CN105705597A

CN105705597A - Water-based paint composition and painted article

Info

Publication number: CN105705597A
Application number: CN201480038672.XA
Authority: CN
Inventors: 古泽智
Original assignee: Kansai Paint Co Ltd
Current assignee: Kansai Paint Co Ltd
Priority date: 2013-08-27
Filing date: 2014-07-16
Publication date: 2016-06-22
Anticipated expiration: 2034-07-16
Also published as: JP5791846B2; JPWO2015029627A1; WO2015029627A1; CN105705597B

Abstract

This water-based paint composition is characterized by containing (A) a non-chlorine based polyolefin resin, (B) a water-based polyurethane resin, (C) a blocked polyisocyanate compound, and (D) an electrically conductive pigment, the water-based polyurethane resin having an acid value of 1-30 mgKOH/g, and a time to film formation of 5-20 minutes at a temperature of 20 DEG C.

Description

Water-based paint compositions and coated article

Technical field

(cross reference of association area)

The application advocates the benefit of priority of the Japanese Patent Application 2013-175248 description (it is entirely through being incorporated by this specification) in application on August 27th, 2013。

(technical field)

The present invention relates to and can be formed no matter relative to metal parts or the water-based paint compositions of the film being respectively provided with the chipping resistance of excellence, tack, polishability and ethanol petrol resistant relative to plastic components and coated article。

Background technology

Generally, car body has the plastic components such as the metal parts forming vehicle body and bumper。

In the coating of this car body, conventional widely used following operation: utilize the different coating being suitable to all parts such as metal parts and plastic components and different painting process to be coated, then, plastic components is arranged on metal parts。

But, in recent years, in order to reduce equipment cost in the manufacturing process of car body and in order to make metal parts consistent with the tone of plastic components, seek a kind of method of coating when plastic components being installed on metal parts。

Such as Patent Document 1 discloses the coating process of a kind of body of a motor car being assembled with acrylic resin parts on metal foil。

But, middle painting coating disclosed in patent documentation 1 does not have electric conductivity, therefore, it is necessary to polypropylene member applying conductive primer base。It is to say, in patent documentation 1, to polypropylene member successively applying conductive primer base → middle painting coating → top coating, be coated with coating → top coating during metal parts is coated with successively。That is, owing to being not all plastic components and metal parts are used identical coating and is coated by identical painting process, therefore, cost reduction consistent with tone in insufficient。

A kind of water-based paint compositions containing specific anionic property urethane resin emulsion and specific urethane resin is had disclosed in patent documentation 2。But, when by this coatings in metal parts and plastic components, even if chipping resistance and light transmittance are no problem, compared with waterborne conductive priming paint, it is also difficult to say abundant relative to the tack of plastic components。

Patent Document 3 discloses a kind of water-borne primer coating composition formed so that specific ratio contains water polyolefin system resin (A), the water-base resin (B) of at least one in waterborne polyurethane resin and water-borne acrylic resin, polyester resin (C) and cross-linking agent (D)。But, when by this coatings in metal parts and plastic components, though no problem relative to the tack of plastic components, compared with being coated with coating with aqueous, it is also difficult to say that chipping resistance and light transmittance are abundant。

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2012-213692 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2005-330339 publication

Patent documentation 3:WO2007/66827 publication

Summary of the invention

The problem that invention to solve

The present invention considers that these aspects complete, and its object is to provide and can be formed no matter relative to metal parts or the water-based paint compositions of the film being respectively provided with excellent chipping resistance, tack, polishability and ethanol petrol resistant relative to plastic components and coated article。

Means needed for solution problem

The present inventor etc. have concentrated on studies to achieve these goals, found that above-mentioned problem can be solved by using containing chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the water-based paint compositions of blocked polyisocyanate compound (C) and conductive pigment (D) with nonionic hydrophilic group, thus completing the present invention。

That is, the present invention provides following water-based paint compositions and the article being coated with this water-based paint compositions and obtaining。

In first form of the present invention, a kind of water-based paint compositions can be provided, it contains chlorine-free polyolefin-based resins (A), waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D), it is characterized in that, the acid number of waterborne polyurethane resin (B) is 1mgKOH/g～35mgKOH/g, and at the temperature of 20 DEG C time to film forming be 5 minutes～20 minutes。

In one embodiment, there is the blocked polyisocyanate compound (C) of nonionic hydrophilic group for having the blocked polyisocyanate compound of at least one blocked isocyanate base in the blocked isocyanate base shown in the blocked isocyanate base shown in following formula (I), following formula (II) and the blocked isocyanate base shown in following formula (III)。

[chemical formula 1]

[in formula (I), R¹、R²、R⁴And R⁵Represent the alkyl of carbon number 1～12, R independently³Represent the straight-chain of carbon number 1～12 or the alkylidene of branched。]

[chemical formula 2]

[in formula (II), R²、R³、R⁴And R⁵With above-mentioned R²、R³、R⁴And R⁵Identical。]

[chemical formula 3]

[in formula (III), R²、R³、R⁴And R⁵With above-mentioned R²、R³、R⁴And R⁵Identical, R⁶Represent the alkyl of carbon number 1～12。]

In another embodiment, water-based paint compositions is possibly together with the base acrylic resin containing hydroxyl。

In further embodiment, the conductive pigment (D) of chlorine-free polyolefin-based resins (A) that water-based paint compositions contains 10 mass %～60 mass % with the total resin solid content quality in water-based paint compositions for benchmark, the waterborne polyurethane resin (B) of 10～50 mass %, the blocked isocyanate compounds (C) with nonionic hydrophilic group of 5 mass %～40 mass % and 0.5 mass %～40 mass %。

In second form of the present invention, it is possible to provide a kind of at the coating film-forming methods as the water-based paint compositions being coated with on the metal parts of coated article and plastic components described in any of the above-described item。

In the 3rd form of the present invention, it is possible to provide a kind of metal parts being included in coated article and plastic components are coated with the article of the film of water-based paint compositions described in any of the above-described item。

Invention effect

By the water-based paint compositions of the present invention, can be formed and no matter be respectively provided with the chipping resistance of excellence, tack, polishability with the film of ethanol petrol resistant relative to metal parts or relative to plastic components。

Detailed description of the invention

Hereafter, the water-based paint compositions of the present invention is illustrated in further detail。

In this manual, except there is situation about additionally expressing in this specification or except the situation that context is clearly contradicted, singulative includes single and multiple。

The water-based paint compositions of the present invention contains chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D)。

Chlorine-free polyolefin-based resins (A)

In the present invention, chlorine-free polyolefin-based resins (A) for main framing with molecular polyolefin and introduces the hydrophilic radicals such as carboxyl in the molecule thereof and is formed, it is usually preferred to unsaturated carboxylic acid or anhydride modified polyolefin (a)。

Unsaturated carboxylic acid or anhydride modified polyolefin (a) generally can be obtained to polyolefin graft copolymerization unsaturated carboxylic acid or anhydride by method known per se。As can be used for the unsaturated carboxylic acid or the anhydride that modifiy, including in 1 molecule containing at least 1, preferably comprise 1 polymerism double bond and do not contain chlorine, carbon number be 3～10 aliphatic carboxylic acid or its acid anhydride, specifically, such as can enumerate: (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride etc., wherein, it is particularly preferred to maleic acid and maleic anhydride。According to this unsaturated carboxylic acid or its anhydride, can change according to desired physical property of improved polyalkene etc. relative to polyolefinic graft copolymerization amount, but with polyolefinic solids by weight for benchmark generally in the scope of 0.5 weight %～4 weight %, in scope preferably in 1 weight %～3 weight %, it is preferred that in the scope of 1.2 weight %～2.8 weight %。

On the other hand, such as include making a kind in the alkene that carbon number is 2～10 such as ethylene, propylene, butylene, hexene or two or more (being total to) to be polymerized the polyolefin not being chlorinated formed for modified polyolefin, it is particularly preferred to containing the propylene polyolefin as polymerized unit。Consider from viewpoints such as the tacks with the compatibility and formation film of other composition, the weight fraction of the propylene units in improved polyalkene is generally in the scope of 0.5～1, particularly preferably in the scope of 0.7～0.99, further particularly preferably in the scope of 0.8～0.99。

As said polyolefins, use the polyolefin known per se not being chlorinated with can be without restriction, but from the viewpoint of the polyolefinic narrow molecular weight distribution obtained and random copolymerization etc. also excellence, it is preferred to use single site catalysts manufactures as polymerization catalyst and by (being total to) olefin polymerization。

Single site catalysts is the polymerization catalyst of active site even structure (unit point), particularly preferably metallocene series catalysts in this single site catalysts。This metallocene series catalysts is by combining the metallocene (double; two (cyclopentadienyl group) metal complexs and derivant thereof) as the periodic table of elements IVB～group vib or VIII transistion metal compound or IIIB race terres rares transistion metal compound at least with a conjugation five-membered ring part, being prepared by its organo-aluminum compound such as promoter and trimethyl aluminium such as the aikyiaiurnirsoxan beta activated or boron system。

(being total to) polymerization of alkene can according to method known per se, such as by while being supplied in reaction vessel by the alkene such as propylene or ethylene and hydrogen, interpolation alkyl aluminum and metallocene series catalysts carry out continuously on one side。

Above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can also carry out acrylic acid modified further。As can be used for this acrylic acid modified acrylic acid series unsaturated monomer, it is possible to enumerate not chloride acrylic acid series unsaturated monomer, (methyl) acrylic acid C1～C20 Arrcostab such as such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) octadecyl acrylate；(methyl) acrylic acid C1～C21 hydroxy alkyl esters such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester；(methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) acrylamide, (methyl) acrylonitrile etc. other acrylic monomer or enumerate styrene etc. further, these can individually use or two or more combination use。

It addition, in this manual, " (methyl) acrylic acid " refers to " acrylic or methacrylic acid ", and " (methyl) acrylate " refers to " acrylate or methacrylate "。

