,
1,3- or bis- (isocyanatomethyl) hexamethylenes of Isosorbide-5-Nitrae-(trivial name: hydrogenated dimethylbenzene diisocyanate) or its mixing
The alicyclic diisocyanates such as object, norcamphane diisocyanate；1,3,5- tri- isocyanatocyclohexane, 1,3,5- trimethyls are different
Cyanate radical trimethylcyclohexane, 2- (3- isocyanatopropyl) -2,5- bis- (isocyanatomethyl)-bicyclic [2.2.1] heptane, 2-
(3- isocyanatopropyl) -2,6- bis- (isocyanatomethyl)-bicyclic [2.2.1] heptane, 3- (3- isocyanato- third
Base) -2,5- bis- (isocyanatomethyl)-bicyclic [2.2.1] heptane, 5- (2- isocyanatoethyl) -2- isocyanato-
Methyl -3- (3- isocyanatopropyl)-bicyclic [2.2.1] heptane, 6- (2- isocyanatoethyl) -2- isocyanato- first
Base -3- (3- isocyanatopropyl)-bicyclic [2.2.1] heptane, 5- (2- isocyanatoethyl) -2- isocyanato- first
Base -2- (3- isocyanatopropyl)-bicyclic [2.2.1]-heptane, 6- (2- isocyanatoethyl) -2- isocyanato- first
Alicyclic triisocyanates such as base -2- (3- isocyanatopropyl)-bicyclic [2.2.1] heptane etc..
About aforementioned fragrance aliphatic polyisocyante, for example, can enumerate 1,3- or Isosorbide-5-Nitrae-xylene diisocyanate or
Its mixture, ω, ω '-diisocyanate root conjunction-Isosorbide-5-Nitrae-diethylbenzene, 1,3- or the bis- (1- isocyanato- -1- methyl second of Isosorbide-5-Nitrae -
Base) araliphatic diisocyanates such as benzene (trivial name: tetramethylxylene diisocyanate) or its mixture；1,3,5-
Aromatic-aliphatics triisocyanate such as three isocyanatomethylbenzenes etc..
As aforementioned fragrance race polyisocyanates, for example, m-benzene diisocyanate, paraphenylene diisocyanate, 4 can be enumerated,
4 '-diphenyl diisocyanates, 1,5- naphthalene diisocyanate, 2,4 '-perhaps 44 '-'-diphenylmethane diisocyanates or it is mixed
Close object, 2,4- perhaps 2 6- toluene di-isocyanate(TDI)s or its mixture, 4,4 '-toluidine diisocyanates, 4,4 '-diphenyl
The aromatic diisocyanates such as ether diisocyanate；4,4 ', 4 "-triisocyanate of triphenyl methane-, 1,3,5- tri- isocyanos
Close benzene, 2, the aromatic tri-isocyanates such as 4,6- tri- isocyanato- toluene；4,4 '-diphenyl methane -2,2 ', 5,5 '-four is different
Aromatic series tetraisocyanate such as cyanate etc..
In addition, the derivative as aforementioned polyisocyanates, for example, the two of above-mentioned polyisocyanate compound can be enumerated
Polymers, trimer, biuret, allophanate, urea diketone (ウ レ ト ジ オ Application), uretonimine (ウ レ ト イ ミ Application), isocyanide urea
Acid esters, oxadiazines triketone, polymethylene polyphenyl Quito isocyanates (crude MDI, polymeric MDI), crude TDI etc..
Above-mentioned polyisocyanates and its derivative can also be used individually or be also used in combination of two or more.In addition, these
It is preferably that aliphatic diisocyanate, alicyclic diisocyanate and their derivative is single respectively among polyisocyanates
It solely uses or combines two or more and use.
