CN101273103A - Water-based metallic coating composition and method of forming multilayered coating film - Google Patents

Abstract

A water-based metallic coating composition which retains excellent properties of water-based metallic coating materials, such as coloration, adhesion in re-coating, unsusceptibility to chipping, and wet adhesion, and which, when applied by the two-coat one-bake coating method, gives a coating film less apt to suffer the disordering of brightening-pigment orientation through the application of a clear coating material. The coating film does not change in flip-flop effect and retains the excellent flip-flop effect. Also provided are: a method of two-coat one-bake coating which employs the coating composition; and a multilayered coating film which is obtained from the coating composition and has excellent flip-flop effect. The water-based metallic coating composition comprises a film-forming resin, a hardener, and a brightening pigment, and is characterized in that the film-forming resin comprises an acrylic resin emulsion, the acrylic resin emulsion being one obtained by two-stage emulsion polymerization, the solid resin ingredient in the emulsion having an acid value of 1-30 mg-KOH/g and a hydroxyl value of 10-150 mg-KOH/g, and the emulsion having a particle diameter of 20-140 nm and the hardener is an aqueous hydrophobic-melamine-resin dispersion having a particle diameter of 20-140 nm.

Description

The method of waterborne metallic paint composition and formation multilayer film

Technical field

[0001] the present invention relates to the water-based metal colored paint composition, form the method for multilayer film and the multilayer film that can obtain by described method with described composition.

Background technology

[0002] water-based paint compositions that uses at the motor vehicle coating step comprises a kind of coating composition, and this coating composition comprises resin (acrylic resin that for example, has functional group such as carboxyl and hydroxyl) and melamine resin as linking agent.The hydrophobicity melamine resin often is used for water-based paint compositions as linking agent, although it uses in water-bearing media.

[0003] when the hydrophobicity melamine resin is used for water-based paint compositions as linking agent, there is the problem that bad water dispersible is provided.A kind of technology as head it off, Japan patent applicant announce S53-99232 and 2004-315623 propose with a kind of aqueous resin dispersion as linking agent, this dispersion is obtained by the reaction of hydrophobic melamine resin with the resin (as acrylic resin, Synolac etc.) with specific acid number, specific hydroxyl value and specified molecular weight, but required water dispersible can not be provided.

[0004] Japan patent applicant announce 2002-308993 discloses a kind of aqueous resin dispersion, this dispersion comprises the reaction product that is obtained by the following component of heating: (A) acrylic resin, it has the weight-average molecular weight of 5000-100000, the acid number of 10-100mgKOH/g and the hydroxyl value of 20-200mgKOH/g; (B) hydrophobic melamine resin; (C) vibrin.Described aqueous resin dispersion has the viscosity ratio (that is the viscosity before the viscosity/heating after the heating) that 20-200% increases.In order to improve some performances such as water dispersible, available have the resin (as acrylic resin) of high acid value with hydrophobic melamine resin modified.

[0005] on the other hand, Japan patent applicant announce S63-193968 and H07-041729 propose with a kind of aqueous resin dispersion as linking agent, this dispersion obtains by dispersing hydrophobic melamine resin in the water-based metal colored paint composition and a kind of resin, described resin has specific acid number, specific hydroxyl value and specified molecular weight, as graft resin, acrylic resin, Synolac etc., but can not provide required water dispersible.

The invention approach

[0006] inventor has submitted several patent applications to, and the aqueous pigmented coating composition that is proposed comprises acrylic resin and hydrophobicity melamine resin (Japanese patent application 2004-332110 and 2004-349019) basically.These technology can be improved the dispersiveness of hydrophobicity melamine resin, and can provide and have good look performance, goodly be coated with filming of adhesive power, good cracking resistance and good water-fast adhesive power again.

[0007] yet, be used as under the situation of the coloured primer composition of metal at above-mentioned aqueous pigmented coating composition, when using the coloured primer composition of metal in the method that is forming the coloured multilayer film of metal, the coloured coloured outward appearance of filming of metal of filming outward appearance own and covering with transparent coating of metal just has notable difference, said method comprising the steps of, the coloured primer composition of metallizing is to form the coloured undercoat of metal; On the coloured undercoat of uncured metal, apply clear coating composition, to form Clear coating; And heating immediately (or curing) coloured undercoat of metal and Clear coating, described method are commonly called two and are coated with single baking coating method.Usually, form the coloured bottom coating of metal and above two being coated with in single baking coating method of transparent coating, between coloured primer composition of metallizing and coating clear coating composition, insert wherein and carry out exsiccant pre-heating step (for example, experiencing about 5 minutes) at about 80 ℃ in the low temperature short period of time.Yet flash of light colored pigment wherein can not be suitably fixed in preheating.As shown in Figure 1, during applying clear coating composition on the coloured primer composition of uncured metal, clear coating composition (most of in organic solvent) the coloured bottom coating of disadvantageous effect metal.As shown in Figure 1, can think the flash of light colored pigment orientation be interfered.The orientation ideal of flash of light colored pigment is arranged in parallel, as shown in Figure 2.

Disclosure of the Invention

Problem to be solved

[0008] the object of the present invention is to provide two of a kind of water-based metal colored paint composition, composition utilization to be coated with single multilayer film that dries by the fire coating method and have good down flop property, wherein the water-based metal colored paint composition has premium properties, as good tinctorial property, be coated with adhesive power, cracking resistance, water-fast adhesive power etc. again, those performances of the aforementioned coating composition that provided by the contriver are provided these performances.Utilize two to be coated with single baking coating method, water-based metal colored paint composition of the present invention can provide has filming of superior top-ranking performance and good down flop property, before applying clear coating composition/and do not disturb the orientation of flash of light colored pigment wherein afterwards, also can sharp influence down flop property.

The method of head it off:

[0009] therefore, the present invention can provide a kind of water-based metal colored paint composition that comprises film-forming resin, solidifying agent and flash of light colored pigment, wherein

Film-forming resin comprises acrylic resin emulsion, described emulsion can be obtained by the two-stage letex polymerization, and have the acid number (based on the solid resin content) of 1-30mgKOH/g, the hydroxyl value (based on the solid resin content) of 10-150mgKOH/g and the particle diameter of 20-140nm, and

Solidifying agent is the aqueous dispersion with hydrophobic melamine resin of 20-140nm particle diameter.

[0010] acrylic resin emulsion of the present invention can be preferably by a kind of two-stage emulsion polymerization acquisition of monomer mixture, and described monomer mixture comprises the unsaturated monomer with at least two unsaturated double-bonds with respect to film-forming resin solids content weight 0.05-30.0% weight.

[0011] unsaturated monomer with at least two unsaturated double-bonds is selected from ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate and (methyl) allyl acrylate.

[0012] film-forming resin can further comprise the polyoxyalkylene compounds with formula (1) with respect to solid resin content weight 0.01-10% weight in the coating composition:

H(-OR) _f-OH (1)

Wherein

R is the alkyl with 2-5 carbon atom that can have side chain, and

F is 100 to 18000 integer.

[0013] polyoxyalkylene compounds of the present invention preferably has the weight-average molecular weight (Mw) of 10000-1000000.

[0014] water-based metal colored paint composition of the present invention can further comprise viscosity modifier, and described viscosity modifier comprises the carbamate compounds (A) by general formula (1) expression

With carbamate compounds (B) by general formula (2) expression

Mixture,

Wherein

R ₁Identical or different, expression has the alkyl of 8 to 24 carbon atoms,

Y represents to eliminate the reactive residue that isocyanate group obtains from vulcabond,

OA and AO independently represent to have the oxyalkylene group of 2 to 4 carbon atoms,

O represents Sauerstoffatom,

C represents carbon atom,

N represents nitrogen-atoms,

M and n independently represent 20 to 500 integer,

A and d independently represent 1 to 100 integer,

B represents 40 to 500 integer,

C represents 1 to 5 integer,

(bxc) be 150 to 2500,

F represents 200 to 25000 integer, and

R, Y and P can be independently identical or different,

Wherein each carbamate compounds has the oxyethylene group with respect to oxyalkylene group gross weight at least 80% weight, and

Wherein the weight ratio of carbamate compounds (A)/carbamate compounds (B) is 95/5-5/95, and carbamate compounds (A) and total content (B) are 0.2-4.0% weight with respect to solid resin content in the water-based metal colored paint composition.

[0015] the present invention further provides a kind of method that forms multilayer film, described method comprises:

Step (I) applies aqueous primer composition on goods, to form undercoat;

Step (II) is not making undercoat apply clear coating composition under solidifying on undercoat, to form Clear coating; With

Step (III) heats undercoat and Clear coating simultaneously,

Wherein aqueous primer composition is above-mentioned water-based metal colored paint composition.

The invention effect

[0016] water-based metal colored paint composition of the present invention comprises acrylic resin emulsion as film-forming resin, described emulsion can be obtained by the two-stage letex polymerization, and has the acid number of 1-30mgKOH/g, the hydroxyl value of 10-150mgKOH/g and the particle diameter of 20-140nm.Can prevent to disturb the wherein orientation of metal colored pigment effectively.Specifically, comprising as the acrylic resin emulsion of film-forming resin under monomer for example has at least two unsaturated double-bonds in molecule the situation of unsaturated monomer, emulsion has three-dimensional structure in nuclear part, shell part or two parts.Therefore, after applying clear coating composition thereon, can prevent to disturb the orientation of metal colored pigment in the water-based metal colored paint composition more effectively, even clear coating composition (especially type of organic solvent clear coating composition) exerts an influence to it.

[0017] water-based metal colored paint composition of the present invention can further comprise specific polyoxyalkylene compounds.This compound can prevent to disturb the orientation of flash of light colored pigment very effectively.

[0018] water-based metal colored paint composition of the present invention can further comprise to certainty ratio by the carbamate compounds (A) of general formula (1) expression with by the mixture of the carbamate compounds (B) of general formula (2) expression.This mixture also can prevent to disturb the orientation of metal colored pigment.

[0019] water-based metal colored paint composition of the present invention can provide and have filming of natural good color performance.In addition, the method for utilizing the water-based metal colored paint composition to form multilayer film can provide and have good adhesive power, cracking resistance, water-fast adhesive power and the look performance multi-layer of being coated with again and film.

The accompanying drawing summary

[0020] Fig. 1 is for utilizing the schematic section of filming that worsens down flop property that has that applies clear coating composition after applying aqueous primer composition, and it is presented at the state of flash of light colored pigment in the bottom coating.

Fig. 2 is the schematic section of filming with good down flop property.

Best mode is implemented in invention

[0021] following detailed description the present invention.

The water-based metal colored paint composition

Water-based metal colored paint composition of the present invention comprises film-forming resin, solidifying agent and flash of light colored pigment.Film-forming resin can be obtained by the two-stage emulsion polymerization.Film-forming resin comprises acrylic resin emulsion, and described emulsion has the acid number (based on the solid resin content) of 1-30mgKOH/g, the hydroxyl value (based on the solid resin content) of 10-150mgKOH/g and the particle diameter of 20-140nm.Solidifying agent comprises the aqueous dispersion of the hydrophobic melamine resin with 20-140nm particle diameter.The monomer that is used for the two-stage emulsion polymerization is preferably a kind of monomer mixture, and described monomer mixture comprises the unsaturated monomer with at least two unsaturated double-bonds with respect to film-forming resin solids content 0.05-30.0% weight.

[0022] as mentioned above, preferably when preparing acrylic resin emulsion as film-forming resin, acrylic monomer comprises the unsaturated monomer with at least two unsaturated double-bonds.Use under the situation of the unsaturated monomer with at least two unsaturated double-bonds at the formation acrylic resin emulsion, crosslinking reaction is carried out in acrylic resin emulsion, and obtains three-dimensional acrylic resin emulsion.

[0023] although the present invention is not bound by any particular theory, should understand according to following reason, available three-dimensional acrylic resin emulsion prevents to disturb the orientation of metal colored pigment.Believe the orientation that can prevent by the metallizing primer composition effectively according to the present invention and apply the interference metal colored pigment that clear coating composition causes then in the above.Believe this interference seemingly since in the above the solvent that clear coating composition comprises when applying clear coating composition infiltrate due to the swelling particle that produces in metal bottom coating and the acrylic resin emulsion.Therefore, the swelling that the solvent that uses three-dimensional acrylic resin emulsion can prevent to comprise in the clear coating composition causes also can prevent to disturb the orientation of metal colored pigment.

[0024] in addition, available above-mentioned water-based metal colored paint composition forms multilayer film by the motor vehicle coating method, wherein use a kind of coating composition, this coating composition comprises the aqueous dispersion of the hydrophobic melamine resin of aforesaid propylene acid resin emulsion and the above-mentioned 20-140nm of having particle diameter.Therefore, the gained multilayer film has good adhesive power, cracking resistance and the water-fast adhesive power of being coated with again.Therefore, in the motor vehicle coating step, can preferably in the method that forms multilayer film, use above-mentioned water-based metal colored paint composition.

[0025] Film-forming resin

Above-mentioned film-forming resin comprises acrylic resin emulsion, described emulsion can be obtained by the two-stage letex polymerization, and has the acid number (based on the solid resin content) of 1-30mgKOH/g, the hydroxyl value (based on the solid resin content) of 10-150mgKOH/g and the particle diameter of 20-140nm.The monomer that is used for the two-stage emulsion polymerization is preferably a kind of monomer mixture, and described monomer mixture comprises the unsaturated monomer with at least two unsaturated double-bonds with respect to film-forming resin solids content 0.05-30.0% weight.

[0026] Acrylic resin emulsion

Aforesaid propylene acid resin emulsion has the acid number (based on the solid resin content) of 1-30mgKOH/g.When less than 1mgKOH/g, the stability of emulsion will reduce.When surpassing 30mgKOH/g, the water tolerance that gained is filmed will reduce.Acid number is preferably 3-25mgKOH/g.

[0027] aforesaid propylene acid resin emulsion has the hydroxyl value of 10-150mgKOH/g.When hydroxyl value during less than 10mgKOH/g, the physicals that gained is filmed will worsen.When surpassing 150mgKOH/g, the water tolerance that gained is filmed will reduce.Hydroxyl value is preferably 15-120mgKOH/g.In the present invention, the acid number of aforesaid propylene acid resin emulsion is the experiment measuring value, and the definite calculated value of content that hydroxyl value is served as reasons and synthesized used unsaturated monomer.