The acrylic acid modified of said polyolefins such as can pass through to operate as follows to carry out: first, make for the carboxyl in unsaturated carboxylic acid fabricated as described above or anhydride modified polyolefin, to there is the reaction such as reactive not chloride acrylic acid series unsaturated monomer, such as (methyl) glycidyl acrylate and introduce polymerism unsaturated group to polyolefin, then, make aforesaid propylene acid be unsaturated monomer individually or two or more combination have the polyolefin (being total to) of polymerism unsaturated group to be polymerized with above-mentioned introducing。Polyolefinic acrylic acid modified in aforesaid propylene acid be that the consumption that makes of unsaturated monomer can change according to desired physical property of improved polyalkene etc., but from the viewpoint of the tack etc. with the compatibility and formation film of other composition, with the solids by weight of the unsaturated carboxylic acid obtained or anhydride modified polyolefin (a) for benchmark, generally preferable at below 30 weight %, in scope particularly preferably in 0.1 weight %～20 weight %, further particularly preferably in the scope of 0.15 weight %～15 weight %。

In the present invention, unsaturated carboxylic acid or anhydride modified polyolefin (a) can also be modified by having the compound of polyoxyalkylene chain further。As the polyoxyalkylene chain in the compound with polyoxyalkylene chain, for instance can enumerate: the end-blocking chain etc. of polyoxyethylene chain, polyoxypropylene chains, polyoxyethylene and polyoxypropylene。

There is the compound of polyoxyalkylene chain and generally preferable have 400～3,000, preferably in the number-average molecular weight in the scope of 500～2,000。If this number-average molecular weight is less than 400, then cannot play the effect as hydrophilic group fully, it is possible to resistance to water is had undesirable effect, on the other hand, if more than 3,000, then at room temperature solidify thus dissolubility is deteriorated, it is possible to not easily operate。

For unsaturated carboxylic acid or anhydride modified polyolefin (a), from the viewpoint of the tack with the compatibility of other composition and the plastic components forming film or be coated with the interlayer tack etc. of film layer with top, expect that fusing point is less than 120 DEG C, preferably in the scopes of 60 DEG C～110 DEG C, it is preferred that in the scope of 70 DEG C～100 DEG C, and expect that weight average molecular weight (Mw) is 10,000～230, in the scope of 000, it is preferable that 50,000～200, in the scope of 000, it is preferred that 60,000～150, in the scope of 000。

Additionally, for unsaturated carboxylic acid or anhydride modified polyolefin (a), from the viewpoint of relative to formed film plastic components tack or with top be coated with film layer interlayer tack etc., it is generally desirable to melting caloric in the scope of 1mJ/mg～50mJ/mg, be especially desired in the scope of 2mJ/mg～50mJ/mg。

At this, fusing point and melting caloric for unsaturated carboxylic acid or anhydride modified polyolefin (a), can pass through to utilize Differential Scanning Calorimetry measurement apparatus " DSC-5200 " (Seiko Electronics Industry Company system, trade name), use improved polyalkene 20mg to be warming up to 150 DEG C with programming rate 10 DEG C/min from-100 DEG C and measure heat。The adjustment of the fusing point of unsaturated carboxylic acid or anhydride modified polyolefin (a) can form by changing polyolefinic monomer, particularly change the amount of 'alpha '-olefin monomers and carry out。It addition, when melting caloric is not easily obtained, can passing through temporarily to heat to 120 DEG C measurement sample, after being then cooled to room temperature with 10 DEG C/min, standing more than 2 days, thus measuring heat。

Additionally, the weight average molecular weight of unsaturated carboxylic acid or anhydride modified polyolefin (a) is the value weight average molecular weight recorded by gel permeation chromatography obtained with the weight average molecular weight of polystyrene for basis conversion, use " HLC/GPC150C " (the Waters company system as gel permeation chromatography device, 60cm × 1) and as the o-dichlorohenzene of solvent, with chromatographic column temperature 135 DEG C, flow measurement in 1.0ml/ minute。Injecting sample makes the mode relative to 3.4ml o-dichlorohenzene is the polyolefinic solution concentration of 5mg prepare for 1～3 hour by dissolving at 140 DEG C。It addition, as the chromatographic column for gel permeation chromatography, it is possible to use " GMHHR-H (S) HT " (east Cao (Co., Ltd.) company system, trade name)。

And then, for unsaturated carboxylic acid or anhydride modified polyolefin (a), from the viewpoint of the tack etc. with the compatibility or formation film of other composition, it is generally desirable to the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight in the scope of 1.5～7.0, preferably in the scope of 1.8～6.0, it is preferred that in the scope of 2.0～4.0。

In the present invention, chlorine-free polyolefin-based resins (A) can pass through that unsaturated carboxylic acid described above or anhydride modified polyolefin (a) disperse carry out moisture in an aqueous medium and dissipate, and generally can pass through part or all of the carboxyl in unsaturated carboxylic acid or anhydride modified polyolefin (a) to be neutralized with amines and/or utilize emulsifying agent to carry out moisture to dissipate。From the viewpoint of improving water dispersible, it is desirable to use the moisture dispersion by neutralizing and emulsifying agent carries out simultaneously。

As the amines for neutralizing, for instance can enumerate: the tertiary amines such as triethylamine, tri-n-butylamine, dimethylethanolamine, triethanolamine；The secondary amine such as diethylamine, dibutyl amine, diethanolamine, morpholine；The primary amine such as propylamine, ethanolamine etc.。Its when using these amines makes consumption preferably with respect to the carboxyl in unsaturated carboxylic acid or anhydride modified polyolefin (a) generally just in the scope of 0.1～1.0 molar equivalent。

As mentioned emulsifier, it is possible to enumerate such as, polyoxyethylene list oleyl ether, polyoxyethylene list octadecyl ether, polyoxyethylene list lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, ethylene nonyl phenyl ether, NONIN HS 240, Vinlub 73, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan mono-laurate, sorbitan monostearate, sorbitan monostearate, sorbitan trioleate, the nonionic system emulsifying agents such as polyoxyethylene 20 sorbitan monolaurate, alkyl sulfonic acid, alkyl benzene sulphonate, the anion system emulsifying agents etc. such as the sodium salt of alkyl phosphoric acid etc. or ammonium salt, and then, it is possible to use there is the polyoxyalkylenes such as anionic property group and polyoxyethylene groups or polyoxypropylene base in 1 molecule, anionic emulsifier containing polyoxyalkylenes or there is the reactive anionic emulsifier etc. of this anionic property group and polymerism unsaturated group in 1 molecule。These emulsifying agents can individually use or two or more combination uses。

Relative to solid constituent 100 weight portion of unsaturated carboxylic acid or anhydride modified polyolefin (a), above-mentioned emulsifying agent generally can use in the scope of 1 weight portion～20 weight portion。

The emulsification method of unsaturated carboxylic acid or anhydride modified polyolefin (a) is not particularly limited, it is possible to adopt the known methods such as such as Phase inversion emulsification, D phase emulsifying, forced emulsification, gel emulsifying, self emulsifying, reversion emulsifying, high-pressure emulsification。Wherein, from the viewpoint of the outward appearance of the film obtained and resistance to water, it is preferable that by the method that self emulsifying carries out。

Make containing the chlorine-free polyolefin-based resins (A) through acrylic acid modified unsaturated carboxylic acid or anhydride modified polyolefin by the acrylic acid series listed in acrylic acid modified explanation unsaturated monomer is carried out emulsion polymerization in case it addition, the aqueous dispersion of the unsaturated carboxylic acid as above obtained or anhydride modified polyolefin (a) can also be deposited at the unsaturated carboxylic acid being water dispersible or anhydride modified polyolefin (a)。

In the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, with the total resin solid content quality in coating composition for benchmark, the content of above-mentioned chlorine-free polyolefin-based resins (A) is 10 mass %～60 mass %, it is preferably 20 mass %～50 mass %, more preferably 25 mass %～50 mass %。

Waterborne polyurethane resin (B)

In the present invention, waterborne polyurethane resin (B) refers to can using water as scattered polyurethane resin in the aqueous medium of primary solvent or disperse medium, as the form in aqueous medium, can be any one in water solublity type, colloidal dispersion type, emulsion types and slurry types, but be preferably colloidal dispersion type or emulsion types。

As above-mentioned waterborne polyurethane resin (B), waterborne polyurethane resin known per se can be used, the waterborne polyurethane resin obtained preferably for example by following operation, namely, when there is the glycol as chain elongation agent, when 1 molecule such as diamidogen at least has the low molecular weight compound of 2 reactive hydrogens, polyurethane is optionally carried out further the material that chain elongation is obtained, it can stably disperse in an aqueous medium or dissolve and use, this polyurethane is by making PEPA, polycarbonate polyol, the polyhydric alcohol such as polyether polyol or low-molecular-weight hydroxy-containing compounds react obtained with polyisocyanate。

As above-mentioned polyol component, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and gasohol resistance, it is particularly preferred to PEPA and polyether polyol。

The above-mentioned PEPA used in manufacture as waterborne polyurethane resin (B), such as can enumerate: by making 1, the aliphatic diols such as 4-butanediol, 1,6-hexanediol and the aliphatic dicarboxylic acid such as adipic acid, decanedioic acid react obtained PEPA；By making this aliphatic diol and the aromatic dicarboxylic acids such as p-phthalic acid react obtained PEPA etc., as polycarbonate polyol, such as can enumerate: by making 1,6-hexanediol, 3-methyl isophthalic acid, the glycol such as 5-pentanediol and the carbonates such as dimethyl carbonate react obtained polycarbonate polyol etc., as polyether polyol, for instance can enumerate: the poly alkylene glycol etc. obtained by making the ring-opening polymerisations such as the oxirane of Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol etc., expoxy propane。Additionally, as above-mentioned polyisocyanate, for instance can enumerate: the aliphatic such as hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and alicyclic diisocyanate and their isocyanurate ring addition product etc.。As above-mentioned polisocyanate component, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, it is particularly preferred to isophorone diisocyanate。

And, for the glycol as chain elongation agent, for instance can enumerate: ethylene glycol, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, cyclohexanediol etc., as diamidogen, for instance can enumerate: ethylenediamine, propane diamine, xylylene diamine etc.。

As making waterborne polyurethane resin (B) method of stably dispersion or dissolving in water, for instance following method can be used。

(1) by using the carboxylic glycol such as dihydromethyl propionic acid, dimethylolpropionic acid to introduce carboxyl as the manufacture raw material of polyurethane to polyurethane, to give hydrophilic to polyurethane by part or all neutralizing this carboxyl, and be dispersed or dissolved in water by self emulsifying。

(2) as the polyhydric alcohol manufacturing raw material of polyurethane, use hydrophilic polyol as Polyethylene Glycol, manufacture water-soluble polyurethane, be dispersed or dissolved in water。