In addition, considering from viewpoints such as the flatness of film obtained, preferably making as polyisocyanate compound (C)
Water-dispersible property polyisocyanate compound.About the water dispersible polyisocyanate compound, if it is can steadily disperse
Polyisocyanate compound in aqueous medium can then use without restriction, but wherein, preferably use: being modified as hydrophilic
Property obtained from hydrophiling polyisocyanate compound (C-1), by advance by polyisocyanate compound (C) and surface-active
Agent is mixed and assigns water dispersible polyisocyanate compound obtained from etc..
It about above-mentioned hydrophiling polyisocyanate compound (C-1), such as enumerates: by making with anionic group
The active hydrogen-based of the compound containing active hydrogen-based reacted and obtained with the isocyanate group of polyisocyanate compound
The Hydrophilicrto polyethers such as anionic hydrophilic polyisocyanate compound (C-1-1), monohydric alcohol by making polyethylene glycol oxide
Alcohol is reacted with polyisocyanate compound and the nonionic hydrophiling polyisocyanate compound (X2-1-2) etc. that obtains,
They can be used alone or combine two or more and use.
It is above-mentioned with the compound containing active hydrogen-based of anionic group in terms of, comprising have carboxyl, sulfonic group, phosphorus
The anionic groups such as acidic group, group containing betaine structure, and have such as hydroxyl that can be reacted with isocyanate group,
The compound of amino isoreactivity hydrogen-based；By reacting the compound with polyisocyanate compound, so as to assign
Polyisocyanate compound is with hydrophily.As anionic hydrophilic polyisocyanate compound (C-1-1), particularly preferably have
There is sulfonic group.
Coating composition is once coated with about aqueous double-formulation of the invention, the acrylic resin (A) of above-mentioned hydroxyl,
The polyester resin (B) of hydroxyl and the content of polyisocyanate compound (C) are from the viewpoint of curability at low temperatures, preferably
For the hydroxyl equivalent in the resin of hydroxyl, isocyanate group in polyisocyanate compound (C) becomes 1.0~
2.0 equivalents, particularly ratio as 1.0~1.7 equivalents.
It about above-mentioned coloring pigment (D), such as can enumerate: titanium oxide, the flowers of zinc (Ami lead powder used in cosmetics), carbon black, chrome vermillion, Prussia
Indigo plant, cobalt blue, azo pigment, phthualocyanine pigment, quinacridone pigment, isoindoline system pigment, anthraquione pigmentss (threne
It pigments), is the coloring pigments such as pigment, dioxazine pigment, diketopyrrolopyrrolecocrystals system pigment, they can be individually
Using or combine two or more and use.
About the compounding amount of coloring pigment (D), the above-mentioned hydroxyl being once coated with aqueous double-formulation in coating composition
Acrylic resin (A), the polyester resin (B) of hydroxyl and 100 matter of total solid content of polyisocyanate compound (C)
On the basis of measuring part, generally in the range of 1~200 mass parts, preferably in the range of 20~150 mass parts, further preferably
In the range of 50~120 mass parts, this is suitable.
In above-mentioned coloring pigment (D), can as needed and and with extender pigment and/or bright pigment.As constitution
Pigment, such as enumerate clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silica, alumina white etc., as bright property face
Material, such as aluminium (comprising AM aluminum metallization) can be enumerated, copper, zinc, brass, nickel, aluminium oxide, mica, carried out by titanium oxide and/or iron oxide
Coating aluminium oxide, the mica, the glass flake that are coated by titanium oxide and/or iron oxide etc., they can individually make
With or combine two or more and use.
In terms of the dispersion of above-mentioned coloring pigment (D), known pigment dispersion resin can be used as needed
And/or dispersing aid.About pigment dispersion resin, usually using water-soluble acrylic resin, in particular, from for coloring
The viewpoints such as the gloss of wetability and dispersion stabilization and the film obtained for pigment under high pigment levels and water resistance
Consider, preferably uses and obtained and being copolymerized following monomer mixture in the presence of radical polymerization initiator
Acrylic copolymer, the monomer mixture include containing be selected from tertiary amino, quaternary ammonium base, sulfonic group, carboxylic acid group, phosphate
The polymerism unsaturated monomer of at least one kind of functional group in and/or non-ionic polymeric insatiable hunger with polyoxyalkylene chain
With monomer and other ethylenically unsaturated monomers.