[0028] aforesaid propylene acid resin particle size of emulsion is 20-140nm.During less than 20nm, the solids content in the coating composition (NV) obviously reduces at above-mentioned particle diameter.When surpassing 140nm, the color characteristics that gained is filmed will variation.

[0029] can for example regulate particle diameter by regulating monomer formulation and letex polymerization condition.Particle diameter is 30-120nm more preferably, more preferably 50-100nm.In the present invention, acrylic resin emulsion of the present invention or hydrophobic melamine resin particle size of emulsion average dispersion particle diameters for using ELS-800 (by OTSUKA ELECTRONICS CO., LTD. makes) to measure under the following conditions:

Sample: use the ion exchanged water infinite dilution

Measure temperature: 25 ℃.

[0030] specifically, aforesaid propylene acid resin emulsion preferably includes the emulsion that is obtained by following letex polymerization, and the letex polymerization utilization has the unsaturated monomer of at least two unsaturated double-bonds and carboxy-containing acid group's unsaturated monomer, the unsaturated monomer of hydroxyl etc. as raw material.In the present invention, the acrylic resin emulsion of utilization of the present invention is preferably the what is called nuclear-shell type acrylic resin emulsion that has nuclear part and shell part according to the two-stage letex polymerization.

[0031] when above-mentioned film-forming resin comprises nuclear-shell type acrylic resin emulsion, above-mentioned nuclear partly is preferably the nuclear part that is obtained by letex polymerization, the letex polymerization utilization comprises the nuclear monomer mixture of the unsaturated monomer that contains hydroxy-acid group, and described nuclear partly has the acid number of 0-100mgKOH/g.When surpassing 100mgKOH/g, the water tolerance that gained is filmed will reduce.Acid number is 0-50mgKOH/g more preferably.In the present invention, the acid number of above-mentioned nuclear part is the acid number by the acrylic resin emulsion of first letex polymerization acquisition, and this acid number is the calculated value of being determined by monomer content in the above-mentioned nuclear monomer mixture.

[0032] above-mentioned shell partly is preferably the shell part that is obtained by letex polymerization, and the letex polymerization utilization comprises the shell monomer mixture of the unsaturated monomer that contains hydroxy-acid group, and described shell partly has the acid number of 25-200mgKOH/g.When above-mentioned acid number during less than 25mgKOH/g, the stability of emulsion will reduce, and execution of coating is also insufficient.When surpassing 200mgKOH/g, the water tolerance that gained is filmed will reduce.Acid number is 30-180mgKOH/g more preferably.In the present invention, the acid number of above-mentioned shell part is the calculated value of being determined by monomer content in the above-mentioned shell monomer mixture.

[0033] above-mentioned nuclear monomer mixture and/or above-mentioned shell monomer mixture comprise conventional acrylic monomer.Preferred acrylic monomer comprise have at least two unsaturated double-bonds unsaturated monomer as basic monomer.Unsaturated monomer with at least two unsaturated double-bonds forms the crosslinking structure in the emulsion particle.The clear coating composition disadvantageous effect that is not subjected to apply thereon can be more effective.Can or in nuclear monomer mixture and shell monomer mixture, comprise unsaturated monomer at nuclear monomer mixture or shell monomer mixture with at least two unsaturated double-bonds.Nuclear monomer mixture and shell monomer mixture all comprise the disadvantageous effect that the unsaturated monomer with at least two unsaturated double-bonds preferably farthest reduces clear coating composition.The amount of the unsaturated monomer with at least two unsaturated double-bonds that uses is 0.05-30.0% weight with respect to solids content weight in the film-forming resin, preferred 0.5-10.0% weight, more preferably 1.0-5.0% weight.When being lower than 0.05% weight, just can not obtain adding this monomeric effect.When surpassing 30.0% weight, just be difficult to prepare acrylic resin emulsion.

[0034] above-mentioned nuclear monomer mixture and/or above-mentioned shell monomer mixture can have hydroxyl.Above-mentioned hydroxyl value is 10-150mgKOH/g, preferred 15-120mgKOH/g.When above-mentioned hydroxyl value during, just can not obtain enough curing performances less than 10mgKOH/g.When surpassing 150mgKOH/g, the various performances that gained is filmed will reduce.

[0035] in addition, above-mentioned nuclear monomer mixture and/or above-mentioned shell monomer mixture can comprise above-mentioned other ethylenically unsaturated monomers.In the present invention, from the physicals viewpoint that gained is filmed, the second-order transition temperature (Tg) of above-mentioned nuclear-shell type acrylic resin emulsion is preferably-20 to 80 ℃.

[0036] carboxy-containing acid group's unsaturated monomer comprises but the indeterminate for example vinylformic acid that is limited to; methacrylic acid; propylene dimer acid; Ba Dousuan; phthalic acid 2-acryloxy ethyl ester; succsinic acid 2-acryloxy ethyl ester; phosphoric acid 2-acryloxy ethyl ester (2-acryloyloxyethylacid phosphate); 2-acrylamide-2-methyl propane sulfonic acid ester; ω-carboxyl-polycaprolactone list (methyl) acrylate; iso-crotonic acid; α-hydrogen-ω-[(1-oxo-2-propenyl) oxygen base]-poly-[oxygen base (1-oxo-1,6-hexane two bases)]; toxilic acid; fumaric acid; methylene-succinic acid; 2-vinyl Whitfield's ointment; 3-vinyl acetylsalicylic acid etc.

[0037] unsaturated monomer of hydroxyl for example comprises the affixture of (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, vinyl carbinol, methylallyl alcohol (methacryl alcohol) and (methyl) Hydroxyethyl Acrylate and 6-caprolactone.In these monomers, the affixture of (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxyl butyl ester and (methyl) Hydroxyethyl Acrylate and 6-caprolactone etc. is preferred.

[0038] above-mentioned other ethylenically unsaturated monomers comprise, for example, wherein ester moiety has (methyl) acrylate of 1 or 2 carbon atom, i.e. (methyl) methyl acrylate and (methyl) ethyl propenoate; Wherein ester moiety has 3 or (methyl) acrylate of more a plurality of carbon atoms, for example (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, lauryl methacrylate(LMA), phenyl acrylate, (methyl) isobornyl acrylate, cyclohexyl methacrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid dihydro dicyclopentadienyl ester etc.; Polymerisable amido compounds, for example (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N, N-dioctyl (methyl) acrylamide, N-monobutyl (methyl) acrylamide, single octyl group (methyl) acrylamide of N-, 2,4-dihydroxyl-4 '-vinyl benzophenone, N-(2-hydroxyethyl) acrylamide, N-(2-hydroxyethyl) Methacrylamide etc.; Polymerisable aromatic substance, for example vinylbenzene, alpha-methyl styrene, vinyl ketone, t-butyl styrene, to chloro-styrene, vinyl naphthalene etc.; Polymerisable nitrile, for example vinyl cyanide, methacrylonitrile etc.; Alpha-olefin, for example ethene, propylene etc.; And vinyl ester, for example vinyl-acetic ester, propionate etc.

[0039] unsaturated monomer that more preferably will have at least two unsaturated double-bonds is used for above-mentioned nuclear monomer mixture and/or above-mentioned shell monomer mixture.Unsaturated monomer with at least two unsaturated double-bonds comprises but the indeterminate vinyl monomer that has two radical polymerizable unsaturated groups in molecule that is limited at least.Specifically, the example comprises, vinyl compound is as Vinylstyrene and divinylsulfone; (first generation) allylic cpd, as (methyl) vinylformic acid (first generation) allyl ester (after, the two is represented allyl group and methylallyl by (first generation) allyl group), Phthalic acid, diallyl ester or phthalic acid diformazan for allyl ester, two (first generation) allyl group (methyl) acrylamide, cyanuric acid three (first generation) allyl ester or tricarbimide three (first generation) allyl ester, tri trimellitate (first generation) allyl ester and two ((first generation) allyl groups receive enlightening imide (nadimide)); List or polyoxyalkylene diols two (methyl) acrylate are as list or polyoxyethylene glycol two (methyl) acrylate and list or polypropylene glycol two (methyl) acrylate; (methyl) acrylic compound is as trimethylolpropane tris (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate and glycerine three (methyl) acrylate.In addition, the following monomer of commercially available acquisition: allyl group oxygen base polyoxyethylene glycol polypropylene glycol mono acrylic ester (BLEMMER AKEP is made by NOFCorporation), vinylformic acid two rings

Alkenyl esters (FANCRYL FA-511A, by Hitachi Chemical Co., Ltd. makes), vinylformic acid two rings Thiazolinyl oxygen base ethyl ester (FANCRYL FA-512A, by Hitachi Chemical Co., Ltd. makes), methacrylic acid two rings

Thiazolinyl oxygen base ethyl ester (FANCRYL FA-512M, by Hitachi Chemical Co., Ltd. manufacturing), vinylformic acid dihydro dicyclopentadienyl ester (available from BASF Gesellshaft), methacrylic acid 3-cyclohexenyl methyl esters (available from DAICEL Chemical Industries Ltd.), vinylformic acid 3-cyclohexenyl methyl esters (available from DAICEL Chemical Industries Ltd.), butyleneglycol-1,4-divinyl ether (available from BASF Gesellshaft) and triallyl isocyanurate (TAIC, by NipponKasei Chemical Co., Ltd. makes).Wherein allyl methacrylate(AMA) and ethylene glycol bisthioglycolate (methyl) acrylate is preferred in the present invention.Especially under the situation that the distance between the unsaturated double-bond is represented by atomicity, wherein atomicity be 4 or still less, preferred 3 or unsaturated monomer still less with at least two unsaturated double-bonds be preferred.It clearly is allyl methacrylate(AMA).In the present invention, the unsaturated monomer with at least two unsaturated double-bonds can use separately, perhaps can use the mixture of 2 or more kinds of unsaturated monomers with at least two unsaturated double-bonds.

[0040] monomer weight ratio of above-mentioned nuclear monomer mixture/above-mentioned shell monomer mixture [nuclear part/shell part] is preferably 50/50 to 98/2, and more preferably 65/35 to 95/5.When ratio less than 50/50 the time, the stability of emulsion reduces.When ratio was higher than 98/2, the water tolerance that gained is filmed reduced.

[0041] in the present invention, the Tg of the acid number of the acid number of the nuclear part that is obtained by above-mentioned nuclear monomer mixture letex polymerization and hydroxyl value, the shell part that obtained by above-mentioned shell monomer mixture letex polymerization and hydroxyl value and above-mentioned nuclear-shell type acrylic resin emulsion be the definite calculated value of content by unsaturated monomer in the content of unsaturated monomer in the above-mentioned nuclear monomer mixture and/or the above-mentioned shell monomer mixture.

[0042] in order to prepare aforesaid propylene acid resin emulsion, the available ordinary method that those skilled in the art are afamiliar with is carried out letex polymerization.Specifically, emulsifying agent can be dissolved in aqueous aqueous medium and (as needs) organic solvent such as alcohol, under heating, stir the mixture then, and drip above-mentioned nuclear monomer mixture or above-mentioned shell monomer mixture and polymerization starter.The above-mentioned nuclear monomer mixture or the above-mentioned shell monomer mixture of emulsifying agent and emulsifying water have been used before also can dripping.

[0043] above-mentioned polymerization starter preferably includes, azo-group oiliness compound, azo two (isopropyl cyanides), 2 for example, 2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile) etc.; Aqueous compounds, for example, anion-radicals 4,4 '-azo two (4-cyanopentanoic acid) and cation radicals 2,2 '-azo two (2-methyl-prop amidine); With redox base oil superoxide, for example benzoyl peroxide, chloro benzoyl peroxide, lauroyl peroxide, t-butylperoxyl benzoate etc.; With water-based superoxide, for example Potassium Persulphate, ammonium peroxide etc.

[0044] mentioned emulsifier comprises the emulsifying agent that those skilled in the art are familiar with.Specifically, reactive emulsifier is preferred, as Antox MS-60 (by Nippon Nyukazai Co., Ltd. manufacturing), ELEMINOL JS-2 (making), ADEKAREA SOAP NE-20 (making) and AQUARONHS-10 (by Daiichi Kogyo Seiyaku Co., Ltd. makes) etc. by ADEKA Corporation by Sanyo Chemical Industries Ltd..

[0045] in order to control molecular weight, can use chain-transfer agent, for example mercaptan such as lauryl mercaptan, α-Jia Jibenyixierjuwu etc. if desired.

[0046] temperature of reaction can be decided according to polymerization starter.For example,, be preferably 60 ℃-90 ℃,, be preferably 30-70 ℃ for redox initiator for the azo-group initiator.Reaction times was generally 1-8 hour.The content of polymerization starter is 0.1-5% weight with respect to the gross weight of above-mentioned nuclear monomer mixture and above-mentioned shell monomer mixture generally, is preferably 0.2-2% weight.

[0047] if necessary, the neutralization of aforesaid propylene acid resin emulsion available bases, and in the pH of 3-10 use.Reason is high in the stability of above pH scope.Preferably before or after letex polymerization, neutralize by adding tertiary amine, as adding dimethylethanolamine and triethylamine to reactive system.

[0048] content of the aforesaid propylene acid resin emulsion in the above-mentioned water-based metal colored paint composition is preferably 5-95% weight with respect to solids content weight in the coating composition, more preferably 10-85% weight, further preferred 20-70% weight.When content departed from above restricted portion, the outward appearance that coating application and gained are filmed will variation.

[0049] Solidifying agent

The used solidifying agent of preparation method of the present invention is the aqueous dispersion with hydrophobic melamine resin of 20-140nm particle diameter.The aqueous dispersion of hydrophobic melamine resin has the particle diameter of 20-140nm separately for resin particle wherein is scattered in the dispersion of water, and can be by the reaction acquisition of concrete acrylic resin and hydrophobic melamine resin.Owing to utilize this aqueous dispersion of hydrophobic melamine resin, therefore can obtain to have filming of good color performance.