(3) end-capping reagents such as oxime, alcohol, phenol, mercaptan, amine, sodium sulfite are used to terminate to reacting complete polyurethane or terminal isocyanate group, by the polyurethane nonionic obtained and/or cationic emulsifier and mechanical shear stress Forced Dispersion in water。

(4) urethane prepolymer with terminal isocyanate group is mixed with water/emulsifying agent/chain elongation agent, carry out dispersion with mechanical shear stress simultaneously and quantify with macromolecule。

As waterborne polyurethane resin (B), it is not limited to the polyurethane obtained by single manufacture method, it is possible to use by the mixture of the polyurethane that various methods obtain。

From the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, the acid number of waterborne polyurethane resin (B) is in the scope of 1mgKOH/g～30mgKOH/g, preferably in the scope of 3mgKOH/g～25mgKOH/g, it is preferred that in the scope of 5mgKOH/g～20mgKOH/g。

From the viewpoint of the chipping resistance of the film obtained, tack, polishability and gasohol resistance, waterborne polyurethane resin (B) time to film forming at the temperature of 20 DEG C is 5 minutes～20 minutes, it is preferably 10 minutes～20 minutes, more preferably 12 minutes～18 minutes。

At this, the so-called time to film forming refers to that waterborne polyurethane resin forms the time needed for continuous film。The waterborne polyurethane resin time to film forming measures in the following way。

Room temperature 20 DEG C, humidity 60% environment under to use the waterborne polyurethane resin solution coating that solid constituent is adjusted to 28% by metering bar coater to make wet-film thickness on a pet film be 40 μm。The starting point of measure of time will be set to after being just coated with, on film, the height of 1cm uses dropper dropping 0.3mL ion exchange water at regular intervals, the change of the drop diameter just dripped in latter 1 second is set to terminal in the time of below 1mm, the time of origin-to-destination is set to " waterborne polyurethane resin time to film forming "。

Waterborne polyurethane resin (B) is from the viewpoint of the chipping resistance of the film obtained, tack, polishability and gasohol resistance, mean diameter in preferred aqueous medium is 70nm～250nm, it is preferably 80nm～230nm, more preferably 100nm～200nm。

In this manual, mean diameter is for using dynamic light scattering method particle size distribution measurement apparatus, after using deionized water dilution by conventional method, and the value recorded at 20 DEG C。As this dynamic light scattering method particle size distribution measurement apparatus, for instance " sub-micron grade particle analyzer N5 " (trade name, Beckmancoulter company system) can be used。

In the water-based paint compositions of the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, with the total resin solid content quality in coating composition for benchmark, the content of above-mentioned waterborne polyurethane resin (B) is 10 mass %～50 mass %, it is preferably 10 mass %～40 mass %, more preferably 15 mass %～30 mass %。

There is the blocked polyisocyanate compound (C) of nonionic hydrophilic group

A part of NCO that blocked polyisocyanate compound (C) is the polyisocyanate compounds in 1 molecule with more than 2 NCOs with nonionic hydrophilic group is blocked, by the modification of nonionic hydrophilic group, part or all of NCO remaining, the compound that agent is closed。

The blocked polyisocyanate compound (C) with nonionic hydrophilic group such as can be reacted with the NCO in the polyisocyanate compounds (c1) in 1 molecule with more than 2 NCOs by the active hydrogen-contg compound (c2) and end-capping reagent (c3) making to have nonionic hydrophilic group and obtain (following, the blocked polyisocyanate compound with nonionic hydrophilic group as above obtained is called " (C1) ")。

When the NCO in making above-mentioned polyisocyanate compounds (c1) and the above-mentioned active hydrogen-contg compound (c2) with nonionic hydrophilic group and end-capping reagent (c3) react, this polyisocyanate compounds (c1), the active hydrogen-contg compound (c2) and end-capping reagent (c3) with hydrophilic group reaction sequence be not particularly limited。Specifically, can enumerate: remaining NCO is used, after reacting, the method that end-capping reagent (c3) terminates by a part for the active hydrogen-contg compound (c2) and the NCO in polyisocyanate compounds (c1) that make to have hydrophilic group；After a part for NCO in polyisocyanate compounds (c1) being terminated with end-capping reagent (c3), make the method that the active hydrogen-contg compound (c2) with hydrophilic group reacts with remaining NCO；And make the method etc. that the active hydrogen-contg compound (c2) with hydrophilic group and end-capping reagent (c3) react simultaneously with the NCO in polyisocyanate compounds (c1)。

Polyisocyanate compounds (c1)

Polyisocyanate compounds (c1) is the compound at least in 1 molecule with 2 NCOs, for instance can enumerate: aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polyisocyanate, aromatic poly-isocyanate, this polyisocyanate derivant etc.。

As above-mentioned aliphatic polymeric isocyanate, such as can enumerate: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-trimethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 2,4,4-or 2,2, the aliphatic diisocyanates such as 4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, 2,6-bis-isocyanato-methyl caproates (common first names: lysinediisocyanate)；2,6-bis-isocyanato-caproic acid-2-isocyanato ethyl, 1,6-bis-isocyanato--3-isocyanatomethyl hexane, 1,4,8-tri-isocyanato-octane, 1,6,11-tri-isocyanato-hendecane, 1,8-bis-isocyanato--4-two isocyanatomethyl octane, 1,3,6-tri-isocyanato-hexane, 2,5, the aliphatic triisocyanates etc. such as 7-trimethyl-1,8-two isocyanato--5-isocyanatomethyl octane。

As above-mentioned alicyclic polymeric isocyanate, such as can enumerate: 1, 3-cyclopentene diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexylisocyanate (common first names: isophorone diisocyanate), 4-methyl isophthalic acid, 3-cyclohexene diisocyanate (common first names: hydrogenation TDI), 2-methyl isophthalic acid, 3-cyclohexene diisocyanate, 1, 3-or 1, double, two (isocyanatomethyl) hexamethylene (common first names: hydrogenated xylene diisocyanate) of 4-or its mixture, di-2-ethylhexylphosphine oxide (4, 1-hexamethylene two base) diisocyanate (common first names: hydrogenation MDI), the alicyclic diisocyanates such as norbornene alkyl diisocyanate；1, 3, 5-tri-isocyanatocyclohexane, 1, 3, 5-trimethyl isocyanatocyclohexane, 2-(3-isocyanatopropyl)-2, 5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 2-(3-isocyanatopropyl)-2, 6-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 3-(3-isocyanatopropyl)-2, 5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1)-heptane, the alicyclic triisocyanates etc. such as 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane。

As above-mentioned aromatic-aliphatic polyisocyanate, such as can enumerate: di-2-ethylhexylphosphine oxide (4,1-phenylene) diisocyanate (common first names: MDI), 1,3-or 1,4-XDI or its mixture, ω, ω '-two isocyanato--1,4-diethylbenzene, 1,3-or Isosorbide-5-Nitrae-bis-(1-isocyanato--1-Methylethyl) araliphatic diisocyanate such as benzene (common first names: tetramethylxylene diisocyanate) or its mixture；The aromatic-aliphatic triisocyanates etc. such as 1,3,5-tri-isocyanatomethylbenzene。

As above-mentioned aromatic poly-isocyanate, such as can enumerate: metaphenylene diisocyanate, to phenylene vulcabond, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4 toluene diisocyanate (common first names: 2,4-TDI) or 2,6-toluene di-isocyanate(TDI) (common first names: 2,6-TDI) or its mixture, 4,4 '-toluidine diisocyanate, 4, the aromatic diisocyanate such as 4 '-diphenyl ether diisocyanate；Triphenyl methane-4,4 ', 4 " aromatic tri-isocyanates such as-triisocyanate, 1,3,5-tri-isocyanato-benzene, 2,4,6-tri-isocyanato-toluene；4,4 '-diphenyl methane-2,2 ', the aromatic series tetraisocyanate etc. such as 5,5 '-tetraisocyanate。

Additionally, derivant as above-mentioned polyisocyanate, for instance can enumerate: the dimer of above-mentioned polyisocyanate, trimer, biuret, allophanate, urea diketone, urea imines, isocyanuric acid ester, diazine triketone, polymethylene polyphenyl base polyisocyanate (thick MDI, polycondensation MDI), thick TDI etc.。

As above-mentioned polyisocyanate and derivant thereof, it is possible to individually use and can also use two or more simultaneously。Additionally, in these polyisocyanate, as above-mentioned polyisocyanate compounds (c1), it is not likely to produce xanthochromia when heating, it is preferable that aliphatic diisocyanate, alicyclic diisocyanate and their derivant from the viewpoint of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained。Wherein, from the viewpoint of the flexible raising of the film formed, it is preferred that aliphatic diisocyanate and derivant thereof。

It addition, as above-mentioned polyisocyanate compounds (c1), it is possible to use make above-mentioned polyisocyanate and derivant thereof react when NCO is excessive with the compound that can react with this polyisocyanate and the prepolymer that generates。As the compound that can react with this polyisocyanate, for instance can enumerate: there is the compound of hydroxyl, amino isoreactivity hydrogen, specifically, for instance polyhydric alcohol, low molecular weight polyester resin, amine, water etc. can be used。

Additionally, as above-mentioned polyisocyanate compounds (c1), it is possible to use the polymer of the polymerism unsaturated monomer containing NCO, maybe should polymerism unsaturated monomer containing NCO with should the copolymer of polymerism unsaturated monomer beyond the polymerism unsaturated monomer containing NCO。

From the viewpoint of the compatibility of the reactivity of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and this blocked polyisocyanate compound (C) and other paint ingredient, several mean molecule quantities of above-mentioned polyisocyanate compounds (c1) are preferably in 300～20, in the scope of 000, more preferably in 400～8, in the scope of 000, it is preferred that 500～2, in the scope of 000。

Additionally, from the viewpoint of the compatibility of the reactivity of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and this blocked polyisocyanate compound (C) with nonionic hydrophilic group and other paint ingredient, the average isocyanate ester functional group number in above-mentioned polyisocyanate compounds (c1) preferably 1 molecule is in the scope of 2～100。As lower limit, consider from the reactive viewpoint improving the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained, more preferably 3。As the upper limit, from the viewpoint of prevent gelation when manufacturing blocked polyisocyanate compound (C) with nonionic hydrophilic group, more preferably 20。