Once be coated with coating composition about aqueous double-formulation of the invention, can further as needed and be suitable for containing:
Resin component, curing catalysts, thickener, ultraviolet absorbing agent, light stabilizer, defoaming other than (A) and (B) ingredient
The additive for coatings such as agent, plasticizer, organic solvent, surface conditioner, sedimentation preventing agent.
The solid concentration of coating composition is once coated with about aqueous double-formulation of the invention, it is often preferred that 30~70
Quality %, more preferably 35~65 mass %, more preferably 40~60 mass %.
It is once coated with coating composition about aqueous double-formulation of the invention, is typically set to pair comprising host agent and curing agent
Dosage form coating, the host agent contain the polyester resin (B) and coloring pigment of the acrylic resin (A) of hydroxyl, hydroxyl
(D), the curing agent contains polyisocyanate compound (C).
It is once coated with coating composition about aqueous double-formulation of the invention, itself known method such as air can be utilized
Atomized spray painting, airless spray coating, rotary-atomizing coating, curtain coating coating etc. and be coated on coated article, can also be in coating
When, carry out electrostatic application.Among them, preferably the methods of air-atomizing coating, rotary-atomizing coating.About its coating
Amount is usually the amount for becoming 10~80 μm according to film thickness is solidified, preferably becomes 10~50 μm of amount.By film obtained
Heated and in the case where curing and drying, for example, using Hot-blast Heating, infrared heating, inductive heating etc., with 50~120
DEG C, preferably with 60~110 DEG C of temperature, heat 10 minutes~40 minutes or so, this is appropriate.
Coated article is not particularly limited, such as can enumerate the coated article formed by raw material such as metal, plastics.Wherein, exist
It, can be according to logical in terms of made of metal and/or the car body or its component, particularly automobile body-used steel plate of plastics manufacture
The mode often carried out carries out chemical conversion treatment as needed, in addition, can also implement cationic electrodeposition coating in advance.
In addition, can in advance as needed and on plastic cover coating prime lacquer.
Embodiment
Hereinafter, enumerating embodiment and comparative example and being more particularly described the present invention.But the present invention is not only limited to these realities
Apply example.It is explained, any one of " part " and " % " are all based on quality criteria.
The manufacture of the acrylic resin (A) of hydroxyl
Production Example 1
The third two are added into the glass system four-hole boiling flask for having thermometer, blender, reflux condensing tube, nitrogen inlet
50 parts of alcohol list propyl ether, unders nitrogen flowing while stirring and is warming up to 120 DEG C.4 hours are spent after reaching exactly to 120 DEG C and are dripped
Add following mixed solutions 1, further the temperature after completion of dropwise addition at 120 DEG C is kept for 1 hour.
" mixed solution 1 "
Then in the state of keeping 120 DEG C of temperature, spend following mixed solutions 2 are added dropwise within 1 hour in Xiang Shangshu flask,
The acrylic resin solution of hydroxyl is further kept for 1.5 hours and obtained at 120 DEG C after completion of dropwise addition.
" mixed solution 2 "
The resin solid content of acrylic acid multielement alcoholic solution obtained is 77.5%, weight average molecular weight 15000.Then,
From acrylic acid multielement alcoholic solution obtained, propylene glycol monopropyl ether is subjected to distillation removal under reduced pressure, until solid content becomes
Until 85%.95 DEG C are cooled to, 2.41 parts of dimethylethanolamine is added and stirs 30 minutes.Further, it stirs on one side
2 hours dropwise addition deionized waters are spent in such a way that resin solid content becomes 45% on one side, to obtain per resin solid
The acid value of object is 21mgKOH/g, the hydroxyl value of per resin solid content is 112mgKOH/g, 0.12 μm of average grain diameter of hydroxyl
Acrylic resin aqueous dispersion (A-1).