[0050] when using the above-mentioned aqueous dispersion of hydrophobic melamine resin, can provide to have the good multilayer film that is coated with adhesive power, good cracking resistance and good water-fast adhesive power again.During less than 20nm, the solids content of coating composition obviously reduces at particle diameter.When particle diameter surpassed 140nm, water dispersible reduced, so adhesion property and surface flatness that gained is filmed reduce.Particle diameter is preferably 30-120nm, more preferably 50-100nm.In the present invention, above-mentioned particle diameter is by being similar to the numerical value that the described method of aforesaid propylene acid resin emulsion particle diameter is measured.

[0051] the above-mentioned aqueous dispersion of hydrophobic melamine resin is preferably the dispersion that obtains with the preparation method who may further comprise the steps:

Step (1) makes acrylic resin and hydrophobic melamine resin mix and reaction with the weight ratio (acrylic resin/hydrophobic melamine resin) of 5/95-50/50, described acrylic resin have the hydroxyl value (based on the solid resin content) of acid number (based on the solid resin content), 100-200mgKOH/g of 105-200mgKOH/g and 1000-5000 number-average molecular weight and

Step (2) is distributed in the water reaction product that obtains in step (1).

Color characteristics that gained films be can improve thus, adhesive power, cracking resistance and water-fast adhesive power are coated with again.

[0052] at first, according to above-mentioned steps (1), acrylic resin and hydrophobic melamine resin are mixed and reaction with the weight ratio (acrylic resin/hydrophobic melamine resin) of 5/95-50/50, and described acrylic resin has the acid number (based on the solid resin content) of 105-200mgKOH/g, the hydroxyl value (based on the solid resin content) of 100-200mgKOH/g and the number-average molecular weight of 1000-5000.Step (1) can provide the reaction product of aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin.

[0053] the aforesaid propylene acid resin has the acid number (based on the solid resin content) of 105-200mgKOH/g.When being lower than 105mgKOH/g, particle diameter will surpass 140nm.When surpassing 200mgKOH/g, reaction control is difficulty very.This acid number is preferably 105-180mgKOH/g.

[0054] the aforesaid propylene acid resin has the hydroxyl value of 100-200mgKOH/g.When being lower than 100mgKOH/g, particle diameter will surpass 140nm.When surpassing 200mgKOH/g, reaction control is difficulty very.This hydroxyl value is preferably 120-180mgKOH/g.

[0055] the aforesaid propylene acid resin has the number-average molecular weight of 1000-5000.When less than 1000 the time, particle diameter will surpass 140nm.When surpassing 5000, reaction control is difficulty very.This molecular weight is preferably 1500-4000.

[0056] in the present invention, number-average molecular weight (Mw) can be passed through gel permeation chromatography (GPC) mensuration, utilizes to have the polystyrene of known molecular amount as standard substance.For example, can utilize GPC equipment [Model HLC-8120GPC, make by Tosoh Corporation, connect two post (Model Super H-4000 in its center line, make by Tosoh Corporation) and a post (Model Super H-3000)], differential refraction detector and data processor (Model SC-8020, make by Tosoh Corporation), measure number-average molecular weight under the following conditions:

Column temperature: 40 ℃,

Elutriant: THF (one-level reagent, by Katayama Chemical Industry Co., Ltd. makes),

Flow velocity: 0.5mL/min,

Sample concentration: 1% weight and

Sample solution heap(ed) capacity: 10 μ L.

[0057] above-mentioned hydrophobic melamine resin comprises those melamine resins that those skilled in the art are familiar with.Preferred hydrophobic melamine resin has solubility parameter (SP) δ of 9.0≤SP≤11.5.When the SP value less than 9.0 the time, particle diameter will surpass 140nm.When the SP value surpassed 11.5, particle diameter will surpass 140nm, and performance such as water tolerance that gained is filmed reduce.The SP value is more preferably in the scope of 9.5＜SP＜11.0.

[0058] above-mentioned solubility parameter (δ) generally also is called SP (solubility parameter) by those skilled in the art.SP is resin wetting ability or hydrophobic index.SP also is the important indicator of consistency between the research resin.Can for example measure solubility parameter, promptly to solubility parameter quantitative (reference: K.W., Suh, D.H.Clarke, J.Polymer.Sci., A-1,5,1671 (1967)) according to detection method (for example turbidimetric titration).Solubility parameter in this specification sheets (δ) is the parameter of measuring according to turbidimetric titration.Solubility parameter can be determined by turbidimetric titration described in the above-listed document and known method of calculation etc.For example, titration method comprises, solid resin content (a certain amount of) is dissolved in a certain amount of good solvent (for example acetone) as measuring target, drips poor solvent (for example water or hexane) then.Insoluble and observe the point of solution turbidity at resin, the titer of good solvent and the titer of poor solvent are calculated.

[0059] in step (1), the ratio of mixture of aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin is preferably 5/95 to 50/50 (weight ratio, acrylic resin/hydrophobic melamine resin).When weight ratio was lower than 5/95, particle diameter will surpass 140nm.Surpass at 50/50 o'clock in weight ratio, the NV in coating composition (being solid content concentration) obviously reduces, reaction control significant difficulties.Weight ratio more preferably 10/90 to 40/60.In the present invention, the blending means of acrylic resin and hydrophobic melamine resin can be undertaken by conventional currently known methods.

[0060] according to the present invention, acrylic resin is low with respect to the amount of hydrophobic melamine resin in step (1).Therefore, under the situation of gained aqueous dispersion, reduce hardly as the effect of solidifying agent as solidifying agent with hydrophobic melamine resin.In addition, although the amount of acrylic resin is little, the particle diameter after water-dispersion is 20-140nm.Therefore, the gained aqueous dispersion of hydrophobic melamine resin of the present invention can preferably be used for the water-based metal colored paint composition as solidifying agent.In addition, in step (1), except aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin, can be comprising other resins in the scope of sharp influence improvement provided by the invention, as vibrin.

[0061] in step (1), the reaction conditions of aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin is as follows.Temperature of reaction is preferably 70-100 ℃, more preferably 75-90 ℃.In addition, preferred 1-10 of reaction times hour, more preferably 1-5 hour.When being lower than down in limited time, particle diameter will surpass 140nm.When surpassing last prescribing a time limit, reaction control is difficulty very.

[0062] step (2) comprises the reaction product that obtains from step (1) is distributed to the water, with the step of aqueous dispersion that the hydrophobic melamine resin with 20-140nm particle diameter is provided.The aqueous dispersion (or water dispersion) that step (2) can provide the resin particle that wherein has the 20-140nm particle diameter to be scattered in water.

[0063] in step (2), the method that makes the reaction product that obtains from step (1) be scattered in water comprises but indeterminate being limited to makes the ordinary method of resin dispersion to the water.Preferably above-mentioned reaction product is cooled to 50 ℃ or low temperature more, thin up then is to provide aqueous dispersion.Therefore, but preferred preparation has the aqueous dispersion of the hydrophobic melamine resin of 20-140nm particle diameter.Be not cooled to 50 ℃ or more during low temperature, then can not obtaining having the aqueous dispersion of the hydrophobic melamine resin of 20-140nm particle diameter.More preferably after being cooled to 30-40 ℃, prepare aqueous dispersion by thin up.

[0064] if necessary, can in step (2), use in the alkali and the aqueous dispersion of hydrophobic melamine resin, and can use the aqueous dispersion of pH as 6.5-10.Reason is high in the stability of this pH scope.Preferably before or after aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin reaction, neutralize by adding tertiary amine (for example, dimethylethanolamine, triethylamine) to reactive system.Especially preferably add tertiary amine at aforesaid propylene acid resin and above-mentioned hydrophobic melamine resin reaction back, making reaction product be cooled to 50 ℃ or more behind the low temperature, obtain aqueous dispersion subsequently by adding the entry dilution.Thus, can preferably obtain having the aqueous dispersion of the hydrophobic melamine resin of 20-140nm particle diameter.

[0065] Polyoxyalkylene compounds

According to the present invention, if necessary, coating composition can comprise the polyoxyalkylene compounds with formula (1) with respect to solid resin content weight 0.01-10% weight in the coating composition:

H(-OR) _f-OH (1)

Wherein

R is the alkyl with 2-5 carbon atom that can have side chain, and

F is 100 to 18000 integer.

Polyoxyalkylene compounds preferably has the weight-average molecular weight of 10000-1000000, especially preferred 30000-500000.Polyoxyalkylene compounds has high molecular more (especially surpassing 10000 molecular weight) can prevent to disturb the flash of light colored pigment when applying clear coating composition orientation.When molecular weight was lower than 10000, technique effect or prevent disturbed the orientation of flash of light colored pigment can be insufficient.On the other hand, surpass at 1000000 o'clock in weight-average molecular weight, the non-volatile content of coating composition reduces, so the coating property variation.In the formula (1) of above expression, R is ethylidene, propylidene, butylidene or pentylidene, can have side chain, is preferably ethylidene or propylidene, more preferably ethylidene.When R was ethylidene, polyoxyalkylene compounds was for most preferably having the polyoxyethylene ene compound of 10000-1000000 weight-average molecular weight.

[0066] content of polyoxyalkylene compounds is 0.01-10% weight with respect to solid resin content weight in the water-based metal colored paint composition of the present invention, preferred 0.5-5.0% weight.When being lower than 0.01% weight, just can not obtain by adding the effect that polyoxyalkylene compounds provides.When surpassing 10% weight, the non-volatile content of coating composition reduces, so the coating property variation.

[0067] Viscosity modifier

If necessary, water-based metal colored paint composition of the present invention can comprise viscosity modifier.Used viscosity modifier is preferably the carbamate compounds (A) by general formula (1) expression

With carbamate compounds (B) by general formula (2) expression

Mixture,

Wherein

R ₁Identical or different, expression has the alkyl of 8 to 24 carbon atoms,

Y represents to eliminate the reactive residue that isocyanate group obtains from vulcabond,

OA and AO independently represent to have the oxyalkylene group of 2 to 4 carbon atoms,

O represents Sauerstoffatom,

C represents carbon atom,

N represents nitrogen-atoms,

M and n independently represent 20 to 500 integer,

A and d independently represent 1 to 100 integer,

B represents 40 to 500 integer,

C represents 1 to 5 integer,

(bxc) be 150 to 2500,

F represents 200 to 25000 integer, and

R, Y and P can be independently identical or different,

Wherein each carbamate compounds has the oxyethylene group with respect to oxyalkylene group gross weight at least 80% weight.

[0068] has the alkyl (R of 8 to 24 carbon atoms ₁) example comprise, linear alkyl is as n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base, heneicosane base, n-docosane base etc.; Branched-alkyl is as 2-ethylhexyl, isodecyl, isotridecyl, iso stearyl etc.; Linear thiazolinyl is as positive octenyl, positive decene base, positive undecenyl, positive dodecenyl succinic, positive tridecylene base, positive tetradecene base, positive 15 carbene bases, positive cetene base, positive heptadecene base, positive vaccenic acid base etc.; The branching thiazolinyl is as isooctene base, isodecyl thiazolinyl, different undecenyl, different dodecenyl succinic, different tridecylene base, different tetradecene base, different 15 carbene bases, different cetene base, different heptadecene base, different vaccenic acid base etc.From aspects such as covering with paint performances, linear alkyl and linear thiazolinyl are especially preferred.Linear alkyl more preferably.N-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base, heneicosane base and n-docosane base are especially preferred.

[0069] is used for eliminating the vulcabond that isocyanate group obtains reactive residue (Y) and comprises aliphatic vulcabond, aromatic diisocyanate, alicyclic diisocyanate etc. from vulcabond.

[0070] example of aliphatic vulcabond comprises the aliphatic vulcabond with 3-15 carbon atom, as methylene diisocyanate, 1, the 2-ethylidene diisocyanate, 1, the 3-trimethylene diisocyanate, 1,4-butylidene vulcabond, 1,5-pentylidene vulcabond, 1, the 6-hexylidene diisocyanate, 1, the inferior heptyl vulcabond of 7-, the octamethylene vulcabond, 1, the nonamethylene vulcabond of 9-, 1, the inferior decyl vulcabond of 10-, two (isocyanato propyl group) ether, 1,1-dimethylbutane-1,4-vulcabond, 3-methoxyhexane-1, the 6-vulcabond, 2,2,4-trimethylpentane-1,5-vulcabond, 3-butoxy-1, the 6-hexane diisocyanate, 1, two (isocyanato propyl group) ethers of 4-butyleneglycol etc.

[0071] aromatic diisocyanate comprises the aromatic diisocyanate with 8-20 carbon atom, as m-benzene diisocyanate, PPDI, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, the dimethyl benzene vulcabond, the ethylbenzene vulcabond, the isopropyl benzene vulcabond, biphenyl diisocyanate, 4,4 '-two isocyanatos-2,2 '-dimethyl diphenyl, 4,4 '-two isocyanatos-3,3 '-dimethoxy-biphenyl, 1,5-two isocyanato naphthalenes, 4,4 '-two isocyanato ditans, 4,4 '-two isocyanatos-2,2 '-dimethyl diphenylmethane, 4,4 '-two isocyanatos-3,3 '-dimethoxy ditan, 3,3 '-two isocyanatos-4,4 '-dimethoxy ditan, 3,3 '-two isocyanatos-4,4 '-diethoxy ditan, 4,4 '-two isocyanatos-2,2 '-dimethyl-5,5 '-dimethoxy ditan, between the xylylene vulcabond, terephthaldehyde's group diisocyanate, tetramethyl-benzene dimethyl vulcabond etc.

[0072] alicyclic diisocyanate comprises the alicyclic diisocyanate with 8-20 carbon atom, as 1,3-two isocyanato hexanaphthenes, 1, two (isocyanato methyl) hexanaphthenes of 3-, 1-isocyanato-3-isocyanato methyl-3,5,5-trimethyl-cyclohexane, 4,4 '-two isocyanato dicyclohexyl methyl hydrides etc.

[0073] in these vulcabond, aliphatic vulcabond and alicyclic diisocyanate are preferred.Aliphatic vulcabond is more preferred.Hexamethylene vulcabond and octamethylene vulcabond are preferred especially.