There is the active hydrogen-contg compound (c2) of nonionic hydrophilic group

As the active hydrogen-contg compound with nonionic hydrophilic group, for instance the active hydrogen-contg compound with polyoxyalkylenes can be preferably used。As above-mentioned polyoxyalkylenes, for instance can enumerate: polyoxyethylene groups, polyoxypropylene base, polyoxyethylene (oxypropylene) base etc., these can be used alone or combine and use two or more。Wherein, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained, it is preferable that have the active hydrogen-contg compound of polyoxyethylene groups。

Considering from viewpoints such as the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and the resistances to water of film that formed, the above-mentioned active hydrogen-contg compound with polyoxyethylene groups has more than 3 continuous print oxyethylene groups, preferably has 5～100 continuous print oxyethylene groups, more preferably has 8～45 continuous print oxyethylene groups。

It addition, the above-mentioned active hydrogen-contg compound with polyoxyethylene groups is except continuous print oxyethylene group, it is also possible to containing the oxyalkylene group beyond oxyethylene group。As the oxyalkylene group beyond this oxyethylene group, for instance can enumerate: oxypropylene group, oxygen cyclobutenyl, oxygen hexenyl etc.。From the viewpoint of the blocked polyisocyanate compositions obtained moisture dissipate after storage stability, in the molar ratio of the oxyethylene group in oxyalkylene in the above-mentioned active hydrogen-contg compound with the polyoxyethylene groups scope preferably in 20 moles of %～100 mole %, in the scope more preferably in 50 moles of %～100 mole %。If the molar ratio of the oxyethylene group in oxyalkylene group is lower than 20 moles of %, then cannot fully giving hydrophilic, the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained reduces sometimes。

Additionally, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and the resistance to water of film that formed, the number-average molecular weight of the above-mentioned active hydrogen-contg compound with nonionic hydrophilic group is preferably in 200～2, in the scope of 000。As the lower limit of number-average molecular weight, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained, more preferably 300, more preferably 400。As the upper limit, from the viewpoint of the resistance to water of the film formed by the water-based paint compositions of the present invention, more preferably 1,500, more preferably 1,200。

As the above-mentioned active hydrogen-contg compound with nonionic hydrophilic group, such as can enumerate: the polyalkylene glycol monoalkyl ethers such as poly glycol monomethyl ether and polyethyleneglycol ether (another name: ω-alkoxy polyoxy), the polypropylene glycol monoalky lethers such as polypropylene glycol monomethyl ether and polypropylene glycol list ether (another name: ω-alkoxyl polyoxypropylene), ω-methoxy polyoxyethylene (oxypropylene), ω-the alkoxy polyoxy (oxypropylene) such as ω-ethyoxyl polyoxyethylene (oxypropylene), Polyethylene Glycol (propylene glycol) monomethyl ether, Polyethylene Glycol (propylene glycol) monoalky lethers such as the single ether of Polyethylene Glycol (propylene glycol), Polyethylene Glycol, polypropylene glycol, Polyethylene Glycol (propylene glycol), α-(aminoalkyl)-ω-alkoxy polyoxy, α-(aminoalkyl)-ω-alkoxyl polyoxypropylene, α-(aminoalkyl)-ω-alkoxy polyoxy (oxypropylene) etc., these can be used alone or combine and use two or more。Wherein, it is preferable that poly glycol monomethyl ether, polyethyleneglycol ether and Polyethylene Glycol, more preferably poly glycol monomethyl ether。

It addition, in this manual, " Polyethylene Glycol (propylene glycol) " refers to the copolymer of ethylene glycol and propylene glycol, comprises any one in end-capped copolymer and random copolymer。

It addition, as the market sale product of above-mentioned poly glycol monomethyl ether, for instance can enumerate: " UNIOXM-400 ", " UNIOXM-550 ", " UNIOXM-1000 " of Japan Oil Co, " UNIOXM-2000 " etc.。Additionally, market sale product as above-mentioned Polyethylene Glycol, for instance can enumerate: " PEG#200 ", " PEG#300 ", " PEG#400 " of Japan Oil Co, " PEG#600 ", " PEG#1000 ", " PEG#1500 ", " PEG#1540 ", " PEG#2000 " etc.。

From the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and curable and the tack of film that formed by the water-based paint compositions of the present invention, flatness, the viewpoint of distinctiveness and resistance to water considers, when a part of NCO in making polyisocyanate compounds (c1) reacts with the above-mentioned active hydrogen-contg compound (c2) with nonionic hydrophilic group, reaction ratio for isocyanate compound (c1) with the active hydrogen-contg compound (c2) with nonionic hydrophilic group, with 1 mole isocyanate base in polyisocyanate compounds (c1) be the reactive hydrogen in the preferred active hydrogen-contg compound of benchmark molal quantity in the scope of 0.03 mole～0.6 mole。As the upper limit, from the viewpoint of the curable of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and the resistance to water of film that formed by the water-based paint compositions of the present invention, it is more preferably 0.4, more preferably 0.3。As lower limit, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and the tack of film, flatness, distinctiveness and the resistance to water that are formed by the water-based paint compositions of the present invention, it is more preferably 0.04, more preferably 0.05。

End-capping reagent (c3)

As end-capping reagent, such as can enumerate: phenol system, alcohol system, active methylene group system, mercaptan system, acid amide system, acid imide system, imidazoles system, Urea Series, oxime system, carbamic acid system, amine system, imines system etc., these can be used alone or use two or more simultaneously。End-capping reagent is as follows more specifically。

(1) phenol system；Phenol, cresol, ethyl-phenol, butylphenol etc.,

(2) alcohol system；Ethylene glycol, benzyl alcohol, methanol, ethanol etc.,

(3) active methylene group system；Diester malonate, acetoacetic ester, isobutyryl acetas etc.,

(4) mercaptan system；Butyl mercaptan, lauryl mercaptan etc.,

(5) acid amide system；Acetanilide, amide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.,

(6) acid imide system；Butanimide, maleimide etc.,

(7) imidazoles system；Imidazoles, 2-methylimidazole etc.,

(8) Urea Series；Carbamide, thiourea, ethylidene-urea etc.,

(9) oxime system；Formaldoxime, aldoxime, methyl ethyl ketone oxime, cyclohexyl ketoxime etc.,

(10) carbamic acid system；N-phenylcarbamic acid phenyl ester etc.,

(11) amine system；Diphenylamine, aniline, carbazole etc.,

(12) imines system；Aziridine, polymine etc.。

The end-blockingization reaction utilizing the NCO of end-capping reagent (c3) optionally uses catalysts。As this catalysts, for instance can enumerate: alkali compoundss such as metal hydroxides, metal alkoxide, metal carboxylate, metal acetyl acetate, the hydroxide of salt, carboxylate, the slaine of activity methene compound, the salt of activity methene compound, amino silicone alkanes, amine, phosphine classes。Wherein, as salt, it is preferable that ammonium salt, salt, sulfonium salt。Generally, with the total solid composition quality of polyisocyanate compounds (c1) and end-capping reagent (c3) for benchmark, this catalysts make consumption preferably in 10ppm～10, in the scope of 000ppm, it is preferred that in 20ppm～5, in the scope of 000ppm。

It addition, utilize the end-blocking reaction of the NCO of above-mentioned end-capping reagent (c3) can carry out at 0 DEG C～150 DEG C, it is possible to use solvent。In this case, as solvent, it is preferable that non-protonic solvent, it is particularly preferred to ester, ether, N-alkylamide, ketone etc.。If reaction is it is anticipated that carry out, then can pass through to add acid composition and the alkali compounds as catalyst is neutralized, make reaction stop。

In utilizing the reaction of the end-blockingization of NCO of end-capping reagent (c3), the consumption that makes of end-capping reagent (c3) is not particularly limited, but use 0.1 mole～3 moles preferably with respect to 1 mole isocyanate base in polyisocyanate compounds (c1), it is preferred to use 0.2 mole～2 moles。It addition, the end-capping reagent not reacted with the NCO in polyisocyanate compounds (c1) can remove after end-blockingization reaction terminates。

Wherein, from the viewpoint of the curability at low temperatures of the film formed by the water-based paint compositions of the present invention, end-capping reagent (c3) is preferably active methylene group system。

From the viewpoint of the stability of the water-based paint compositions of the present invention, as the particularly preferably form of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group, it is possible to enumerate: have following formula (IV)

[chemical formula 4]

[in formula (IV), R¹Represent the alkyl of carbon number 1～12 independently, it is possible to identical, it is also possible to different。]

Shown blocked isocyanate base and there is the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group and there is following logical formula V

[chemical formula 5]

[in formula (V), R⁶And R⁷Represent the alkyl of carbon number 1～12 independently。]

Shown blocked isocyanate base and there is the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group。

There is the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group

There is the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group for having the blocked polyisocyanate compound of the blocked isocyanate base shown in above-mentioned formula (IV)。

Wherein, as the above-mentioned end-capping reagent (c3) of one of the raw material of this blocked polyisocyanate compound, from the viewpoint of the end-capping reagent compound that can use the active methylene group system that can manufacture relatively easily, R¹It is preferably the alkyl of carbon number 1～3。Wherein, from the viewpoint of improve obtain there is the blocked polyisocyanate compound (C1) of nonionic hydrophilic group and the compatibility of other paint ingredient, R¹It is preferably the alkyl of carbon number 2 or 3, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the flatness of film formed by the water-based paint compositions of the present invention and distinctiveness, R¹More preferably isopropyl。

The above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group such as by making above-mentioned polyisocyanate compounds (c1) and can have the active hydrogen-contg compound (c2) of nonionic hydrophilic group and obtains with reacting as end-capping reagent (c3), the alkyl with carbon number 1～12 dialkyl malonate。

As above-mentioned dialkyl malonate, such as can enumerating: dimethyl malenate, diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, malonic acid two n-pentyl ester, the just own ester of malonic acid two, malonic acid two (2-ethylhexyl) ester etc., these can be used alone or combine and use two or more。Wherein, preferred dimethyl malenate, diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, more preferably diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, it is preferred that Diisopropyl malonate。

There is the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group

There is the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group for having the blocked polyisocyanate compound of the blocked isocyanate base shown in above-mentioned logical formula V。

Wherein, as the above-mentioned end-capping reagent (c3) of one of the raw material of this blocked polyisocyanate compound, from the viewpoint of the end-capping reagent compound that can use the active methylene group system that can manufacture relatively easily, R⁶And R⁷It is preferably the alkyl of carbon number 1～3。Wherein, from the viewpoint of the compatibility of the blocked polyisocyanate compound (C1) and other paint ingredient with nonionic hydrophilic group obtained improves, R⁶And R⁷It is preferably the alkyl of carbon number 2 or 3, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained, the water-based paint compositions of the present invention flatness of film formed and distinctiveness, R⁶And R⁷More preferably isopropyl。