Production Example 2~9
In Production Example 1, each raw material and compounding amount are set as content shown in following table 1, in addition to this, with manufacture
Example 1 operates in the same way and obtains acrylic resin aqueous dispersion (A-2)~(A-9) of each hydroxyl.
(*) storage stability test
The acrylic resin aqueous dispersion of each hydroxyl obtained in above-mentioned Production Example, according to following test sides
Method has carried out the test of storage stability.
Storage stability: above-mentioned each aqueous dispersion is added to the vial that capacity is about 1L with 800g, in 40 DEG C of perseverance
It is stored 120 days in greenhouse.Thereafter, room temperature is returned to, the state among container is observed by visual observation, is carried out according to following benchmark
Evaluation.Result is shown in table 1 together.
◎: the absolutely not generation of discovery sediment and/or viscosity change.
Zero: finding to pettiness that the generation of sediment and/or viscosity change are still restored using stirring.
△: generation and/or the viscosity change of sediment are found.
×: find sediment it is significant generation and/or significant viscosity change.
Table 1
The manufacture of the polyester resin (B) of hydroxyl
Production Example 10~15
Into the four-hole boiling flask for having heating device, agitating device, thermometer, reflux condenser and rectifying column, add
The sour component and alcohol component for entering molar ratio shown in following table 2, after being warming up to 160 DEG C, DEG C cost 3 is small from 160 DEG C to 230
When heat up while condensation water generated is distilled and removed using rectifying column, carried out at 230 DEG C thereafter 2 hours it is anti-
It answers.
Then, rectifying column is changed to separator, is suitably added toluene, maintained the reflux for state at 230 DEG C, utilize on one side
Condensation water is separated, distills removal by separator, carries out condensation reaction on one side.
Become for 7 time point in resinous acid value, removes toluene under reduced pressure, be cooled to 170 DEG C.It is added into reaction product
The trimellitic anhydride of molar ratio shown in following table 2,170 DEG C progress addition reaction 60 minutes, then add relative to anti-
The propylene glycol monomethyl ether for answering for product 10%, after temperature has been set as 85 DEG C, with N, during N- dimethylethanolamine carries out
With, further slowly add deionized water and aqueous dispersion is made, to obtain each polyester resin (B- of solid content 45%
1)~(B-6) (pH is all adjusted to 8.5).By polyester resin (B-1)~(B-6) acid value, the hydroxyl of each hydroxyl obtained
Value and number-average molecular weight are shown in following table 2 together.
Table 2
| Production Example | 10 | 11 | 12 | 13 | 14 | 15 |
| Polyester resin (B) title | B-1 | B-2 | B-3 | B-4 | B-5 | B-6 |
| 1,2- cyclohexane cyclohexanedimethanodibasic acid anhydride | 0.27 | 0.53 | 0.55 | 0.55 | 0.85 | |
| Phthalic anhydride | 0.32 | |||||
| Adipic acid | 0.58 | 0.32 | 0.25 | 0.3 | 0.55 | |
| Trimethylolpropane | 0.35 | 0.2 | 0.45 | 0.4 | 0.3 | 0.3 |