[0074] (OA AO) comprises oxyethylene group, oxypropylene group and oxybutylene base to have the oxyalkylene group of 2 to 4 carbon atoms.Oxyalkylene group can be their combination.Under the situation of combination, the embodiment of combination comprises the combination of block shape, random shape and block shape and random shape.The combination of block shape and block shape and random shape is preferred.Block shape is more preferred.

[0075] must comprise oxyethylene group by general formula (1) with by every kind of compound of general formula (2) expression.Every kind of compound has with respect to oxyalkylene group gross weight preferably at least 80% weight, more preferably 85% weight or more, especially preferred 90% weight or more oxyethylene group.When content (% weight) is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0076] m and n independently be 20 to 500, preferred 30 to 300, more preferably 40 to 200 integer.When m and n are independent in this scope the time, cover with paint, lacquer, colour wash, etc. performance and further improve.

[0077] a and d independently be 1 to 100, preferred 2 to 70, more preferably 3 to 40 integer.When a and d are independent in this scope the time, cover with paint, lacquer, colour wash, etc. performance and further improve.

[0078] b be 40 to 500, preferred 55 to 400, more preferably 70 to 300 integer.When b is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0079] c be 1 to 5, preferred 1 to 4, more preferably 1 to 3 integer.When c is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0080] (bxc) be 150 to 2500, preferred 200 to 2000, more preferably 250 to 1500.As (bxc) in this scope the time, cover with paint, lacquer, colour wash, etc. performance and further improve.

[0081] f be 200 to 25000, preferred 400 to 20000, more preferably 600 to 15000 integer.When f is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0082] since hydrogen carbamate compound (A) in component (for example, (OA) _m(-AO) _n) have certain distribution usually, therefore the carbamate compounds (A) by general formula (1) expression can be mixture.Under the situation of mixture, be preferably 5000-20000 by the weight-average molecular weight of the carbamate compounds (A) of general formula (1) expression, more preferably 7000-15000.When weight-average molecular weight is in this scope, covers with paint, lacquer, colour wash, etc. performance and be further improved.When the molecular weight of above-claimed cpd (A) is lower than 5000, the covering with paint texture variation that gained is filmed.When surpassing 20000, the dilution coating composition makes that the viscosity of being measured by No.4Ford cup (at 20 ℃) was 45 (seconds), and the solids content of gained coating composition is lower than 24% weight, and is therefore unacceptable.

[0083] since carbamate compounds (B) in component (for example, (OA) _a, (OA) _b, (OA) _d[OC (O)-NH-Y-NH-C (O)-(OA) _b-] _c) have certain distribution usually, therefore the carbamate compounds (B) by general formula (2) expression can be mixture.Under the situation of mixture, be preferably 20000-100000 by the weight-average molecular weight of the carbamate compounds (B) of general formula (2) expression, more preferably 20000-60000.When weight-average molecular weight is in this scope, covers with paint, lacquer, colour wash, etc. performance and be further improved.When the molecular weight of above-claimed cpd (B) was lower than 20000, the FF performance that gained is filmed was less than 3.80, and the outward appearance of filming just goes wrong.On the other hand, when surpassing 100000, the dilution coating composition makes that the viscosity of being measured by No.4Ford cup (at 20 ℃) was 45 (seconds), and the solids content of gained coating composition is lower than 24% weight, and is therefore unacceptable.

[0084] in the present invention, weight-average molecular weight can be measured the described mode of detection method of aforesaid propylene acid resin number-average molecular weight to be similar to the GPC method.

[0085] by the carbamate compounds (A) of general formula (1) expression and the available known urethane prepared in reaction of representing by general formula (2) of carbamate compounds (B) (for example Japan patent applicant announce 2000-303006).For example, carbamate compounds (A) can synthesize with di-isocyanate reaction 2-10 hour by polyethers list alcohol.On the other hand, carbamate compounds (B) can and synthesize by the pure and mild polyether glycol of polyethers list in di-isocyanate reaction 2-10 hour.Though during reaction generate by product, but former state is used the reaction mixture that contains by product.

[0086] content of carbamate compounds (A) need be 5-95% weight with respect to the gross weight of carbamate compounds (A) and carbamate compounds (B), preferred 10-80% weight, more preferably 20-70% weight, especially preferred 25-65% weight.When content is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0087] content of carbamate compounds (B) need be 5-95% weight with respect to the gross weight of carbamate compounds (A) and carbamate compounds (B), preferred 10-80% weight, more preferably 15-60% weight, especially preferred 17-40% weight.When content is in this scope, covers with paint, lacquer, colour wash, etc. performance and further improve.

[0088] when the amount of carbamate compounds (A) is higher, it is relatively poor to cover with paint, lacquer, colour wash, etc. texture.On the other hand, when the amount of carbamate compounds (B) was higher, the dilution coating composition made that the viscosity of being measured by No.4Ford cup (at 20 ℃) was 45 (seconds), and the solids content of gained coating composition is lower than 24% weight, so unacceptable.

[0089] uniform mixing carbamate compounds (A) and carbamate compounds (B) can be provided at the viscosity modifier that uses in the water-based metal colored paint composition of the present invention.Mixed uniformly method comprises ordinary method, from viewpoints such as mixing efficiencies, mixes and preferably carries out at about 70-150 ℃.

[0090] if necessary, viscosity modifier of the present invention can comprise organic solvent and water.Organic solvent comprises but indeterminate for example isopropylcarbinol, ethylene glycol butyl ether, diethylene glycol monobutyl ether, the Virahol etc. of being limited to.The total content of organic solvent and water is 10 to 99% weight based on the gross weight of composition.

[0091] content of viscosity modifier of the present invention is preferably 0.2-4.0% weight with respect to solid resin content in the water-based metal colored paint composition, more preferably 0.5-3.0% weight.When content was in this scope, the viscosity of water-based metal colored paint composition was further improved.

[0092] The flash of light colored pigment

The flash of light colored pigment that comprises in water-based metal colored paint composition of the present invention comprises but the indeterminate pigmentable flash of light colored pigment that for example preferably has 2-50 μ m median size (D50) and 0.1-5 μ m thickness on form that is limited to.In addition, the flash of light colored pigment with 10-35 μ m median size has good flash of light color, more preferably and more suitable.Specifically, the flash of light colored pigment comprises the colourless or colored flash of light colored pigment that is made of metal, for example aluminium, copper, zinc, iron, nickel, tin and aluminum oxide or its alloy and composition thereof etc.In addition, the flash of light colored pigment comprises interference pigments, mica, white pigments, mica, graphite pigment etc.

[0093] if necessary, water-based metal colored paint composition of the present invention can further comprise colored pigment.Colored pigment comprises, for example, organic colored pigment is as azo chelating pigment, insoluble azo colour, condense azo pigment, phthalocyanine pigment, diketopyrrolo-pyrrole pigment, benzimidazolone pigment, indigo pigment, perinone pigment, perylene dye, dioxane pigment, quinacridone pigment, iso-dihydro-indole pigment, metal complex pigment etc.; Inorganic colored pigment is as chrome yellow, Zh 1, colcother, barium sulfate, carbon black, titanium dioxide etc.

[0094] in the present invention, preferably the glisten pigment weight concentration (PWC) of colored pigment is generally 18.0% or still less.When prescribing a time limit the degraded appearance of filming above last.0.01-15.0% more preferably, especially preferred 0.01-13.0%.In the present invention, pigment weight concentration (PWC) numerical value that following formula calculates of serving as reasons:

(pigment weight)/(weight of solid resin content in the coating composition) * 100.

[0095] total pigment weight concentration (PWC) is preferably 0.1-50% in the water-based metal colored paint composition.0.5-40% more preferably, especially preferred 1.0-30%.When prescribing a time limit the degraded appearance of filming above last.

[0096] if necessary, the water-based metal colored paint composition can comprise other film-forming resins.Other film-forming resins comprise but clearly are not limited to for example film-forming resin of aforesaid propylene acid resin emulsion acrylic resin, vibrin, Synolac, Resins, epoxy and carbamate resins in addition.

[0097] in the present invention, the number-average molecular weight of other film-forming resins is 3000-50000, preferred 6000-30000.When less than 3000 the time, application property and curing performance deficiency.Surpassing at 50000 o'clock, the non-volatile content during the coating step is too low, so the unfavorable reduction of application property.

[0098] other film-forming resins have 10-100mgKOH/g, the more preferably acid number of 20-80mgKOH/g (based on the solid resin content).When surpassing last prescribing a time limit, the water tolerance that gained is filmed reduces.When being lower than down in limited time, the water dispersible of resin reduces.In addition, other film-forming resins preferably have 20-180mgKOH/g, the more preferably hydroxyl value of 30-160mgKOH/g.When surpassing last prescribing a time limit, the water tolerance that gained is filmed reduces.When being lower than down in limited time, the curing performance of filming reduces.

[0099] about the ratio of acrylic resin emulsion and other film-forming resins in the water-based metal colored paint composition, the content of acrylic resin emulsion is 5-95% weight with respect to solid resin content gross weight, preferred 10-85% weight, more preferably 20-70% weight; The content of other film-forming resins is 95-5% weight with respect to solid resin content gross weight, preferred 90-15% weight, more preferably 80-30% weight.When the content of acrylic resin emulsion was lower than 5% weight, application property reduced.When surpassing 95% weight, form the variation of filming.

[0100] as other film-forming resins, from the consistency viewpoint of acrylic resin emulsion, preferably use the water-soluble acrylic resin.Unsaturated monomer by above-mentioned carboxy-containing acid group can prepare the water-soluble acrylic resin as the solution polymerization of basal component and other ethylenically unsaturated monomers.

[0101] in the present invention, used water-soluble acrylic resin neutralizes with basic cpd usually, for example organic amine as monomethyl amine, dimethyl amine, Trimethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine and dimethylethanolamine, is dissolved in water then.Self can be neutralized the water-soluble acrylic resin.As selection, can during preparation water-based metal colored paint composition, neutralize.

[0102] in the present invention, the water-based metal colored paint composition also can comprise polyether glycol.The adding polyether glycol can provide has further the filming of performance of improving.Described polyether glycol comprises preferably having at least one primary hydroxyl in molecule, has the number-average molecular weight of 300-3000, the hydroxyl value of 30-700mgKOH/g and 2.0 or the polyether glycol of bigger fastness to water (water tolerance).When not satisfying above-mentioned condition, water tolerance reduces sometimes, can not carry out target to outward appearance sometimes and improve.

[0103] this type of polyether glycol comprises the compound that wherein oxirane (as propylene oxide) is added to active hydrogen-contg compound, active hydrogen-contg compound such as polyvalent alcohol, polyphenol and polycarboxylic acid.Specific examples comprises buys product, as PRIMEPOLE PX-1000, SANNIX SP-750 (above-mentioned two kinds of products are made by Sanyo Chemical Industries Ltd.) and PTMG-650 (being made by Mitsubishi Chemical Corporation).The content of polyether glycol is preferably 1-40% weight with respect to solid resin content weight in the coating composition, more preferably 3-30% weight.

[0104] the water-based metal colored paint composition can further comprise other solidifying agent that can sharp influence solidified amount of the present invention.Other solidifying agent comprise the aqueous dispersion conventional solidifying agent that is used for coating composition in addition of above-mentioned hydrophobic melamine resin, for example blocked isocyanate, epoxy compounds, aziridine cpd, carbodiimide compound, oxazoline compound, hydrophilic melamine resin, metal ion etc.

[0105] blocked isocyanate can be added to polyisocyanates by the encapsulant with active hydrogen and obtain polyisocyanates such as trimethylene vulcabond, hexamethylene vulcabond, xylylene vulcabond and isophorone diisocyanate.Blocked isocyanate comprises that wherein isocyanate group is by adding those isocyanic ester that the thermal dissociation encapsulant produces.

[0106] when the water-based metal colored paint composition comprises above-mentioned solidifying agent, the content of solidifying agent is preferably the 10-100 weight part based on 100 weight part solid resin contents in the water-based metal colored paint composition.When content exceeds above restricted portion, the curing performance deficiency.

[0107] in addition, other viscosity control agents can be added the water-based metal colored paint composition,, and guarantee coating application with the consistency that prevents to film and cause owing to face.Viscosity control agent comprises, can provide thixotropic conventional viscosity control agent, as crosslinked or uncrosslinked resin particle; The polymeric amide agent, as the swelling dispersion of phosphoric acid ester of fatty acid amide, acid amides lipid acid, long-chain polyaminoamide etc.; The polyethylene agent, as the colloid swelling dispersion of polyoxyethylene etc.; The organobentonite agent, as organic acid-smectic clays, polynite etc.; Mineral dye is as pure aluminium silicate, barium sulfate etc.; Viscosity depends on the no delustering pigment of pigment form etc.

[0108] except said components, the water-based metal colored paint composition also can comprise the conventional additives that is used for coating composition, as surface conditioner, thickening material, antioxidant, ultraviolet protective agent, defoamer etc.In the known scope of additive level those skilled in the art.

[0109] preparation method of water-based metal colored paint composition comprises but indeterminate following method and all methods appreciated by those skilled in the art of being limited to, for example, comprise by kneading such as sand mill, glen grinding machine, kneader, roller and disperse to comprise the method for these materials of pigment.

[0110] Form the method for multilayer film

Described water-based metal colored paint composition can be preferably used as the water-based metal primer composition of motor vehicle.Therefore, it is applicable to the method that forms the multilayer film that can be coated to motor-vehicle bodies (as motor vehicle, its parts etc.).The method that forms multilayer film for example comprises a kind of method, and described method comprises:

Step (I) applies above-mentioned water-based metal colored paint composition on goods, to form undercoat;

Step (II) is not making undercoat apply clear coating composition under solidifying on undercoat, to form Clear coating; With

Step (III) heats undercoat and Clear coating simultaneously.

[0111] goods that will apply in the method that forms multilayer film comprise various base materials, as metal pattern goods, moulded goods, foam article etc.Preferred goods are for applying the metal pattern goods of cationic electrodeposition coating in the above.

[0112] example of metal pattern goods comprises plate and the moulded product that is made of metal, as iron, copper, aluminium, tin and zinc or its alloy.Specifically, goods comprise the car body and the parts thereof of car, truck, motorcycle, motorbus etc.Preferable alloy is used chemical treatments such as phosphoric acid salt, chromic salt in advance.