The above-mentioned blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group such as by making above-mentioned polyisocyanate compounds (c1) and can have the active hydrogen-contg compound (c2) of nonionic hydrophilic group and reacts with the isobutyryl acetas as end-capping reagent (c3), the alkyl with carbon number 1～12 acetoacetic ester or the alkyl with carbon number 1～12 and obtain。Wherein, as end-capping reagent (c3), it is preferable that obtain with reacting to react as end-capping reagent (c3), the alkyl with carbon number 1～12 isobutyryl acetas。

Additionally, as above-mentioned acetoacetic ester, such as can enumerating: methyl acetoacetate, ethyl acetoacetate, acetoacetic acid n-propyl, isopropyl acetoacetate, the positive butyl ester of acetoacetic acid, isobutyl acetoacetate, acetoacetic acid second butyl ester, tert-butyl acetoacetate, acetoacetic acid n-pentyl ester, the just own ester of acetoacetic acid, acetoacetic acid 2-Octyl Nitrite, acetoacetic acid phenyl ester, acetoacetic acid benzene methyl etc., these can be used alone or combine and use two or more。Wherein, it is preferable that methyl acetoacetate, ethyl acetoacetate and isopropyl acetoacetate。

As above-mentioned isobutyryl acetas; such as can enumerating: isobutyryl methyl acetate, ethyl isobutyryl acetate, isobutyryl n-propyl acetate, isobutyryl isopropyl acetate, isobutyryl n-butyl acetate, isobutyryl isobutyl acetate, isobutyryl sec-butyl acetate, isobutyryl tert-butyl acetate, isobutyryl n-amyl acetate, isobutyryl n-hexyl acetate, isobutyryl acetic acid 2-Octyl Nitrite, isobutyryl phenylacetate, isobutyryl phenylmethyl acetate etc., these can be used alone or combine and use two or more。Wherein, it is preferable that isobutyryl methyl acetate, ethyl isobutyryl acetate and isobutyryl isopropyl acetate。

In the present invention, particularly consider in the stability water, as the blocked polyisocyanate compound (C) with nonionic hydrophilic group, further secondary alcohol (c4) and the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group the is reacted obtained blocked polyisocyanate compound (following, the blocked polyisocyanate compound with nonionic hydrophilic group that as above obtain is called " (C2) ") with nonionic hydrophilic group is preferably used。

There is the blocked polyisocyanate compound (C2) of nonionic hydrophilic group

The blocked polyisocyanate compositions (C2) with nonionic hydrophilic group such as can by making the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group react with the secondary alcohol (c4) shown in following formula (VI) and obtain。

[chemical formula 6]

[in formula (VI), R²、R⁴And R⁵Represent the alkyl of carbon number 1～12, R independently³Represent the straight-chain of carbon number 1～12 or the alkylidene of branched。]

Secondary alcohol (c4)

Secondary alcohol (c4) is the compound shown in above-mentioned formula (VI)。Wherein, consider from the reactive viewpoint improving the above-mentioned blocked polyisocyanate compound (C1) and above-mentioned secondary alcohol (c4) with nonionic hydrophilic group, R²It is preferably methyl。If it addition, R³、R⁴And R⁵Respective carbon number is many, then the polarity of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group obtained reduces, and the compatibility with other paint ingredient reduces sometimes, therefore, and R³It is preferably the alkylidene of carbon number 1～3, R⁴And R⁵It is preferably methyl。

As above-mentioned secondary alcohol (c4), for instance can enumerate: 4-methyl-2-amylalcohol, 5-methyl-2-hexanol, 6-methyl-2-enanthol, 7-methyl-sec-n-octyl alcohol etc., these can be used alone or combine and use two or more。Wherein, after the reaction of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and above-mentioned secondary alcohol (c4), when part or all of unreacted secondary alcohol (c4) is distilled off, from the viewpoint of being easier to remove this secondary alcohol (c4), more preferably there is more lower boiling 4-methyl-2-amylalcohol。

For the blocked polyisocyanate compound (C2) with nonionic hydrophilic group, from the viewpoint of the stability of the water-based paint compositions of the present invention, as particularly preferred form, it is possible to enumerate following compound (C2-1) and (C2-2)。

There is the blocked polyisocyanate compound (C2-1) of nonionic hydrophilic group

Having the blocked polyisocyanate compound (C2-1) of nonionic hydrophilic group specifically such as can pass through to make that records in the explanation of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group to have following formula (IV)

[chemical formula 7]

Shown NCO and there is the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group react with above-mentioned secondary alcohol (c4) and obtain。

In this case, the R in the blocked isocyanate base in the above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group¹At least one be substituted by the group shown in following formula (VII)。

[chemical formula 8]

[in formula (VII), R²、R⁴And R⁵Represent the alkyl of carbon number 1～12, R independently³Represent the straight-chain of carbon number 1～12 or the alkylidene of branched。]

It addition, in this case, the blocked polyisocyanate compound obtained has the blocked isocyanate base shown in following formula (I) or the blocked isocyanate base shown in following formula (II)。

[chemical formula 9]

[chemical formula 10]

The reaction of the above-mentioned blocked polyisocyanate compound (C1-1) and secondary alcohol (c4) with nonionic hydrophilic group is not particularly limited, as long as such as can by the R in the blocked isocyanate base in the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group¹At least one method being substituted by the group shown in above-mentioned formula (VII)。Wherein, it is preferable that by the R that heat and decompression etc. will be derived from the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group¹, at least one part or all of alcohol be distilled off to the external promotion reaction of system, the method obtaining having the blocked polyisocyanate compound of the blocked isocyanate base shown in above-mentioned formula (I) or (II) and nonionic hydrophilic group。

As above-mentioned manufacture method, specifically, optionally reduce pressure under at 20 DEG C～150 DEG C, preferably in the temperature of 75～95 DEG C, through 5 minutes～20 hours, preferably through 10 minutes～10 hours by part or all removing of above-mentioned alcohol。If said temperature is too low, the exchange reaction then with the alkoxyl in the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group becomes slow, manufacture efficiency reduces, on the other hand, if temperature is too high, then having the decomposition deterioration of blocked polyisocyanate compound (C) of nonionic hydrophilic group acutely, curable reduces sometimes, and this is not desired。

There is the blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group

Additionally, for having the blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group, specifically, for instance can pass through make above-mentioned in there is the explanation of blocked polyisocyanate compound (C1) of nonionic hydrophilic group record there is following logical formula V

[chemical formula 11]

Shown NCO and there is the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group react with above-mentioned secondary alcohol (c4) and obtain。

In this case, the R in the blocked isocyanate base in the above-mentioned blocked polyisocyanate compound (C1-2) with hydrophilic group⁷It is substituted by the group shown in following formula (VII)。

[chemical formula 12]

In this case, the blocked polyisocyanate compositions obtained has the blocked isocyanate base shown in following formula (III)。

[chemical formula 13]

[in formula (III), R²、R³、R⁴And R⁵With described R²、R³、R⁴And R⁵Identical, R⁶Represent the alkyl of carbon number 1～12。]

The reaction of the above-mentioned blocked polyisocyanate compound (C1-2) and secondary alcohol (c4) with nonionic hydrophilic group is not particularly limited, as long as such as can by the R in the blocked isocyanate base in the blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group⁷The method being substituted by the group shown in above-mentioned formula (VII)。Wherein, it is preferable that by the R that heat and decompression etc. will be derived from the blocked polyisocyanate compound (C1-2) with hydrophilic group⁷, alcohol part or all be distilled off to system external promotion reaction, obtain having the blocked isocyanate base shown in above-mentioned formula (III) and there is the method for blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group。

As above-mentioned manufacture method, specifically, optionally reduce pressure under at 20 DEG C～150 DEG C, preferably in the temperature of 75 DEG C～95 DEG C, through 5 minutes～20 hours, preferably through 10 minutes～10 hours by part or all removing of above-mentioned alcohol。If said temperature is too low, the exchange reaction then with the alkoxyl in the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group becomes slow, manufacture efficiency reduces, on the other hand, if temperature is too high, acutely, curable reduces sometimes, and this is not desired in the decomposition deterioration of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group then obtained。

Additionally, from the viewpoint of the reactivity of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and manufacture efficiency, for in the manufacture of blocked polyisocyanate compound (C2) with nonionic hydrophilic group, the mixing ratio of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4), with solid constituent 100 mass parts of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group for benchmark, in the secondary alcohol (c4) scope preferably in 5 mass parts～500 mass parts, it is preferred that in the scope of 10 mass parts～200 mass parts。When lower than 5 mass parts, the blocked polyisocyanate compound (C1) with hydrophilic group is sometimes excessively slow with the response speed of secondary alcohol (c4)。If it addition, more than 500 mass parts, then the concentration of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group generated becomes too low, manufacture efficiency and sometimes reduce。

Additionally, in the reaction of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4), in order to adjust the molecular weight of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group, it is possible to carry out above-mentioned removing operation after adding polyol compound in this blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4)。

Compound (C2-1) or the compound (C2-2) stability in water in the blocked polyisocyanate compound (C) with nonionic hydrophilic group are also excellent especially, supposition is following reason: owing to having nonionic hydrophilic group, therefore more stably exist in water, and then, owing to comprising the alkyl with branched structure, therefore, the polarity of blocked isocyanate base is low, not facile hydrolysis。

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

Consider from the viewpoint such as the compatibility of other paint ingredient, the water-based paint compositions of the present invention flatness of coating, distinctiveness, tack, resistance to water and the chipping resistance that are formed, there is the number-average molecular weight of blocked polyisocyanate compound (C) of nonionic hydrophilic group preferably in 600～30, in the scope of 000。From the viewpoint of with the compatibility of other paint ingredient and the flatness of film formed by the water-based paint compositions of the present invention and distinctiveness, the upper limit as above-mentioned number-average molecular weight is more preferably 10,000, more preferably 5,000。It addition, from the viewpoint of the tack of the film formed by the water-based paint compositions of the present invention, resistance to water and chipping resistance, lower limit is more preferably 900, more preferably 1,000。

It addition, the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic group can also mix with surfactant in advance。In this case, from the viewpoint of the stability of the water-based paint compositions of the present invention, this surfactant is preferably nonionic surfactant。