| Neopentyl glycol | 0.15 | 0.4 | ||||
| 1,3-PD | 0.3 | |||||
| 1,6- hexylene glycol | 0.7 | |||||
| 2- butyl -2- ethyl -1,3-PD | 0.65 | 0.8 | 0.4 | 0.6 | ||
| Trimellitic anhydride (addition of acid sour component) | 0.028 | 0.028 | 0.02 | 0.0165 | 0.023 | 0.028 |
| The mol% of (× 1) in sour component | 31 | 60 | 67 | 63 | 0 | 97 |
| The mol% of (× 2) in alcohol component | 65 | 80 | 55 | 60 | 40 | 0 |
| Hydroxyl value (mgKOH/g) | 142 | 105 | 195 | 151 | 149 | 138 |
| Acid value (mgKOH/g) | 19 | 19 | 16 | 12 | 19 | 19 |
| Number-average molecular weight | 1400 | 1500 | 1000 | 1500 | 1400 | 1400 |
Aqueous double-formulation is once coated with the production of coating
Embodiment 1
The pigment dispersion paste agent (P-1) (note 1) that is 100 parts according to solid content is added, according to solid content is 30 parts and is making
It makes the acrylic resin aqueous dispersion (A-1) of hydroxyl obtained in example 1, be 20 parts according to solid content in Production Example 10
Obtained in hydroxyl polyester resin (B-1), 2- (dimethylamino) ethyl alcohol and deionized water and carry out pH adjustment, into
One step by as " the Bayhydur XP-2655 " of curing agent No.1 (trade name, Sumika Covestro Urethane Co.,
Ltd. manufacture, polyisocyanate compound) 30 parts (NC0/OH ratio is 1.0), 20 parts of diethylene glycol monoethyl ether acetic acid esters carry out it is uniform
Mixing, obtaining solid content is at 45%, 20 DEG C based on 20 seconds water of viscosity obtained from Ford cup (Ford cup) No.4
Property double-formulation is once coated with coating (X-1).
Embodiment 2~19 and comparative example 1~2
In embodiment 1, the formula composition of table 3 is made, in addition to this, operates similarly with example 1, obtains aqueous
Double-formulation is once coated with coating (X-2)~(X-21).It is explained, table 3 is indicated with solid content.
(note 1) pigment dispersion paste agent (P-1): to being stirred in container, point for being 20 parts according to solid quality is added
Scattered acrylic resin (i) solution (note 3), 80 parts of " JR-806 " (trade name, the manufacture of Tayca company, rutile-type dioxy
Change titanium) and 30 parts of deionized water, equably mix, further, add 2- (dimethylamino) ethyl alcohol, so as to adjust for
pH8.0.Then, mixed liquor obtained is incorporated in wide mouth glass bottle, be added as decentralized medium diameter aboutBead and seal, using paint shaker (paint shaker) disperse 4 hours, thus obtain white
Dispersible pigment dispersion (P-1).
(note 2) pigment dispersion paste agent (P-2): to being stirred in container, point for being 20 parts according to solid quality is added
Scattered acrylic resin (ii) solution (note 4), " IRGAZINRED L3660HD " (trade name, BASF AG's manufacture, diketone
Base pyrrolopyrrole system red pigment) 15 parts and 30 parts of deionized water, it equably mixes, further adds 2- (dimethylamino)
Ethyl alcohol, so as to adjust for pH8.0.Then, mixed liquor obtained is incorporated in wide mouth glass bottle, is added and is used as decentralized medium
Diameter aboutBead and seal, dispersed 4 hours using paint shaker, to obtain red pigment point
Dispersion liquid (P-2).