[0113] can form electrodeposition coating through on the chemically treated metal pattern goods.Electrodeposition coating composition comprises cationic and the anionic electrodeposition coating composition.From the viewpoint of Corrosion Protection, the cationic electro-dipcoat paint composition is preferred.

[0114] moulded goods comprises the plate made by acrylic resin, polycarbonate resin, urethane resin, vibrin, polystyrene resin, ABS resin, polyvinyl chloride (PVC) RESINS, polyamide resin etc., moulded product etc., specifically, moulded goods comprises automotive component, as turbulence generator, snubber, minute surface, grid, door knob etc.Among the present invention, moulded goods preferably cleans with the trichloroethane steam purge or with mild detergent.In addition, coating base coat in the above is to accept the electrostatic coating step.

[0115] if necessary, can also on goods, form middle filming.In the middle of being used to form, midcoat composition films.Midcoat composition can comprise film-forming resin, solidifying agent, organic or inorganic colouring component, filler pigments etc.Film-forming resin and solidifying agent comprise but indeterminate film-forming resin and the solidifying agent of describing in the water-based metal colored paint composition front that be limited to.Their uses capable of being combined.From the middle cost of filming of gained and the aspect of different performance, use the combination of acrylic resin and/or vibrin and aminoresin and/or isocyanic ester.Coloured component that can comprise in midcoat composition comprises those coloured components that the front is described in the water-based metal colored paint composition.Usually, preferred use mainly comprise carbon black and titanium dioxide the grey midcoat composition, provide with the particular gray midcoat composition of filming of overcoat layer color-match and with so-called coloured midcoat composition of coloured combination of components.Midcoat composition also can comprise no delustering pigment, as aluminium powder form and mica powder.

[0116] except said components, midcoat composition also can comprise the conventional additives that is used for coating composition, as surface conditioner, antioxidant, defoamer etc.

[0117] in order to improve appearance of coat, the step that applies the water-based metal colored paint composition on goods comprises the multistage coating step that utilizes the air electrostatic spraying, preferred two-stage coating step, or the coating step of air electrostatic spraying step and rotary-atomizing type electrostatic coating machine (being called the metal clock) combination.

[0118] can change the thickness of filming that when applying, obtains according to required application by the water-based metal colored paint composition.In general, dry film thickness is preferably 10-30 μ m.When dry film thickness during less than 10 μ m, goods to be coated may not cover, so that produce film defects.When surpassing 30 μ m, sharpness reduces, and may produce some problems, for example inhomogeneous and sagging when applying.For the multilayer film with excellent appearance is provided, preferably before applying clear coating composition, the gained bottom coating was heated 2-10 minute at 40-100 ℃.

[0119] method of formation multilayer film is included in and does not heat undercoat or undercoat is solidified down, applies clear coating composition at the undercoat that obtains from coating water-based metal colored paint composition, to form the step of Clear coating.The gained transparent coating suppresses because the ununiformity of undercoat, confused etc., thereby the film below smooth film, the protection is provided, and splendid outward appearance is provided.

[0120] clear coating composition comprises but the indeterminate clear coating composition that comprises film-forming resin, solidifying agent etc. that is limited to.Clear coating composition can further include the colour cell branch, only otherwise disturb the pattern of surface layer down.

[0121] clear coating composition comprises the clear coating composition of the clear coating composition of any type of solvent, any water-based type and the clear coating composition of any powder type.

[0122] from for example transparency and resistance to acid attack aspect of performance, the preferred embodiment of the clear coating composition of type of solvent comprises the combination of acrylic resin and/or vibrin and aminoresin and/or isocyanic ester; And have carboxylic acid/epoxy cure system acrylic resin and/or have the vibrin etc. of the cure system of carboxylic acid/epoxy.

[0123] in the present invention, the example of the clear coating composition of water-based type comprises the coating composition that comprises a kind of resin, and the film-forming resin that described resin can comprise described in the example of type of solvent clear coating composition by the alkali neutralization that is used in solubilising in the water obtains.Can before or after polymerization, neutralize by adding tertiary amine, as adding dimethylethanolamine and triethylamine.

[0124] in addition, in order to guarantee coating application, clear coating composition preferably comprises viscosity control agent.Usually, viscosity control agent comprises having thixotropic viscosity control agent.This viscosity control agent comprises for example common known viscosity control agent.If necessary, viscosity control agent also can comprise curing catalysts, surface conditioner etc.

[0125] in the present invention, from comprising the viewpoint of organic solvent to environmental influence, the clear coating composition that forms the method use of multilayer film comprises type of solvent clear coating composition or water-based type clear coating composition, described clear coating composition has preferred 50% weight or higher solids content with respect to clear coating composition weight, described composition makes that through dilution the viscosity of being measured by No.4 Ford cup (at 20 ℃) is 20-50 (second).The powder type clear coating composition also is preferred.

[0126] specifically, the step of coating clear coating composition comprises the coating step that utilizes rotary-atomizing type electrostatic coating machine (being also referred to as little-little clock or little clock) on undercoat.

[0127] on the other hand, the powder type clear coating composition comprises powder paint compositions commonly used, as thermoplastic powder coating composition and powdered thermosetting compositions for coatings.Powdered thermosetting compositions for coatings is preferred, has good physicals because gained is filmed.The specific examples of powdered thermosetting compositions for coatings comprises epoxy powder clear coating composition, acrylic acid or the like powder clear coating composition, polyester powder clear coating composition etc.Acrylic acid or the like powder clear coating composition particularly preferably provides the film with excellent weather resistance.

[0128] common, be preferably 10-80 μ m, more preferably 20-60 μ m by the dry film thickness that applies the transparent coating that clear coating composition forms.When dry film thickness during less than 10 μ m, because the ununiformity of undercoat just can not be capped.When surpassing 80 μ m, just some problems may appear, for example coating composition explosion or sagging during applying.

[0129] heating simultaneously so the Clear coating that forms and the undercoat that forms previously can provide solidified to film.From the curing performance of gained multilayer film and the viewpoint of physicals, the solidified Heating temperature is preferably 80-180 ℃, more preferably 120-160 ℃.Being used for solidified is fit to determine according to temperature heat-up time.Be used for the solidified Heating temperature and be suitably for 120-160 ℃, be used for solidified and be suitably for 10-30 minute heat-up time.

[0130] so the thickness of the multilayer film of preparation is generally 30-300 μ m, preferred 50-250 μ m.When coating thickness during less than 30 μ m, itself the intensity of filming reduces.When surpassing 300 μ m, the physicals of filming behind thermal cycling test reduces.The multilayer film that the present invention further comprises so prepares.

[0131] method of above-mentioned formation multilayer film can provide the multilayer film that has very bright-coloured flash of light look and look performance, is coated with adhesive power, cracking resistance and water-fast adhesive power again on goods.

[0132] water-based metal colored paint composition of the present invention comprises, and contains the film-forming resin of specific acrylic resin emulsion; The solidifying agent that contains the aqueous dispersion of hydrophobic melamine resin with 20-140nm particle diameter, specific acrylic resin and specific hydrophobic melamine resin are mixed and reaction with specified proportion, to obtain reaction product, reaction product is scattered in the water, to obtain aqueous dispersion; And colored pigment.Therefore, water-based metal colored paint composition of the present invention can provide and have filming of good color performance.In addition, the described water-based metal colored paint composition aqueous primer composition that can be used as the method that is suitable for forming multilayer film is used for the motor vehicle coating step.The water-based metal colored paint composition can provide has the good multilayer film that is coated with adhesive power, good cracking resistance and good water-fast adhesive power again.Therefore, water-based metal colored paint composition of the present invention can be preferably used as aqueous primer composition.

Embodiment

[0133] about following examples the present invention is described in further detail below.The invention is not restricted to these embodiment.In this article, unless mention in addition, " part " and " % " refers to " weight part " and " % weight " respectively.

[0134] Preparation embodiment A 1: preparation acrylic resin emulsion Em-A1

In reactor, add 135.400 parts of ion exchanged waters and 1.100 parts of AQUARONHS-10 (polyxyethylated allyl phenyl ether sulfuric esters; By Dai-ichi Kogyo SeiyakuCo., Ltd. makes), and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, for the fs, dripped α simultaneously to reactor respectively through 2 hours, β-ethylenically unsaturated monomers mixture and initiator solution, monomer mixture comprise 35.730 parts of methyl acrylates, 8.570 parts of butyl methacrylate, 5.700 parts of 2-hydroxyethyl methacrylates, 20.000 parts of vinylbenzene, 0.500 part of AQUARON HS-10,0.500 part of ADEKAREASOAP NE-20 (α-[1-[(allyl group oxygen base) methyl]-the 2-Nonylphenoxy] ethyl)-ω-hydroxyl oxidize ethene; Make 80% aqueous solution by ADEKA CORPORATION) and 49.700 parts of ion exchanged waters, initiator solution comprises 0.210 part of ammonium persulphate and 8.600 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0135] in addition, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 25.300 parts of butyl methacrylate, 2.400 parts of 2-hydroxyethyl methacrylates, 2.300 parts of methacrylic acids, 0.100 part of AQUARON HS-10 and 24.700 parts of ion exchanged waters, and initiator solution comprises 0.080 part of ammonium persulphate and 7.400 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0136] subsequently, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.140 parts of ion exchanged waters and 0.240 part of dimethylaminoethanol then, to regulate pH to 6.5, obtain emulsion resin Em-A1, emulsion resin Em-A1 has median size, 30% non-volatile content, the acid number (based on solids content) of 15mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0137] Preparation embodiment A 2: preparation acrylic resin emulsion Em-A2

In reactor, add 135.400 parts of ion exchanged waters and 1.100 parts of AQUARONHS-10 (polyxyethylated allyl phenyl ether sulfuric esters; By Dai-ichi Kogyo SeiyakuCo., Ltd. makes), and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, for the fs, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 2 hours, monomer mixture comprises 35.695 parts of methyl acrylates, 8.570 parts of butyl methacrylate, 5.700 parts of 2-hydroxyethyl methacrylates, 20.000 parts of vinylbenzene, 0.035 part of ethylene glycol dimethacrylate, 0.500 part of AQUARONHS-10,0.500 part of ADEKA REASOAP NE-20 (α-[1-[(allyl group oxygen base) methyl]-the 2-Nonylphenoxy] ethyl)-ω-hydroxyl oxidize ethene; Make 80% aqueous solution by ADEKA CORPORATION) and 49.700 parts of ion exchanged waters, initiator solution comprises 0.210 part of ammonium persulphate and 8.600 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0138] in addition, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 25.285 parts of butyl methacrylate, 2.400 parts of 2-hydroxyethyl methacrylates, 2.300 parts of methacrylic acids, 0.015 part of ethylene glycol dimethacrylate, 0.100 part of AQUARON HS-10 and 24.700 parts of ion exchanged waters, and initiator solution comprises 0.080 part of ammonium persulphate and 7.400 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0139] subsequently, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.140 parts of ion exchanged waters and 0.240 part of dimethylaminoethanol then, to regulate pH to 6.5, obtain emulsion resin Em-A2, emulsion resin Em-A2 has median size, 30% non-volatile content, the acid number (based on solids content) of 15mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0140] Preparation embodiment A 3: preparation acrylic resin emulsion Em-A3

Prepare Em-A3 in the mode that is similar to preparation embodiment 2 (Em), different is the monomer formulation of change emulsion as shown in table 1, and the Em-A3 that makes has median size, 30% non-volatile content, the acid number (based on solids content) of 15mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0141] Preparation embodiment A 4: preparation acrylic resin emulsion Em-A4

In reactor, add 135.400 parts of ion exchanged waters and 1.100 parts of AQUARONHS-10 (polyxyethylated allyl phenyl ether sulfuric esters; By Dai-ichi Kogyo SeiyakuCo., Ltd. makes), and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, for the fs, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 2 hours, monomer mixture comprises 35.695 parts of methyl acrylates, 8.570 parts of butyl methacrylate, 5.700 parts of 2-hydroxyethyl methacrylates, 20.000 parts of vinylbenzene, 0.035 part of allyl methacrylate(AMA), 0.500 part of AQUARONHS-10,0.500 part of ADEKA REASOAP NE-20 (α-[1-[(allyl group oxygen base) methyl]-the 2-Nonylphenoxy] ethyl)-ω-hydroxyl oxidize ethene; Make 80% aqueous solution by ADEKA CORPORATION) and 49.700 parts of ion exchanged waters, initiator solution comprises 0.210 part of ammonium persulphate and 8.600 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0142] in addition, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 25.285 parts of butyl methacrylate, 2.400 parts of 2-hydroxyethyl methacrylates, 2.300 parts of methacrylic acids, 0.015 part of allyl methacrylate(AMA), 0.100 part of AQUARON HS-10 and 24.700 parts of ion exchanged waters, and initiator solution comprises 0.080 part of ammonium persulphate and 7.400 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0143] subsequently, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.140 parts of ion exchanged waters and 0.240 part of dimethylaminoethanol then, to regulate pH to 6.5, obtain emulsion resin Em-A4, emulsion resin Em-A4 has median size, 30% non-volatile content, the acid number (based on solids content) of 15mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0144] Preparation embodiment A 5: preparation acrylic resin emulsion Em-A5

Prepare Em-A5 in the mode that is similar to preparation embodiment 4 (Em), different is the monomer formulation of change emulsion as shown in table 1, and the Em-A5 that makes has median size, 30% non-volatile content, the acid number (based on solids content) of 15mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0146] Preparation embodiment A 6: preparation water-soluble acrylic resin

In reactor, add 23.89 parts of dipropylene glycol methyl ethers and 16.11 parts of methyl proxitols, and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 105 ℃ simultaneously.Then, dripped 13.1 parts of methyl methacrylates, 68.4 parts of ethyl propenoates, 11.6 parts of 2-hydroxyethyl methacrylates and 6.9 parts of methacrylic acids and initiator solution simultaneously to reactor respectively through 3 hours, initiator solution comprises 10.0 parts of dipropylene glycol methyl ethers and 1 part of 2-ethyl is crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 0.5 hour.