In the water-based paint compositions of the present invention, the content of the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic group is from the viewpoint of the chipping resistance of the film obtained, tack, polishability and gasohol resistance, it is preferably 5 mass %～40 mass % with the total resin solid content quality in coating composition for benchmark, it is preferably 7 mass %～35 mass %, more preferably 10 mass %～30 mass %。

Conductive pigment (D)

Be not particularly limited as the conductive pigment (D) used in the present invention, as long as the film that formed can be given electric conductivity, particle shape, lamellar, fiber (comprising whisker) shape the pigment of any shape all can use。Specifically, for instance can enumerate: the conductive carbon such as conductive carbon black, CNT, carbon nano-fiber, the micro-coil of carbon；The metal powders such as silver, nickel, copper, graphite, aluminum, and then, it is possible to enumerate: antimony-doped tin oxide, phosphorus doping stannum oxide, carried out with stannum oxide/antimony surface-coated acicular titanium oxide, stibium oxide, zinc antimonates, tin indium oxide, at the pigment of the surface-coated stannum oxide of whisker etc. of carbon or graphite；The pigment of the coating conductive metal oxide such as stannum oxide or antimony-doped tin oxide of mica surface in lamellar；Pigment etc. contain stannum oxide and phosphorus on TiO 2 particles surface, that there is electric conductivity。These can individually use or combine and use two or more。Wherein, conductive carbon can particularly preferably be used。

In the water-based paint compositions of the present invention, the content of conductive pigment is from the viewpoint of the electric conductivity of the film obtained, it is preferably 0.5 mass %～40 mass % with the total resin solid content quality in coating composition for benchmark, it is preferably 1 mass %～35 mass %, more preferably 3 mass %～30 mass %。

In one embodiment, with the total resin solid content quality in coating composition for benchmark, the water-based paint compositions of the present invention contains the chlorine-free polyolefin-based resins (A) of 10 mass %～60 mass %, the waterborne polyurethane resin (B) of 10～50 mass %, the blocked isocyanate compounds (C) with nonionic hydrophilic group of 5 mass %～40 mass % and the conductive pigment (D) of 0.5 mass %～40 mass %, the acid number of waterborne polyurethane resin (B) is 1mgKOH/g～30mgKOH/g, and at the temperature of 20 DEG C time to film forming be 5 minutes～20 minutes。

Other composition

The water-based paint compositions of the present invention, with above-mentioned chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D) for required composition, can suitably contain the resinous principles such as the blocked polyisocyanate compound beyond hydroxy acryl acid resin, hydroxyl group containing polyester resin, composition (C), melmac, phenolic resin, polycarbonate resin and epoxy resin further。

Hydroxy acryl acid resin can use the hydroxy acryl acid resin of the water solublity known per se or water dispersible used in current water paint。Hydroxy acryl acid resin such as by making hydroxyl polymerism unsaturated monomer and can be manufactured by method copolymerization such as methods known per se, such as polymerisation in solution with other polymerism unsaturated monomer of this hydroxyl polymerism unsaturated monomer copolymerization。

Hydroxyl polymerism unsaturated monomer is the compound being respectively provided with more than 1 hydroxyl and polymerism unsaturated bond in 1 molecule, for instance can enumerate: the monoesters compound of the glycol such as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate and polyethyleneglycol (methyl) acrylate and acrylic or methacrylic acid；The compound etc. that the monoesters compound making 6-caprolactone sour with above-mentioned polyhydric alcohol and acrylic or methacrylic carries out ring-opening polymerisation and formed。

Can use according to the desired characteristic of hydroxy acryl acid resin is suitably selected with other polymerism unsaturated monomer of hydroxyl polymerism unsaturated monomer copolymerization。The concrete example of this monomer is set forth below。These can individually use or combine and use two or more。

(i) (methyl) acrylic acid alkyl or cycloalkyl ester: such as, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid iso stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid cyclo-dodecyl ester, (methyl) acrylic acid tricyclodecyl etc.。

(ii) there is the polymerism unsaturated monomer of isobornyl: such as, (methyl) isobornyl acrylate etc.。

(iii) there is the polymerism unsaturated monomer of adamantyl: such as, (methyl) acrylic acid adamantane esters etc.。

(iv) there is the polymerism unsaturated monomer of tricyclic decenyl: such as, (methyl) acrylic acid tricyclodecenyl esters etc.。

(v) polymerism unsaturated monomer containing aromatic rings: such as, (methyl) benzyl acrylate, styrene, α-methyl styrene, vinyltoluene etc.。

(vi) there is the polymerism unsaturated monomer of alkoxysilyl: such as, vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane etc.。

(vii) there is the polymerism unsaturated monomer of fluoro-alkyl: such as, (methyl) perfluoroalkyl acrylate such as (methyl) perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl octyl group ethyl ester；Fluoroolefin etc.。

(viii) there is the polymerism unsaturated monomer of the optical polymerism functional groups such as dimaleoyl imino。

(ix) vinyl compound: such as, NVP, ethylene, butadiene, chlorobutadiene, propionate, vinyl acetate etc.。

The polymerism unsaturated monomer of (x) phosphorous acidic group: such as, 2-acryloyl-oxyethyl phosphate ester acid, 2-methacryloxyethyl phosphate ester acid, 2-acryloxypropyl phosphate ester acid, 2-methacryloxypropyl phosphate ester acid etc.。

(xi) carboxylic polymerism unsaturated monomer: such as, (methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, P-carboxy ethyl acrylates etc.。

(xii) nitrogenous polymerism unsaturated monomer: such as, (methyl) acrylonitrile, (methyl) acrylamide, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, the addition product etc. of N-diethylamino ethyl ester, N, N-dimethylaminopropyl (methyl) acrylamide, di-2-ethylhexylphosphine oxide (methyl) acrylamide, ethylenebis (methyl) acrylamide, 2-(methacryloxy) ethyl-trimethyl salmiac, (methyl) glycidyl acrylate and amine。

(xiii) at least there is the polymerism unsaturated monomer of 2 polymerism unsaturated groups in 1 molecule: such as, (methyl) allyl acrylate, 1,6-hexanediol two (methyl) acrylate etc.

(xiv) the polymerism unsaturated monomer containing epoxy radicals: such as, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (methyl) acrylic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl propyl ester, allyl glycidyl ether etc.。

(xv) there is (methyl) acrylate of the polyoxyethylene chain that molecular end is alkoxyl。

(xvi) there is sulfonic polymerism unsaturated monomer: such as, 2-acrylamide-2-methylpro panesulfonic acid, (methyl) acrylic acid 2-sulphur ethyl ester, allyl sulphonic acid, 4-styrene sulfonic acid etc.；The sodium salt of these sulfonic acid and ammonium salt etc.。

(xvii) there is the polymerism unsaturated monomer of ultraviolet-absorbing functional group: such as, 2-hydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2-hydroxyl-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone, 2,2,-dihydroxy-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone, 2-(2 '-hydroxyl-5 '-methaciylyloxyethylphenyl)-2H-benzotriazole etc.。

(xviii) light stability polymerism unsaturated monomer: such as, 4-(methyl) acryloxy-1, 2, 2, 6, 6-pentamethvl, 4-(methyl) acryloxy-2, 2, 6, 6-tetramethyl piperidine, 4-cyano group-4-(methyl) Acryloyl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryloyl group-4-(methyl) Acryloyl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryloyl group-4-cyano group-4-(methyl) Acryloyl amino-2, 2, 6, 6-tetramethyl piperidine, 4-Fructus Crotonis acyloxy-2, 2, 6, 6-tetramethyl piperidine, 4-crotonocyl amino-2, 2, 6, 6-tetramethyl piperidine, 1-crotonocyl-4-Fructus Crotonis acyloxy-2, 2, 6, 6-tetramethyl piperidine etc.。

(xix) there is the polymerism unsaturated monomer of carbonyl: such as; acrylic aldehyde, N-[2-(2-methyl-4-oxopentyl), diacetone methacrylamide, acetoacetoxyethyl methacrylate, formoxyl styrene, have 4～7 carbon atoms vinyl alkyl ketone (such as, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc.。

(xx) there is the polymerism unsaturated monomer of anhydride group: such as, maleic anhydride etc., itaconic anhydride, citraconic anhydride etc.。

For hydroxy acryl acid resin, usual hydroxyl value is preferably in the scope of 10～150, be particularly preferably the scope of 50～100 in, acid number is preferably less than 60, is particularly preferably less than 50, weight average molecular weight be 1000～100000 scope in, be particularly preferably in the scope of 2000～60000。

Additionally, in this manual, the weight average molecular weight of above-mentioned hydroxy acryl acid resin and the number-average molecular weight of above-mentioned hydroxyl group containing polyester resin and above-mentioned melmac are the values tried to achieve using gel permeation chromatography (GPC) retention time (maintenance capacity) of recording to be scaled the molecular weight of polystyrene according to the retention time (maintenance capacity) of the known polystyrene standard of the molecular weight recorded in identical conditions。Specifically, use " HLC-8120GPC " (trade name, Dong Cao company system) as gel permeation chromatography device, use " TSKgelG4000HXL ", " TSKgelG3000HXL ", " TSKgelG2500HXL " and " TSKgelG2000HXL " (trade name, it is Dong Cao company system) amount to 4 as chromatographic column, differential refraction rate is used to be counted as detector, can at mobile phase: oxolane, measure temperature: 40 DEG C, flow velocity: measure when 1mL/min。

In the water-based paint compositions of the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, with the total resin solid content quality in coating composition for benchmark, the consumption that makes when using hydroxy acryl acid resin is 5 mass %～35 mass %, it is preferred to 10 mass %～25 mass %。

Hydroxyl group containing polyester resin can use the hydroxyl group containing polyester resin of the water solublity known per se or water dispersible used in current water paint, for instance can obtain by making polyprotic acid and polyhydric alcohol carry out esterification by method known per se when hydroxyl is excessive。Polyprotic acid is the compound in 1 molecule with more than 2 carboxyls, such as can enumerate: phthalic acid, M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Pyromellitic Acid, itaconic acid, adipic acid, decanedioic acid, Azelaic Acid, dodecanedioic acid, dimeric dibasic acid, humic acids, succinic acid, HET acid and their acid anhydride etc.。Polyhydric alcohol is the compound in 1 molecule with more than 2 hydroxyls, such as can enumerate: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, 2-ethyl-2-butyl-1,3-PD, cyclohexanedimethanol, trimethylolethane, trimethylolpropane, tetramethylolmethane, dipentaerythritol, Sorbitol etc.。The introducing of hydroxyl such as can be carried out by being simultaneously used in the polyhydric alcohol in 1 molecule with more than 3 hydroxyls。It addition, as polyester resin, it is possible to use by the fatty acid modified polyester resin that the fatty acids etc. such as soya fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid are modified。It addition, polyester resin can also be modified by epoxides such as butyl glycidyl base ether, alkyl phenyl glycidyl ethers, glycidyl neodecanoate。