(note 3) disperses acrylic resin (i) solution: to having thermometer, thermostat, agitating device, returned cold
It is 85 DEG C that 35 parts of propylene glycol monopropyl ether is added in the reaction vessel of condenser, nitrogen ingress pipe and Dropping feeder and heats up, so
It spends 4 hours afterwards and 18 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 35 parts of isobornyl acrylate, propylene is added dropwise
10 parts of sour 2- hydroxyl ethyl ester, 1.5 parts of acrylic acid, 0.5 part of 2- methacryloxyethyl phosphate ester acid, " NF BISOMER
20 parts of S20W " (trade name, the first industrial pharmaceutical company manufacture, the polyethylene glycol monomethacrylate of molecular weight 2000), third
15 parts of glycol monopropyl ether and 2, the mixture of 2.3 parts of 2 '-azos bis- (2,4- methyl pentane nitriles), completion of dropwise addition post curing 1
Hour.Thereafter it further spends 1 hour and 10 parts of propylene glycol monopropyl ether and 2 is added dropwise, 2 '-azos are bis- (2,4- methyl pentane nitrile)
1 part of mixture, completion of dropwise addition post curing 1 hour.7.4 parts of diethanol amine are further added, solid content 50% is obtained
Dispersion acrylic resin (i) solution.The acid value of acrylic resin obtained is 15mgKOH/g, and hydroxyl value is
48mgKOH/g。
(note 4) disperses acrylic resin (ii) solution: to having thermometer, thermostat, agitating device, returned cold
It is 85 DEG C that 35 parts of propylene glycol monopropyl ether is added in the reaction vessel of condenser, nitrogen ingress pipe and Dropping feeder and heats up, so
It spends 4 hours afterwards and 30 parts of methyl methacrylate, 20 parts of 2-EHA, 29 parts of n-butyl acrylate, third is added dropwise
15 parts of olefin(e) acid 2- hydroxyl ethyl ester, 6 parts of acrylic acid, 15 parts of propylene glycol monopropyl ether and 2, bis- (2, the 4- methyl pentane nitriles) 2.3 of 2 '-azos
Part mixture, completion of dropwise addition post curing 1 hour.Thereafter further spend 1 hour and be added dropwise 10 parts of propylene glycol monopropyl ether with
And 2, the mixtures of 1 part of 2 '-azos bis- (2,4- methyl pentane nitriles), completion of dropwise addition post curing 1 hour.Diethyl is further added
7.4 parts of hydramine, obtain dispersion acrylic resin (ii) solution of solid content 55%.Acrylic resin obtained
Acid value is 47mgKOH/g, hydroxyl value 72mgKOH/g.
(note 5) curing agent No.2: " Bayhydur 3100 ", trade name, Sumika Covestro Urethane Co.,
Ltd. it manufactures, polyisocyanate compound.
The test production of coated article
On the cold-rolled steel sheet for implementing trbasic zinc phosphate chemical conversion treatment, by " Elecron GT-10 " (trade name,
The manufacture of Kansai Paint Co., Ltd., cation electrodeposition coating) it is carried out in the way of making dry film thickness become 20 μm
Electrodeposition coating heats 30 minutes at 170 DEG C and solidifies that test coated article (1) has been made.
In addition, on polypropylene board (carrying out ungrease treatment), by priming paint " Soflex 3100 " (trade name: Kansai
The manufacture of Paint Co., Ltd., the electric conductivity organic solvent type coatings containing polyolefin) in such a way that dry film thickness becomes 10 μm
Air-atomizing coating is carried out, heated 4 minutes at 80 DEG C and test coated article (2) have been made.
Further, on ABS plate (carrying out ungrease treatment) and FRP plate (carrying out ungrease treatment), respectively by priming paint
" ASX3807CD " (trade name: the manufacture of Kansai Paint Co., Ltd., the electric conductivity water paint containing polyolefin) is according to dry
Dry film thickness carries out air-atomizing coating as 10 μm of mode, heated 4 minutes at 80 DEG C and be made test coated article (3) with
And coated article (4) are used in test.
Test the production of coated plate
In above-mentioned test on coated article (1)~(4), using the electrostatic atomizer of rotary-atomizing type, by above-described embodiment
With each aqueous double-formulation coating obtained in comparative example, electrostatic coat is carried out in such a way that dry film thickness becomes 35~45 μm
Dress, placed 5 minutes.Then, each test coated plate is produced in 80 DEG C of 20 minutes (retention times) of heating.
Evaluation test
For each breadboard obtained in above-described embodiment 1~19 and comparative example 1~2, according to following test sides
Method is evaluated.Evaluation result is shown in following Table 3 together.