[0147] subsequently, dripped to reactor through 0.5 hour and contain the initiator solution that 5.0 parts of dipropylene glycol methyl ethers and 0.3 part of 2-ethyl are crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 2 hours.

[0148] in addition, utilize the equipment that desolventizes, steam down in 110 ℃ of decompressions (70torr) and remove 16.11 parts of solvents, add 204 parts of ion exchanged waters and 714 parts of dimethylethanolamines subsequently, obtain the water-soluble acrylic resin.The non-volatile content of gained acrylic resin solution is 30.0%, and acid number is 40mgKOH/g (based on a solids content), and hydroxyl value is 50mgKOH/g (based on a solids content).

[0149] Preparation embodiment A 7: preparation acrylic resin AcA1

In reactor, add 50 parts of MFDG (methyl propylidene glycol ether (methylpropylene diglycol), by NIPPON NYUKAZAI Co., Ltd. makes), and raise the temperature to 130 ℃, under nitrogen gas stream, stir simultaneously.Then, dripped ethylenically unsaturated monomers mixture (monomer mixture (a)) and initiator solution (b) simultaneously to reactor respectively through 3 hours, monomer mixture (a) comprises 14.77 parts of vinylformic acid, 32.48 parts of 2-hydroxyethyl methacrylates, 47.75 parts of butyl acrylates and 5 parts of MSD-100 (α-Jia Jibenyixierjuwus; Make by Mitsui Chemicals Inc.), initiator solution (b) comprises 13 parts of KAYAESTER O and (crosses the sad tert-butyl ester; Make by KAYAKU-AKUZO Inc.) and 10 parts of MFDG.After being added dropwise to complete, placed 0.5 hour, dripped the initiator solution (c) that contains 0.5 part of KAYAESTER O and 5 parts of MFDG then through 0.5 hour again.After being added dropwise to complete, uniform temp slaking 1 hour.

[0150] subsequently, make mixture be cooled to 50 ℃, obtain having non-volatile content 60%, the acrylic resin Ac1 of acid number 110mgKOH/g (based on solids content), hydroxyl value 140mgKOH/g (based on solids content) and number-average molecular weight (Mn) 3000.

[0151] Preparation embodiment A 8: the aqueous dispersion for preparing hydrophobic melamine resin MFD-A1

Acrylic resin AcA1 and 800 parts of U-VAN 20SB (complete butylated melamine resins with 178.5 parts of preparations in preparation embodiment A 7; Make non-volatile content 75% by CYTEC Japan Ltd.) mix, mixture was stirred 4 hours at 80 ℃.Add 18.3 parts of dimethylethanolamines then, homodisperse is cooled to 40 ℃, with after dripped 1003.2 parts of ion exchanged waters in 1 hour, obtains the aqueous dispersion MFD-A1 of hydrophobic melamine resin.The particle diameter of resin particle is 80nm in the aqueous dispersion.

[0152] Embodiment A 1

Utilize and stir, mix water-soluble acrylic resin, 10 parts of PRIMEPOLEPX-1000 (difunctionality polyether glycols of the acrylic resin emulsion Em-A1 of 153.3 parts of preparations in preparation embodiment A 1,5 part of 10% weight dimethyl ethanol amine aqueous solution, 16.7 parts of preparations in preparation embodiment A 6; Make by Sanyo Chemical Industries Ltd., number-average molecular weight 1000, hydroxyl value 278mgKOH/g, the fastness to water infinity), the MFD-A1 of 100 parts of preparations in preparation embodiment A 8,19 parts of ALPASTE MH8801 are as flash of light colored pigment (aluminium pigment, make by Asahi Kasai Corporation) and 30 parts of ethylene glycol mono hexyl ether, add the 10% weight dimethylaminoethanol aqueous solution then, to regulate pH to 8.5, and make the mixture homodisperse, obtain the water-based metal colored paint composition.Add the ion exchanged water diluted composition in addition,, obtain the water-based metal colored paint composition of coating step use so that the viscosity of measuring (at 20 ℃) coating composition by No.4 Ford cup was 60 (seconds).

[0153] Form multilayer film

On parkerized steel plate, apply in order by Nippon Paint Co., Ltd. the cation electric deposition paint composition of Zhi Zaoing " POWERTOP V-20 (ProductName) " and by Nippon Paint Co., Ltd. the polyester of Zhi Zaoing-melamine grey midcoat composition " ORGAH-870 (ProductName) ", heating, solidify, making the thickness of the dry electrodeposition coating of gained is 25 μ m, and the thickness of filming in the middle of the gained drying is 40 μ m, obtains test board.With electrostatic coating machine AutoREA (ProductName, by Landsberg Inc. make) at 5Kg/cm ²Atomizing pressure is coated to the water-based metal colored paint composition of above preparation on the test board.With plate 80 ℃ of preheatings 5 minutes.Bump wet step by wetting, utilization is sprayed on and applies on the test board by Nippon PaintCo., Ltd. " MACFLOW O-1810 (ProductName) " of Zhi Zaoing (by Nippon Paint Co., acid-curable epoxide type acrylic resin clear coating composition that Ltd makes).Plate was placed about 7 minutes,, thereby be coated with the test board that obtains applying in single baking (2C1B) coating step two then 140 ℃ of oven dry 30 minutes.At this, coloured the filming of solidified metal has 15 μ m dry thickness, and the solidified transparent coating has 40 μ m dry thickness.

[0154] Embodiment A 2-A5

Coating composition is prepared aqueous primer composition (embodiment A 2-A5) in the mode that is similar to embodiment A 1, and different is change emulsion resin as shown in table 2.Subsequently, form multilayer film according to the method that is similar to embodiment A 1.

[0155]

Table 2

[0156] applies also dry a kind of water-based metal colored paint composition (embodiment A 1-A5), to form single bottom coating.Measure the FF value of bottom coating (single) according to following evaluation method.The results are shown in the above table 2.

[0157] in addition, on bottom coating, apply clear coating composition, to form multilayer film.The same FF value of measuring multilayer film.The results are shown in the above table 2.

[0158] in addition, FF value and the aberration between the FF value behind the Clear coating of measuring single bottom coating change, i.e. (the FF value behind the Clear coating)/(the FF value of single bottom coating) * 100 (%) the results are shown in the table 2.

[0159] Evaluation method

Down flop property (FF performance)

Utilize Minolta Co., Ltd. " the MINOLTA Bending ColorDifference Meter CM512-M2 " that makes estimates down flop property, wherein measures with respect to incident light 15 ° the L value of filming with respect to the L value of filming of incident light at 75 °.In the present invention, down flop property can pass through (15 ° L value)/(110 ° L value) ratio and determines.

[0160] phrase used herein " color travel is remarkable " be meant when the anterior optic of filming is observed metal deposit (, with direction) perpendicular to coatingsurface, bright, the bright-coloured and flash of light look of observing is splendid, and on the other hand, when observing metal deposit with the directional vision of the level of filming, flash of light anomalous trichromatism and clearly observe initial look, therefore, the brightness contrast between them is remarkable.Therefore, phrase " color travel is remarkable " meaning metal deposit has the metal color that significantly changes with viewing angle, and this is a kind of splendid design.

Can see from result shown in the above table 2 that [0161] the FF value and the difference between the FF value behind the Clear coating of single bottom coating are less, and the disadvantageous effect of coating clear coating composition is also less.Aberration changes also splendid near 100%.It is about 81% that the aberration of embodiment A 1 is changed to, and the aberration of embodiment A 2-A5 changes respectively and surpasses 90%.The FF value and the difference between the FF value behind the Clear coating of bottom coating are very little.At this, the aberration that the aberration of embodiment A 1 changes less than embodiment A 2-A5 changes.Consideration is because the acrylic resin emulsion Em-A1 that the water-based metal colored paint composition comprises in the embodiment A 1 does not contain the unsaturated monomer with at least two unsaturated double-bonds.

[0162] Preparation Embodiment B 1: preparation acrylic resin emulsion Em-B1

In reactor, add 135.4 parts of ion exchanged waters and 1.1 parts of AQUARONHS-10 (polyxyethylated allyl phenyl ether sulfuric esters; By Dai-ichi Kogyo SeiyakuCo., Ltd. makes), and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, for the fs, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 2 hours, monomer mixture comprises 25.21 parts of methyl acrylates, 22.37 parts of ethyl propenoates, 7.42 parts of 2-hydroxyethyl methacrylates and 15 parts of methyl methacrylates, and initiator solution comprises 0.21 part of ammonium persulphate and 8.6 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0163] subsequently, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 23.54 parts of ethyl propenoates, 1.86 parts of 2-hydroxyethyl methacrylates and 4.60 parts of methacrylic acids, and initiator solution comprises 0.08 part of ammonium persulphate and 7.4 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0164] then, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.14 parts of ion exchanged waters and 0.24 part of dimethylethanolamine then, to regulate pH to 6.5, obtain acrylic resin emulsion Em-B1, resin emulsion Em-B1 has median size, 30% non-volatile content, the acid number (based on solids content) of 30mgKOH/g and the hydroxyl value (based on solids content) of 40mgKOH/g of 80nm.

[0165] Preparation Embodiment B 2: preparation water-soluble acrylic resin is (with above-mentioned preparation Embodiment A 6 is identical)

In reactor, add 23.89 parts of dipropylene glycol methyl ethers and 16.11 parts of methyl proxitols, and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 105 ℃ simultaneously.Then, dripped 13.1 parts of methyl methacrylates, 68.4 parts of ethyl propenoates, 11.6 parts of 2-hydroxyethyl methacrylates and 6.9 parts of methacrylic acids and initiator solution simultaneously to reactor respectively through 3 hours, initiator solution comprises 10.0 parts of dipropylene glycol methyl ethers and 1 part of 2-ethyl is crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 0.5 hour.

[0166] subsequently, dripped to reactor through 0.5 hour and contain the initiator solution that 5.0 parts of dipropylene glycol methyl ethers and 0.3 part of 2-ethyl are crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 2 hours.

[0167] in addition, utilize the equipment that desolventizes, steam down in 110 ℃ of decompressions (70torr) and remove 16.11 parts of solvents, add 204 parts of ion exchanged waters and 714 parts of dimethylethanolamines subsequently, obtain the water-soluble acrylic resin.The non-volatile content of gained acrylic resin solution is 30.0%, and acid number is 40mgKOH/g (based on a solids content), and hydroxyl value is 50mgKOH/g (based on a solids content).

[0168] Preparation Embodiment B 3: preparation acrylic resin Ac-B1 is (with above-mentioned preparation Embodiment A 7 is identical)

In reactor, add 50 parts of MFDG (methyl propylidene glycol ether, by NIPPONNYUKAZAI Co., Ltd. makes), and raise the temperature to 130 ℃, under nitrogen gas stream, stir simultaneously.Then, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 3 hours, monomer mixture comprises 14.77 parts of vinylformic acid, 32.48 parts of 2-hydroxyethyl methacrylates, 47.75 parts of butyl acrylates and 5 parts of MSD-100 (α-Jia Jibenyixierjuwus; Make by Mitsui Chemicals Inc.), initiator solution comprises 13 parts of KAYAESTER O and (crosses the sad tert-butyl ester; Make by KAYAKU-AKUZO Inc.) and 10 parts of MFDG.After being added dropwise to complete, placed 0.5 hour, dripped the initiator solution that contains 0.5 part of KAYAESTER and 5 parts of MFDG then through 0.5 hour again.After being added dropwise to complete, uniform temp slaking 1 hour.

[0169] subsequently, make mixture be cooled to 50 ℃, obtain having non-volatile content 60%, the acrylic resin Ac-B1 of acid number 110mgKOH/g (based on solids content), hydroxyl value 140mgKOH/g (based on solids content) and number-average molecular weight 3000.

[0170] Preparation Embodiment B 4: the aqueous dispersion for preparing hydrophobic melamine resin MFD-B1 (identical) with above-mentioned preparation embodiment A 8

Acrylic resin Ac-B1 and 800 parts of U-VAN 20SB (complete butylated melamine resins with 178.5 parts of preparations in preparation Embodiment B 3; Made by CYTEC Japan Ltd., non-volatile content 75% SP=9.6) mixes, and mixture was stirred 4 hours at 80 ℃.Add 18.3 parts of dimethylethanolamines then, homodisperse is cooled to 40 ℃, with after dripped 1003.2 parts of ion exchanged waters in 1 hour, obtains the aqueous dispersion MFD-B1 of hydrophobic melamine resin.The particle diameter of resin particle is 80nm in the aqueous dispersion.

[0171] Embodiment B 1

Utilize and stir, mix water-soluble acrylic resin, 10 parts of PRIMEPOLEPX-1000 (difunctionality polyether glycols of the acrylic resin emulsion Em-B1 of 153.3 parts of preparations in preparation Embodiment B 1,5 part of 10% weight dimethyl ethanol amine aqueous solution, 16.7 parts of preparations in preparation Embodiment B 2; Make by Sanyo Chemical Industries Ltd., number-average molecular weight 1000, hydroxyl value 278mgKOH/g, the fastness to water infinity), the MFD-B1 of 100 parts of preparations in preparation Embodiment B 4,19 parts of ALPASTE MH8801 are as flash of light colored pigment (aluminium pigment, make by Asahi Kasai Corporation), listed polyoxyalkylene compounds B in 30 parts of ethylene glycol mono hexyl ether and the 0.1 part of following table 1, and add the 10% weight dimethylaminoethanol aqueous solution, to regulate pH to 8.5, make the mixture homodisperse then, obtain water-based metal colored paint composition B1.Add ion exchanged water dilution coating composition in addition,, obtain the water-based metal colored paint composition of coating step use so that the viscosity of measuring (at 20 ℃) coating composition by No.4 Ford cup was 60 (seconds).