For hydroxyl group containing polyester resin, usual hydroxyl value is preferably in the scope of 10mgKOH/g～160mgKOH/g, particularly preferably in the scope of 50mgKOH/g～85mgKOH/g, acid number is preferably in below 50mgKOH/g, particularly preferably in the scope of 1mgKOH/g～30mgKOH/g, number-average molecular weight is preferably in 1,000～20, in the scope of 000, particularly preferably in 1,300～10, in the scope of 000。

In the water-based paint compositions of the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, polishability and ethanol petrol resistant, with the total resin solid content quality in coating composition for benchmark, the consumption that makes when using hydroxyl group containing polyester resin is 2 mass %～20 mass %, it is preferred to 5 mass %～15 mass %。

End-blockingization polyisocyanate compounds beyond composition (C) is that the NCO to polyisocyanate compounds adds end-capping reagent and the compound that formed。The blocked polyisocyanate compound generated by adding is at ambient stable, but during preferably in sintering temperature (normally about 80 DEG C～about 200 DEG C) heated to film, end-capping reagent can dissociate and again generate free NCO。As the end-capping reagent meeting such essential condition, for instance can enumerate: the end-capping reagent such as phenol system, lactams system, alcohol system, ether system, oxime system, active methylene group system, mercaptan system, acid amide system, acid imide system, amine system, imidazoles system, pyrazoles system。

As melmac, it is particularly preferred to carried out the alkyl etherified melamine resin of etherificate by alkyl such as methyl, ethyl, normal-butyl, isobutyl group, hexyl, 2-ethylhexyls。These melmacs can have methylol, imino group etc. further。Number-average molecular weight that melmac is generally preferable to be had in 500～5,000 scopes, the number-average molecular weight particularly preferably having in 800～3,000 scopes。

The water-based paint compositions of the present invention can contain the additive etc. for coating such as coloring pigment, extender pigment, organic solvent, silane coupler, curing catalysts, viscosifier, defoamer, surface conditioner, coalescents further。

As coloring pigment, for instance can enumerate: titanium oxide, white carbon black, chrome yellow, loess, yellow iron oxide, hansa yellow, pigment yellow, chrome orange, molybdate red, forever solid orange, umber, permanent bordeaux, bright carmine, Fast violet, Methyl Violet Lake, ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, naphthol green, naphthol green, aluminum cream。These can individually use or combine and use two or more。

As extender pigment, for instance can enumerate: Talcum, silicon dioxide, calcium carbonate, barium sulfate, the flowers of zinc (zinc oxide) etc.。These can individually use or combine and use two or more。

As organic solvent, it is not particularly limited, as long as such as above-mentioned resinous principle can be mixed and dissolves or scattered organic solvent, it is possible to enumerate such as aliphatic hydrocarbon series solvent, aromatic hydrocarbon series solvent, alcohol series solvent, ester series solvent, ketone series solvent equal solvent。

As silane coupler, such as can enumerate: 2-(3, 4 epoxycyclohexyls) ethyltrialkoxysilanes, 3-glycidoxypropyl group trialkoxy silane, 3-glycidoxypropyl dialkoxy silicane, N-2-(amino-ethyl)-3-amino propyl methyl dialkoxy silicane, N-2-(amino-ethyl)-3-aminopropyltrialkoxy silanes, 3-aminopropyltrialkoxy silanes, 3-amino propyl methyl dialkoxy silicane, 3-mercaptopropyi methyl dioxane TMOS, 3-mercaptopropyi trialkoxy silane, N-phenyl-3-aminopropyltrialkoxy silanes, 3-ureidopropyltrialkoxysilane, 3-chloropropyl trialkoxy silane, double, two (trialkoxysilyl propyl group) tetrasulfide, 3-isocyanates propyl trialkoxy silane etc.。These can individually use or combine and use two or more。

The water-based paint compositions of the present invention can be coated on metal parts and the plastic components surface of coated article as mentioned above。Therefore, the article of the coating film-forming methods being coated with the water-based paint compositions of the present invention on the metal parts of coated article and plastic components surface and the film containing the water-based paint compositions being coated with the present invention on the metal parts and plastic components surface of coated article and obtaining also are contained in the scope of the present invention。As coated article, it does not have be particularly limited to, for instance can enumerate: automobile exterior panel portions such as passenger car, truck, motorcycle, buses；The auto parts such as bumper；The outside plate portion etc. of the household electrical appliance such as mobile phone, stereo set。Coated article as the film containing the present invention, it does not have be particularly limited to, for instance can enumerate: automobile and domestic electrical goods etc.。

As metal parts, for instance can enumerate: ferrum, aluminum, pyrite, copper, tinplate, rustless steel, galvanized steel and galvanized alloy (Zn-Al, Zn-Ni, Zn-Fe etc.) steel etc.。

Above-mentioned metal parts can also be the metal parts that its surface implements the surface treatments such as phosphate treated, chromate process and composite oxides process, and then, it is also possible to it is above defining the metal parts of the primary coat film formed by bottom-coating。As bottom-coating, it is possible to enumerate such as electrocoating paint, wherein, it is preferable that cationic electrocoating paint。

Material as plastic components, the polyolefin such as particularly preferably making a kind of olefines of the carbon numbers such as ethylene, propylene, butylene, hexene 2～10 or two or more (being total to) polymerization and formed, in addition, it is also possible to enumerate: Merlon, ABS resin, urethane resin, polyamide etc.。As plastic components, it is possible to enumerate: the parts of the plastics such as bumper in coated article, spoiler, grid, mud guard。These plastic components can suitably carry out ungrease treatment, washing process etc. before the coating of the water-based paint compositions of the present invention by method known per se。

Above-mentioned metal parts and plastic components can be assembled by known method。

The coating of the water-based paint compositions of the present invention uses aerial spraying, airless spraying, dip coated, brushing etc. to carry out preferably in metal parts and plastic components surface so that with dry film thickness generally in the scope of 1 μm～20 μm, preferably in the scopes of 3 μm～15 μm。After coating said composition, the coated surface obtained at room temperature can be solidified 30 seconds～about 60 minutes or (preheating) can be preheated 1 minute～about 60 minutes at the temperature of about 40 DEG C～about 80 DEG C, or can at about 60 DEG C～about 140 DEG C, preferably at the temperature of about 70 DEG C～about 120 DEG C, heating makes it solidify in 20 minutes～about 40 minutes, but in the present invention, especially, can not carry out preheating after the water-based paint compositions of the coating present invention and carry out being coated with as the top of subsequent processing coating, solidify 60 seconds～about 10 minutes under room temperature (about 20 DEG C～about 35 DEG C) preferably in after the water-based paint compositions of the coating present invention。

In the present invention, top coating can be coated with in the film coated surface utilizing the water-based paint compositions of the present invention to be formed。As top coating, pigmented finiss or clear dope can be individually used to be coated, it is possible to use this pigmented finiss is as two road primers and is coated with two road primer and clear dopes successively。It addition, be coated with such as white two road primers and interference pearly-lustre color two road primer on the film utilizing the water-based paint compositions of the invention described above to be formed successively and form multilayer film as painted base coating film layer。

As above-mentioned pigmented finiss, pigmented finiss known per se can be used, generally can use using organic solvent and/or water as primary solvent and the pigmented finiss containing the coloring components such as coloring pigment, luminous pigment, dyestuff and the resinous principle such as matrix resin, cross-linking agent。

As the matrix resin used in above-mentioned pigmented finiss, for instance can enumerate: have the resins such as hydroxyl, epoxy radicals, carboxyl, the acrylic resin of the such reactive functional groups of silanol group, polyester resin, alkyd resin。It addition, as cross-linking agent, it is possible to enumerate that have can with amino resins or (end-blocking) polyisocyanate, polyepoxide, polycarboxylic acids etc. such as the melmac of the reactive functional groups of above-mentioned functional group reactions, urea resins。

Above-mentioned pigmented finiss can suitably contain the additive for coating such as extender pigment, curing catalysts, UV absorbent, painting face regulator, rheology control agent, antioxidant, defoamer, wax, preservative。

Above-mentioned pigmented finiss can be coated with on the film formed by coating composition of the present invention that is above-mentioned uncured or that be cured, make dry film thickness generally in the scope of 5 μm～50 μm, preferably in the scopes of 5 μm～30 μm, it is preferred that in the scope of 10 μm～20 μm, the coated surface obtained at room temperature solidified 1 minute～60 minutes or preheat 1 minute～about 60 minutes at the temperature of about 40 DEG C～about 80 DEG C, or can at the temperature of about 60 DEG C～about 140 DEG C, preferably at the temperature of about 80 DEG C～about 120 DEG C, heating makes it solidify in 20 minutes～about 40 minutes。In the present invention, in particular it is preferred to it can not be made to solidify after being coated with painted two road primers and then carry out transparent coating。

As above-mentioned clear dope, such as can use the Thermocurable coating containing the resinous principle such as matrix resin, cross-linking agent and organic solvent or water etc. combined with ultraviolet radiation absorbent, light stabilizer, curing catalysts, painting face regulator, rheology control agent, antioxidant, defoamer, wax etc. are formed for the additive of coating further organic solvent system or water system, and there is the coating that permeable formed transparent coating is visually confirmed to be the transparency of lower coating film degree。

As above-mentioned matrix resin, such as can enumerate: the resins such as the acrylic resin of the reactive functional groups of at least one containing hydroxyl, carboxyl, silanol group, epoxy radicals etc., polyester resin, alkyd resin, fluororesin, urethane resin, containing silicone resin, in particular it is preferred to hydroxy acryl acid resin。As above-mentioned cross-linking agent, can enumerate: having can with the melmac of the reactive functional groups of these functional group reactionses, urea resin, (end-blocking) polyisocyanate compounds, epoxide, carboxylated compound, anhydride, compound etc. containing alkoxysilane group, in particular it is preferred to polyisocyanate compounds。