Finish: by it is each test coated plate (1) film coated surface light bright and dark pattern carry out optical scanner, using as pair
The BYK corporation " Wave-Scan " for the device that the contrast (power) of reflected light is parsed, find out wave-length coverage 600~
1000 μm of long wave long values (longterm waviness) measured and the shortwave long value measured at 100~600 μm of wave-length coverage
(shortterm waviness), respectively, the parameter as finish texture is evaluated.They are the luminous intensities of measurement
Dispersion value.It is worth smaller, indicates that finish texture (flatness of coating surface) is the better.
20 ° of gloss: the mirror surface luster (20 degree) of JIS K5600-4-7 (1999) with each test coated plate (1)~(4) is
Benchmark determines the glossiness of each coating surface.As benchmark, if the value of 20 degree of gloss values is 80 or more, finish appearance (light
Pool) it is good.
Hardness: each test coated plate (1) is placed in thermostatic chamber 24 hours of 20 DEG C, TUKON (American is then utilized
The manufacture of Chain&Cable Company company, micro-hardness tester) determine " Tukon hardness ".
Also referred to as the Tukon hardness of Knoop hardness number (KHN) indicates, with certain test load by tetragonal pyramid
Body diamond pressure squeezes into the hard of the film in the test face of material, read according to the size in the hollow portion of diamond shape generated
Degree, the numerical value the big, indicates that hardness is higher.
Table 3
Claims (4)
1. a kind of aqueous double-formulation is once coated with coating composition, which is characterized in that it is the acrylic compounds tree containing hydroxyl
Rouge (A), the polyester resin (B) of hydroxyl, the aqueous double-formulation of polyisocyanate compound (C) and coloring pigment (D) are primary
It is coated with coating composition；
The acrylic resin (A) of hydroxyl is the acrylic compounds tree of 100~200mgKOH/g of hydroxyl value, 5~50mgKOH/g of acid value
Rouge；
The polyester resin (B) of hydroxyl includes alicyclic polycarboxylic acid (the including acid anhydrides) sour component of (x1) as raw material, is contained
Amount is at least 30 moles of % on the basis of the total amount of sour component, and includes that the carbon atom number with branched alkylidene is at least
Alcohol component of 5 glycol (x2) as raw material, content are at least 40 moles of % on the basis of the total amount of alcohol component, and
It is the polyester resin that hydroxyl value is 100~200mgKOH/g, acid value is 10~30mgKOH/g.
2. aqueous double-formulation according to claim 1 is once coated with coating composition, wherein
The acrylic resin (A) of hydroxyl is by presence of organic solvent by the polymerism insatiable hunger of mutually different composition
It is polymerize with being divided into the multistage with monomer component and obtains acrylic resin, and the acrylic resin is subjected to water
Disperse to acquisition,
Polymerism unsaturated monomer ingredient (I) as one of them include polymerism unsaturated monomer (a1) containing epoxy group,
The polymerism unsaturated monomer (a2) of hydroxyl and other polymerism unsaturated monomers (a3),
Other polymerism unsaturated monomer ingredient (II) used in the polymerization at least one stage includes carboxylic polymerization
The polymerism unsaturated monomer (b2) and other polymerism unsaturated monomers (b3) of property unsaturated monomer (b1), hydroxyl.
3. a kind of coating film-forming methods, which is characterized in that
The coating cation electrodeposition coating on made of metal coated article, then coating on it is of any of claims 1 or 2 aqueous
Double-formulation is once coated with coating composition.
4. a kind of coating film-forming methods, which is characterized in that
The coating prime lacquer coating on plastics coated article, the then aqueous double-formulation one of any of claims 1 or 2 of coating on it
Secondary coating coating composition.
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| CN114450363A (en) * | 2019-09-30 | 2022-05-06 | 大日本涂料株式会社 | Two-pack type coating composition and coated article |
| CN115073949A (en) * | 2021-03-02 | 2022-09-20 | 荒川化学工业株式会社 | Aqueous composition, cured product and laminate |
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| JP2019099625A (en) | 2019-06-24 |
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