[0172] Form multilayer film

On parkerized steel plate, apply in order by Nippon Paint Co., Ltd. the cation electric deposition paint composition of Zhi Zaoing " POWERTOP V-20 (ProductName) " and by Nippon Paint Co., Ltd. the polyester of Zhi Zaoing-melamine grey midcoat composition " ORGAH-870 (ProductName) ", heating, solidify, making the thickness of the dry electrodeposition coating of gained is 25 μ m, and the thickness of filming in the middle of the gained drying is 40 μ m, obtains test board.With electrostatic coating machine AutoREA (trade(brand)name, by Landsberg Inc. make) at 5Kg/cm ²Atomizing pressure is coated to the aqueous primer composition of above preparation on the test board.With plate 80 ℃ of preheatings 5 minutes.Bump wet step by wetting, utilization is sprayed on and applies on the test board by Nippon Paint Co., Ltd. " MACFLOW O-1810 (ProductName) " of Zhi Zaoing (by Nippon Paint Co., acid-curable epoxide type acrylic resin clear coating composition that Ltd makes).Plate was placed about 7 minutes,, thereby be coated with the test board that obtains applying in single baking (2C1B) coating step two then 140 ℃ of oven dry 30 minutes.At this, coloured the filming of solidified metal has 15 μ m dry thickness, and the solidified transparent coating has 40 μ m dry thickness.

[0173] Embodiment B 2-B7

Prepare the water-based metal colored paint composition in the mode that is similar to the foregoing description B1, different is change polyoxyalkylene compounds as shown in table 3 and add-on thereof.Subsequently, form multilayer film in the mode that is similar to Embodiment B 1.

[0174] applies also dry a kind of water-based metal colored paint composition (Embodiment B 1-B7), to form single bottom coating.Measure the FF value of single bottom coating according to above-mentioned evaluation method.The results are shown in the following table 4.

[0175] in addition, on bottom coating, apply clear coating composition, film with formation.The same FF value of filming of measuring.The results are shown in the following table 3.

[0176] in addition, FF value and the aberration between the FF value behind the Clear coating of measuring single bottom coating change, i.e. (the FF value behind the Clear coating)/(the FF value of single bottom coating) * 100 (%) the results are shown in the table 4.

[0177] Evaluation method

Down flop property (FF performance) (identical) with above-mentioned down flop property

Utilize Minolta Co., Ltd. " the MINOLTA Bending ColorDifference Meter CM512-M2 " that makes estimates down flop property, wherein measures with respect to incident light 15 ° the L value of filming with respect to the L value of filming of incident light at 110 °.In the present invention, down flop property can pass through (15 ° L value)/(110 ° L value) ratio and determines.

[0178] phrase used herein " color travel is remarkable " be meant when the anterior optic of filming is observed metal deposit (, with direction) perpendicular to coatingsurface, bright, the bright-coloured and flash of light look of observing is splendid, and on the other hand, when observing metal deposit with the directional vision of the level of filming, flash of light anomalous trichromatism and clearly observe initial look, therefore, the brightness contrast between them is remarkable.Therefore, coloured the filming of phrase " color travel is remarkable " meaning metal has the metal color that significantly changes with viewing angle, and this is a kind of splendid design.

[0179]

Table 3

	ProductName ( *1)	Molecular weight (Mw)	OR	f
					Polyoxyalkylene compounds A	SN-4X 5526	6000	The R=ethylidene	136
Polyoxyalkylene compounds B	SN-4X 5527	20000	The R=ethylidene	455
					Polyoxyalkylene compounds C	SN-4X 5406	100000	The R=ethylidene	2273
Polyoxyalkylene compounds D	SN-4X 5528	700000	The R=ethylidene	15900

The ProductName of polyoxyalkylene compounds C, molecular weight and structure:

H(-OR) _f-OH

^*1 all compounds are all available from SAN NOPCO Ltd. (at Kyoto Prefecture).

Can see from result shown in the above table 4 that [0181] the FF value and the difference between the FF value behind the Clear coating of fabulous is bottom coating (single) are less, and it is also less to apply the disadvantageous effect of clear coating composition.Aberration changes also splendid near 100%.The aberration of Embodiment B 6 and B7 changes and is respectively about 81% and about 82%, and the aberration of Embodiment B 1-B5 changes respectively and surpasses 90%.The FF value and the difference between the FF value behind the Clear coating of bottom coating are very little.At this, the aberration that the aberration of Embodiment B 6 and B7 changes less than Embodiment B 1-B5 changes.Can believe that the polyoxyalkylene compounds of adding has less weight-average molecular weight, the amount of adding is also few.

[0182] The preparation viscosity modifier

Preparation embodiment A-1

For moisture content being set in 0.005% or still less (later on also be suitable for) according to Karl Fisher method, 90-100 ℃ of temperature and decompression (0.095 to-dewatered 3 hours from V-1326-oxyethane (50mol) affixture (505 parts (0.2 molar part)) under 0.098MPa) with 822.2mgKOH/g hydroxyl value and 2526 number-average molecular weights, wherein number-average molecular weight is calculated (also being suitable for later on) based on hydroxyl value.Make temperature be reduced to 70 ℃ subsequently, add 16.8 parts of (0.1 molar part) 1, [TAKENATE 700 for the 6-hexylidene diisocyanate, make by Mitsui TakedaChemicals Inc.] and 0.07 part of dibutyl tin laurate [STANN BL, by Sankyo Organic Chemicals Co., Ltd. make], under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (A-1).At this, the disappearance of an isocyanato is passed through to determine (also being suitable for later on) with the method for the dioxane measured in solution isocyanato content of Di-n-Butyl Amine.In addition, utilize polystyrene standards to measure according to GPC, weight-average molecular weight (Mw) is 9000.

[0183] subsequently, with 24 parts of propylene glycol list propyl ethers and 15 parts of A-1 of 61 parts of deionized water dilutions, obtain A-1 solution.The solution of same following A-2 to A-5 of preparation and B-1 to B-6.Can be used as coating composition with them.

[0184] Preparation embodiment A-2

For moisture content being set in 0.003% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from Stearyl alcohol-oxyethane (35mol) affixture (724 parts (0.4 molar part)) under 0.098MPa) with 36.0mgKOH/g hydroxyl value and 1810 number-average molecular weights.Make temperature be reduced to 70 ℃ subsequently, add 44.4 parts of (0.2 molar part) isophorone diisocyanate [IPDI, by Sumitomo Bayer Urethane Co., Ltd. make] and 0.07 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (A-2), wherein Mw is 6000.

[0185] Preparation embodiment A-3

For moisture content being set in 0.004% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from V-1326-oxyethane (70mol) affixture (681 parts (0.2 molar part)) under 0.098MPa) with 16.5mgKOH/g hydroxyl value and 3406 number-average molecular weights.Make temperature be reduced to 70 ℃ subsequently, [TAKENATE 500 to add 18.8 parts of (0.1 molar part) xylylene vulcabond, make by Mitsui Takeda Chemicals Inc.] and 0.07 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (A-3), wherein Mw is 11000.

[0186] Preparation embodiment A-4

For moisture content being set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from V-1326-oxyethane (180mol) affixture (660 parts (0.08 molar part)) under 0.098MPa) with 6.8mgKOH/g hydroxyl value and 8246 number-average molecular weights.Make temperature be reduced to 70 ℃ subsequently, add 8.9 parts of (0.04 molar part) isophorone diisocyanates and 0.07 part of dibutyl tin laurate, make mixture 80-100 ℃ of reaction 5 hours under nitrogen gas stream, obtain white viscous liquid carbamate compounds (A-4), wherein Mw is 20000.

[0187] Preparation embodiment A-5

For moisture content being set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from V-1326-oxyethane (230mol) affixture (627 parts (0.06 molar part)) under 0.098MPa) with 5.4mgKOH/g hydroxyl value and 10446 number-average molecular weights.Make temperature be reduced to 70 ℃ subsequently, add 5.0 parts of (0.03 molar part) 1,6-hexylidene diisocyanate and 0.07 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (A-5), wherein Mw is 25000.

[0188] Preparation Embodiment B-1

Mixing 415 parts of (0.05 molar part) PEG-6000S[is made by Sanyo Chemical IndustriesLtd.; Polyoxyethylene glycol with 13.5mgKOH/g hydroxyl value and 8300 number-average molecular weights] and 329 parts (0.2 molar part) V-1326-oxyethane (30mol) affixture with 34.1mgKOH/g hydroxyl value and 1646 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 33.3 parts of (0.15 molar part) isophorone diisocyanates and 0.1 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (B-1), wherein Mw is 20000.

[0189] Preparation Embodiment B-2

Mix V-1326-oxyethane (10mol) affixture that 1079 parts of (0.13 molar part) PEG-6000S and 153 parts (0.2 molar part) have 733mgKOH/g hydroxyl value and 766 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 38.6 parts of (0.15 molar part) 1,6-hexylidene diisocyanate and 0.15 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (B-2), wherein Mw is 31000.

[0190] Preparation Embodiment B-3

Mixing 1566 parts of (0.12 molar part) PEG-13000[is made by Sanyo ChemicalIndustries Ltd.; Polyoxyethylene glycol with 8.6mgKOH/g hydroxyl value and 13050 number-average molecular weights] and 109 parts (0.2 molar part) V-1326-oxyethane (5mol) affixture with 103mgKOH/g hydroxyl value and 546 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 41.4 parts of (0.22 molar part) xylylene vulcabond and 0.17 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (B-3), wherein Mw is 48000.

[0191] Preparation Embodiment B-4

Mix V-1326-oxyethane (25mol) affixture that 1162 parts of (0.14 molar part) PEG-6000S and 257 parts (0.2 molar part) have 43.6mgKOH/g hydroxyl value and 1286 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 53.3 parts of (0.24 molar part) isophorone diisocyanates and 0.12 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (B-4), wherein Mw is 33000.

[0192] Preparation Embodiment B-5

Mixing 800 parts of (0.04 molar part) PEG-20000[is made by Sanyo Chemical IndustriesLtd.; Polyoxyethylene glycol with 5.6mgKOH/g hydroxyl value and 20000 number-average molecular weights] and 41.7 parts (0.02 molar part) V-1326-oxyethane (40mol) affixture with 26.9mgKOH/g hydroxyl value and 2086 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 8.4 parts of (0.05 molar part) 1,6-hexylidene diisocyanate and 0.1 part of dibutyl tin laurate, under nitrogen gas stream, make mixture 80-100 ℃ of reaction 5 hours, obtain white viscous liquid carbamate compounds (B-5), wherein Mw is 120000.

[0193] Preparation Embodiment B-6

Mixing 660 parts of (0.2 molar part) PEG-4000S[is made by Sanyo Chemical IndustriesLtd.; Polyoxyethylene glycol with 34mgKOH/g hydroxyl value and 3300 number-average molecular weights] and 109 parts (0.2 molar part) V-1326-oxyethane (5mol) affixture with 103mgKOH/g hydroxyl value and 546 number-average molecular weights.For the moisture content with mixture is set in 0.005% or still less, 90-100 ℃ of decompression (0.095 to-dewatered 3 hours from mixture under 0.098MPa).Make mixture be cooled to 70 ℃ subsequently, add 56.4 parts of (0.3 molar part) xylylene vulcabond and 0.1 part of dibutyl tin laurate, make mixture 80-100 ℃ of reaction 5 hours under nitrogen gas stream, obtain white viscous liquid carbamate compounds (B-6), wherein Mw is 10000.

[0194] Preparation Embodiment C 1: preparation acrylic resin emulsion Em-C1

In reactor, add 135.4 parts of ion exchanged waters and 1.1 parts of AQUARON HS-10, and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 2 hours for the fs, monomer mixture comprises 35.73 parts of methyl acrylates, 8.57 parts of butyl methacrylate, 5.70 parts of 2-hydroxyethyl methacrylates, 20.00 parts of vinylbenzene, 0.50 part of AQUARON HS-10,0.50 part of ADEKAREA SOAP NE-20 and 49.70 parts of ion exchanged waters, and initiator solution comprises 0.21 part of ammonium persulphate and 8.60 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0195] in addition, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 26.05 parts of butyl methacrylate, 2.40 parts of 2-hydroxyethyl methacrylates, 1.55 parts of methacrylic acids, 0.10 part of AQUARON HS-10 and 24.70 parts of ion exchanged waters, and initiator solution comprises 0.08 part of ammonium persulphate and 7.40 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0196] subsequently, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.14 parts of ion exchanged waters and 0.16 part of dimethylaminoethanol then, to regulate pH to 6.5, obtain emulsion resin Em-C1, emulsion resin Em-C1 has median size, 30% non-volatile content, the acid number (based on solids content) of 10mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0197] Preparation Embodiment C 2: preparation acrylic resin emulsion Em-C2

In reactor, add 135.4 parts of ion exchanged waters and 1.1 parts of AQUARONHS-10 (polyxyethylated allyl phenyl ether sulfuric esters; By Dai-ichi Kogyo SeiyakuCo., Ltd. makes), and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 80 ℃ simultaneously.Then, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 2 hours for the fs, monomer mixture comprises 35.03 parts of methyl acrylates, 8.57 parts of butyl methacrylate, 0.70 part of allyl methacrylate(AMA), 5.70 parts of 2-hydroxyethyl methacrylates, 20.00 parts of vinylbenzene, 0.50 part of AQUARON HS-10,0.50 part of ADEKAREA SOAP NE-20 and 49.70 parts of ion exchanged waters, and initiator solution comprises 0.21 part of ammonium persulphate and 8.60 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 1 hour.

[0198] in addition, for subordinate phase, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor at 80 ℃ respectively through 0.5 hour, monomer mixture comprises 25.75 parts of butyl methacrylate, 0.30 part of allyl methacrylate(AMA), 2.40 parts of 2-hydroxyethyl methacrylates, 1.55 parts of methacrylic acids, 0.10 part of AQUARON HS-10 and 24.70 parts of ion exchanged waters, and initiator solution comprises 0.08 part of ammonium persulphate and 7.40 parts of ion exchanged waters.After being added dropwise to complete, uniform temp slaking 2 hours.

[0199] subsequently, make mixture be cooled to 40 ℃, filter by 400 order filters, add 2.14 parts of ion exchanged waters and 0.16 part of dimethylaminoethanol then, to regulate pH to 6.5, obtain emulsion resin Em-C2, emulsion resin Em-C2 has median size, 30% non-volatile content, the acid number (based on solids content) of 10mgKOH/g and the hydroxyl value (based on solids content) of 35mgKOH/g of 80nm.

[0200] Preparation Embodiment C 3: preparation water-soluble acrylic resin is (real with above-mentioned preparation It is identical to execute routine A6)

In reactor, add 23.89 parts of dipropylene glycol methyl ethers and 16.11 parts of methyl proxitols, and under nitrogen gas stream, utilize stirring that the mixture blended is raised the temperature to 105 ℃ simultaneously.Then, dripped 13.1 parts of methyl methacrylates, 68.4 parts of ethyl propenoates, 11.6 parts of 2-hydroxyethyl methacrylates and 6.9 parts of methacrylic acids and initiator solution simultaneously to reactor respectively through 3 hours, initiator solution comprises 10.0 parts of dipropylene glycol methyl ethers and 1 part of 2-ethyl is crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 0.5 hour.

[0201] subsequently, dripped to reactor through 0.5 hour and contain the initiator solution that 5.0 parts of dipropylene glycol methyl ethers and 0.3 part of 2-ethyl are crossed hecanoic acid t-butyl ester.After being added dropwise to complete, uniform temp slaking 2 hours.

[0202] in addition, utilize the equipment that desolventizes, steam down in 110 ℃ of decompressions (70torr) and remove 16.11 parts of solvents, add 6.40 parts of dimethylethanolamines and 188.0 parts of ion exchanged waters subsequently, obtain the water-soluble acrylic resin.The non-volatile content of gained acrylic resin solution is 30.0%, and acid number is 40mgKOH/g (based on a solids content), and hydroxyl value is 50mgKOH/g (based on a solids content).

[0203] Preparation Embodiment C 4: the aqueous dispersion for preparing hydrophobic melamine resin MFD-C1 (identical) with above-mentioned preparation embodiment A 8

In reactor, add 50 parts of MFDG (methyl propylidene glycol ether, by NIPPONNYUKAZAI Co., Ltd. makes), and raise the temperature to 130 ℃, under nitrogen gas stream, stir simultaneously.Then, dripped ethylenically unsaturated monomers mixture and initiator solution simultaneously to reactor respectively through 3 hours, monomer mixture comprises 14.77 parts of vinylformic acid, 32.48 parts of 2-hydroxyethyl methacrylates, 47.75 parts of butyl acrylates and 5 parts of MSD-100 (α-Jia Jibenyixierjuwus; Make by Mitsui Chemicals Inc.), initiator solution comprises 13 parts of KAYAESTER O and (crosses the sad tert-butyl ester; Make by KAYAKU-AKUZO Inc.) and 10 parts of MFDG.After being added dropwise to complete, placed 0.5 hour, dripped the initiator solution that contains 0.5 part of KAYAESTER O and 5 parts of MFDG then through 0.5 hour again.After being added dropwise to complete, uniform temp slaking 1 hour.Subsequently, make mixture be cooled to 50 ℃, obtain having non-volatile content 60%, the acrylic resin Ac-C1 of acid number 110mgKOH/g (based on solids content), hydroxyl value 140mgKOH/g (based on solids content) and number-average molecular weight 000.

[0204] with 178.5 parts of gained acrylic resin Ac-C1 and 800 parts of U-VAN20SB (complete butylated melamine resin; Made by CYTEC Japan Ltd., non-volatile content 75% Sp=9.6) mixes, and mixture was stirred 4 hours at 80 ℃.Add 18.3 parts of dimethylethanolamines then, homodisperse is cooled to 40 ℃, with after dripped 1003.2 parts of ion exchanged waters in 1 hour, obtains the aqueous dispersion MFD-C1 of hydrophobic melamine resin.The particle diameter of resin particle is 80nm in the aqueous dispersion.

[0205] Embodiment C 1

Utilize and stir, mix the acrylic resin emulsion Em-C1 of 153.3 parts of preparations in preparation Embodiment C 1 water-soluble acrylic resin, 10 parts of PRIMEPOLEPX-1000 (difunctionality polyether glycols as film-forming resin, 5 part of 10% weight dimethyl ethanol amine aqueous solution, 16.7 parts of preparations in preparation Embodiment C 2; Make by Sanyo Chemical Industries Ltd., number-average molecular weight 1000, hydroxyl value 278mgKOH/g, the fastness to water infinity), the MFD-C1 of 100 parts of preparations in preparation Embodiment C 3,19 parts of ALMINUM PASTE MH8801 are as flash of light colored pigment (aluminium pigment, make by Asahi Kasai Corporation), 30 parts of ethylene glycol mono hexyl ether and A-1 solution and B-1 solution (having solids content listed in the following table 5 respectively), and add the 10% weight dimethylaminoethanol aqueous solution, to regulate pH to 8.5, make the mixture uniform mixing then, obtain the water-based metal colored paint composition.Add ion exchanged water dilution gained water-based metal colored paint composition,, obtain the water-based metal colored paint composition of coating step use so that the viscosity of measuring (at 20 ℃) coating composition by the No.4Ford cup was 45 (seconds).In this solids content (NV) of measuring the water-based metal colored paint composition, the results are shown in the following table 9.

[0206] Form multilayer film

On parkerized steel plate, apply in order by Nippon Paint Co., Ltd. the cation electric deposition paint composition of Zhi Zaoing " POWERTOP V-20 (ProductName) " and by NipponPaint Co., Ltd. the polyester of Zhi Zaoing-melamine grey midcoat composition " ORGA H-870 (ProductName) ", heating, solidify, making the thickness of the dry electrodeposition coating of gained is 25 μ m, and the thickness of filming in the middle of the gained drying is 40 μ m, obtains test board.With electrostatic coating machine Auto REA (ProductName, by Landsberg Inc. make) at 5Kg/cm ²Atomizing pressure is coated to the aqueous primer composition of above preparation on the test board.With plate 80 ℃ of preheatings 5 minutes.Bump wet step by wetting, utilize to be sprayed on to apply " MACFLOW O-1810 (ProductName) " (by Nippon Paint Co., acid-curable epoxide type acrylic resin clear coating composition that Ltd makes) on the test board.Plate was placed about 7 minutes,, thereby be coated with the test board that obtains applying in single baking (2C1B) coating step two then 140 ℃ of oven dry 30 minutes.At this, coloured the filming of solidified metal has 15 μ m dry thickness, and the solidified transparent coating has the 40-dry thickness.Estimate the so down flop property (FF) and the covering with paint texture of the coated test plate of preparation.Evaluation result is shown in the following table 9.Evaluation method is as described below.

[0207] Embodiment C 2-C6 and C9-C24

Prepare the test board of water-based metal colored paint composition and coating in the mode that is similar to Embodiment C 1, different is to change viscosity modifier and amount thereof shown in following table 9-11.With estimating NV, FF and covering with paint texture, the results are shown among the following table 9-11 with Embodiment C 1 described identical mode.

[0208] Embodiment C 7-C8

The test board for preparing water-based metal colored paint composition and coating in the mode that is similar to Embodiment C 1, different is that the acrylic resin emulsion Em-C2 that is used in preparation in the preparation Embodiment C 2 replaces the acrylic resin emulsion Em-C1 of preparation in preparation Embodiment C 1 as film-forming resin, and changes viscosity modifier and amount thereof as shown in the following Table 5.With estimating NV, FF and covering with paint texture, the results are shown in the following table 9 with Embodiment C 1 described identical mode.

[0209]

Table 5

[0210]

Table 6

[0211]

Table 7

Amount listed in the table is based on solids content.

[0212]

Table 8

	Viscosity modifier	Mw
			Explain 1	A-1	9,000
Explain 2	A-2	6,000
			Explain 3	A-3	11,000
Explain 4	A-4	20,000
			Explain 5	A-5	25,000
Explain 6	B-1	20,000
			Explain 7	B-2	31,000
Explain 8	B-3	48,000
			Explain 9	B-4	33,000
Explain 10	B-5	120,000
			Explain 11	B-6	10,000

[0213] Test method

(1) solids content (NV) in the dilution coating composition

By adding ion exchanged water dilution water-based metal colored paint composition, measure the solids content (NV, % weight) of coating composition.Measure (at 20 ℃) by No.4 Ford cup this moment, and the viscosity through diluting coating composition was 45 (seconds).By the solids content of detection computations coating composition, wherein the sample with the 0.50g coating composition is placed on the furnace pot of accurately weighing, and weighs, and evenly stirs, and adds the dilution of 2.00g deionized water, 105 ℃ of dryings 3 hours, weighs, and calculated weight is poor then.

[0214] (2) changeable colors along with angle (FF) performance (identical) with above-mentioned down flop property

Utilize Minolta Co., Ltd. " the MINOLTA Bending Color DifferenceMeter CM512-M2 " that makes estimates down flop property, wherein measures with respect to incident light 15 ° the L value of filming with respect to the L value of filming of incident light at 110 °.In the present invention, down flop property can pass through (15 ° L value)/(110 ° L value) ratio and determines.At this, this ratio is big more, and down flop property is remarkable more.

Phrase used herein " down flop property is remarkable " be meant when the anterior optic of filming is observed metal deposit (, with direction) perpendicular to coatingsurface, bright, the bright-coloured and flash of light look of observing is splendid, and on the other hand, when observing metal deposit with the directional vision of the level of filming, flash of light anomalous trichromatism and clearly observe initial look, therefore, the brightness contrast between them is remarkable.Therefore, phrase " down flop property is remarkable " coloured the filming of meaning metal have the metal color that significantly changes with viewing angle, this is a kind of splendid design.

[0215] (3) cover with paint, lacquer, colour wash, etc. texture (entity texture (solid texture))

Utilization is measured shortwave (SW) value that gained is filmed by " ripple sweep measurement equipment " that BYK-Gardner Co. makes.According to following judgement criteria zero, △ and * estimate the covering with paint texture of filming.The results are shown among the following table 5-7.

Judgement criteria

Zero: SW is 10 or littler.

△: SW is 15 or littler.

*: SW is greater than 15.

[0216] Test-results

Table 9

[0217]

Table 10

[0218]

Table 11

[0219] splendid is that the FF performance is 3.80 or bigger, and NV is 24.0 or bigger.

Can see from above result that [0220] having highly filled Embodiment C 1-C24 provides splendid FF performance and splendid outward appearance.Have very highly filled Embodiment C 1-C8 splendid down flop property and splendid covering with paint texture is provided.These results are equivalent to carbamate compounds (A) as viscosity modifier and carbamate compounds (B) situation of ratio in the regulation preferable range as viscosity modifier, and carbamate compounds (A) and the situation of total content (B) in stipulating preferable range.

[0221] the present invention can set up enough solids content ratios and the splendid down flop property consistent with enough subparticles in the water-based paint compositions that can not obtain with prior art.

Commercial Application

[0222] water-based metal colored paint composition of the present invention can preferably be applicable to utilize the motor vehicle coating step of water-based metal colored paint composition.

Claims (9)

1. water-based metal colored paint composition, described composition comprises film-forming resin, solidifying agent and flash of light colored pigment, wherein

Described film-forming resin comprises acrylic resin emulsion, described emulsion can be obtained by the two-stage letex polymerization, and have the acid number (based on the solid resin content) of 1-30mgKOH/g, the hydroxyl value (based on the solid resin content) of 10-150mgKOH/g and the particle diameter of 20-140nm, and

Described solidifying agent is the aqueous dispersion with hydrophobic melamine resin of 20-140nm particle diameter.

2. the water-based metal colored paint composition of claim 1, wherein said acrylic resin emulsion can be obtained by the two-stage emulsion polymerization of monomer mixture, and described monomer mixture comprises the unsaturated monomer with at least two unsaturated double-bonds with respect to film-forming resin solids content weight 0.05-30.0% weight.

3. the water-based metal colored paint composition of claim 2, wherein said have the unsaturated monomer of at least two unsaturated double-bonds for being selected from least a monomer of ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate and (methyl) allyl acrylate.

4. the water-based metal colored paint composition of claim 1, wherein said film-forming resin further comprises the polyoxyalkylene compounds with formula (1) with respect to solid resin content weight 0.01-10% weight in the coating composition:

H(-OR) _f-OH (1)

Wherein

R is the alkyl with 2-5 carbon atom that can have side chain, and

F is 100 to 18000 integer.

5. the water-based metal colored paint composition of claim 4, wherein said polyoxyalkylene compounds has the weight-average molecular weight (Mw) of 10000-1000000.

6. each water-based metal colored paint composition in the claim 1 to 5, described coating composition further comprises viscosity modifier, and described viscosity modifier comprises the carbamate compounds (A) by general formula (1) expression

With carbamate compounds (B) by general formula (2) expression

Mixture,

Wherein

R ₁Identical or different, expression has the alkyl of 8 to 24 carbon atoms,

Y represents to eliminate the reactive residue that isocyanate group obtains from vulcabond,

OA and AO independently represent to have the oxyalkylene group of 2 to 4 carbon atoms,

O represents Sauerstoffatom,

C represents carbon atom,

N represents nitrogen-atoms,

M and n independently represent 20 to 500 integer,

A and d independently represent 1 to 100 integer,

B represents 40 to 500 integer,

C represents 1 to 5 integer,

(bxc) be 150 to 2500,

F represents 200 to 25000 integer, and

R, Y and P can be independently identical or different,

Wherein each carbamate compounds has the oxyethylene group with respect to oxyalkylene group gross weight at least 80% weight, and

Wherein the weight ratio of carbamate compounds (A)/carbamate compounds (B) is 95/5-5/95, and carbamate compounds (A) and total content (B) are 0.2-4.0% weight with respect to solid resin content in the water-based metal colored paint composition.

7. the water-based metal colored paint composition of claim 6 wherein in the two-stage emulsion polymerization, is had the acid number of 25-200mgKOH/g by the acrylic resin emulsion of emulsion polymerization acquisition in subordinate phase.

8. method that forms multilayer film, described method comprises:

Step (I) applies aqueous primer composition on goods, to form undercoat;

Step (II) is not making undercoat apply clear coating composition under solidifying on undercoat, to form Clear coating; With

Step (III) heats undercoat and Clear coating simultaneously,

Wherein said aqueous primer composition is each a water-based metal colored paint composition in the claim 1 to 7.

9. multilayer film, described multilayer film forms by the method for the formation multilayer film of claim 8.

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