The coating of above-mentioned clear dope can carry out in the following manner: is coated with this clear dope on painted base coating film that is uncured or that be cured, make dry film thickness generally in the scope of 10 μm～50 μm, preferably in the scopes of 20 μm～45 μm, after the film coated surface obtained at room temperature being solidified 1 minute～60 minutes or preheating 1 minute～60 minutes at the temperature of about 40 DEG C～about 80 DEG C, at the temperature of about 60 DEG C～about 140 DEG C, preferably at the temperature of about 70 DEG C～about 120 DEG C, heating makes it solidify in 20 minutes～about 40 minutes。

By the water-based paint compositions of the present invention, the film relative to metal parts and plastic components with the chipping resistance of excellence, tack, polishability and ethanol petrol resistant can be formed。

Embodiment

Hereinafter, enumerate embodiment and the present invention is specifically illustrated by comparative example further。But, the present invention is not limited to these embodiments。It addition, " part " and " % " is all according to quality criteria。It addition, the thickness of film is based on cured coating film。

The manufacture of chlorine-free polyolefin-based resins (A)

Manufacture example 1

The mixture being made up of the maleation polypropylene resin (chlorination rate 22%, maleic acid modified amount 2.0%, acid number 30mgKOH/g) 500 parts of weight average molecular weight 80000, normal heptane 150 parts and N-Methyl pyrrolidone 50 parts is heated to 50 DEG C, add dimethylethanolamine 12 parts and " NOIGENEA-140 " (nonionic system surfactant, the 1st industrial pharmaceutical (strain) system, trade name) 5 parts, after synthermal lower stirring 1 hour, it is slowly added to deionized water 2000 parts, carries out stirring in 1 hour further。

Then, reduce pressure at the temperature of 70 DEG C, normal heptane and water totally 600 part are distilled off, obtain chlorine-free vistanex dispersion liquid (A-1) of solid constituent containing ratio 23.6%。

Manufacture example 2

In the 4 mouthfuls of flasks being provided with agitator, condensing tube, thermometer and Dropping funnel, by maleic anhydride inoculated polypropylene (relative to the polypropylene using metallocene series catalysts to obtain, add 4 mass % with maleic acid to be modified and the material that obtains, fusing point 80 DEG C, Mw about 150,000, Mw/Mn about 2.5) 100g adds heat fusing at 140 DEG C, add polyoxyethylene stearyl base ether (" Newcol1820 ", single end hydroxyl polyoxyethylene compound, emulsifying agent company of Japan system) 15g, stir at 140 DEG C, carry out reaction in 4 hours。After reaction, it is cooled to 90 DEG C, adds deionized water and be filtered, obtain chlorine-free vistanex dispersion liquid (A-2) of solid constituent 30%。

The manufacture of waterborne polyurethane resin (B)

Manufacture example 3

The reactive tank with thermometer, blender, reflux condenser adds polytetramethylene glycol (number-average molecular weight 1000) 211.9 parts, α, α-dihydromethyl propionic acid 11.5 parts, trimethylolpropane 6.9 parts, isophorone diisocyanate 112.2 parts and methyl ethyl ketone 298.5 parts, after reaction system is replaced with nitrogen, make it react when stirring in 80 DEG C, obtain the NCO end urethane prepolymer of free isocyanate group content 3.2%。This methyl ethyl ketone solution obtained is cooled to 40 DEG C, after adding the deionized water 493.2g emulsifying containing triethylamine 5.2 parts, add 5% ethylenediamine solution 159.2 parts wherein, after stirring 60 minutes, methyl ethyl ketone is distilled off when heating under reduced pressure, carry out concentration adjustment with deionized water, obtain the waterborne polyurethane resin dispersion liquid (B-1) of solid constituent 35%, film forming required time 15 minutes, acid number 14mgKOH/g, mean diameter 120nm。

Manufacture example 4～13

In manufacturing example 3, cooperation composition is set as shown in table 1, in addition, obtains each waterborne polyurethane resin dispersion liquid by the operation identical with manufacturing example 3。

It addition, the cooperation of table 1 represents with solids content, (note 1) in table 1 is as shown in following。

The manufacture of (note 1) PEPA A

The sodium salt 49 parts of Polyethylene Glycol (number-average molecular weight 300) 67 parts and 5-dimethyl sulfoisophthalate and Dibutyltin oxide 0.2 part are incorporated in reaction vessel, 190 DEG C it are warming up under the decompression state of 5mmHg, distillation for removing methanol is while carrying out 6 hours ester exchange reactions on one side, obtains the PEPA A on average in 1 molecule with 5 sodium sulfonate groups, hydroxyl value 29.6mgKOH/g, number-average molecular weight 3700。

[table 1]

Table 1

There is the manufacture of the blocked polyisocyanate compound (C) of nonionic hydrophilic group

Manufacture example 14

There is thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, dropper and except the simple and easy catcher of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company system, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 1610 parts, " UNIOXM-550 " (You company system, MPEG-550, mean molecule quantity about 550) 275 parts and 2, 6-di-tert-butyl-4-methy phenol 0.9 part, it is sufficiently mixed, heat 3 hours in 130 DEG C under nitrogen flowing。Then, add ethyl acetate 550 parts and Diisopropyl malonate 1150 parts, under state under nitrogen flowing, stir 28% methanol solution 14 parts adding Feldalat NM, stir 8 hours at 65 DEG C。Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg。Add 4-methyl-2-amylalcohol 3110 parts wherein, the temperature of system is maintained at 80 DEG C～85 DEG C one side and solvent was distilled off through 3 hours at reduced pressure conditions, obtain blocked polyisocyanate composition solution (C-1) 4920 parts。Except the simple and easy catcher of solvent contains 585 parts of isopropanols。The solid component concentration of the blocked polyisocyanate composition solution (C-1) obtained is about 60%。

Manufacture example 15

Possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except the simple and easy catcher of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company system, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 1610 parts, " UNIOXM-550 " (You company system, MPEG-550, mean molecule quantity about 550) 275 parts and 2, 6-di-tert-butyl-4-methy phenol 0.9 part, it is sufficiently mixed, state under nitrogen flowing heats 3 hours in 130 DEG C。Then, adding ethyl acetate 550 parts and Diisopropyl malonate 1150 parts, state under nitrogen flowing stirs 28% methanol solution 14 parts adding Feldalat NM, stirs 8 hours at 65 DEG C。Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg。The solid component concentration of the blocked polyisocyanate composition solution (C-2) obtained is about 60%。

Manufacture example 16

" SumiduleN-3300 " 1610 parts and hydroxy new pentane acid 236 parts is added in there is thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and the reaction vessel except the simple and easy catcher of solvent, stirring while being sufficiently mixed, state under nitrogen flowing heats 3 hours in 130 DEG C。Then, adding ethyl acetate 550 parts and Diisopropyl malonate 930 parts, state under nitrogen flowing stirs 28% methanol solution 14 parts adding Feldalat NM, stirs 8 hours at 65 DEG C。Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg。Add 4-methyl-2-amylalcohol 2530 parts wherein, the temperature of system is maintained at 80 DEG C～85 DEG C one side and solvent was distilled off through 3 hours at reduced pressure conditions, obtain blocked polyisocyanate composition solution (C-3) 4450 parts。Except the simple and easy catcher of solvent contains 475 parts of isopropanols。The solid component concentration of the blocked polyisocyanate composition solution (C-3) obtained is about 60%。

Manufacture example 17

There is thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except the simple and easy catcher of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company system, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 480 parts, ethyl acetate 150 parts and Diisopropyl malonate 365 parts, state stirring under nitrogen flowing is while adding 28% methanol solution 4 parts of Feldalat NM on one side, stir 8 hours at 65 DEG C。Amount of isocyanate in the resin solution obtained is 0.07 mole/kg。Add 4-methyl-2-amylalcohol 870 parts wherein, while the temperature of system being maintained at 80 DEG C～85 DEG C solvent was distilled off through 3 hours at reduced pressure conditions, add 4-methyl-2-amylalcohol 120 parts, obtain blocked polyisocyanate composition solution (C-4) 1400 parts。Except the simple and easy catcher of solvent contains 183 parts of isopropanols。The solid component concentration of the blocked polyisocyanate compound solution (C-4) obtained is about 60%。

Additionally, and (C-2) blocked polyisocyanate compound solution for using in embodiment described later, (C-3) and (C-4) blocked polyisocyanate compound solution for using in comparative example described later (C-1)。

The manufacture of hydroxy acryl acid resin

Manufacture example 18

Propylene glycol monopropyl ether 35 parts is added in there is thermometer, thermostat, mix the reaction vessel of device, reflux condenser, nitrogen ingress pipe and Dropping feeder, after being warming up to 85 DEG C, last 4 hours dropping methyl methacrylates 30 parts, 2-EHA 20 parts, n-butyl acrylate 29 parts, acrylic acid 2-hydroxy methacrylate 15 parts, 6 parts of acrylic acid, propylene glycol monopropyl ether 15 parts and 2,2 '-azo double; two (2,4-methyl pentane nitrile) mixture of 2.3 parts, completion of dropwise addition post curing 1 hour。Then last 1 hour dropping propylene glycol monopropyl ether 10 parts and 2, the mixture of 2 '-azo pair (2,4-methyl pentane nitrile) 1 part, completion of dropwise addition post curing 1 hour then,。Add diethanolamine 7.4 parts, obtain the hydroxy acryl acid resin solution (E-1) of solid constituent 55%。The acid number of the hydroxy acryl acid resin obtained is 47mgKOH/g, hydroxyl value is 72mgKOH/g。

The manufacture of hydroxyl group containing polyester resin

Manufacture example 19

The reaction vessel possessing thermometer, thermostat, agitating device, reflux condenser and water separator adds adipic acid 192 parts, hexahydrophthalic anhydride 307 parts, 2-butyl-2-ethyl-1, ammediol 439 parts, 1,6-hexanediol 88.7 parts and trimethylolpropane 36.0 parts, after lasting 3 hours and being warming up to 230 DEG C from 160 DEG C, while utilizing water separator that condensation water is distilled off, while being maintained at 230 DEG C so that it is reaction is until becoming desired acid number。This reaction product adds trimellitic anhydride 20.2 parts, after carrying out additive reaction in 30 minutes at 170 DEG C, it is cooled to less than 50 DEG C, it is neutralized with 2-(dimethylamino) ethanol, it is slowly added deionized water, thus obtains the hydroxyl group containing polyester resin aqueous dispersions (F-1) of solid component concentration 45%。The acid number of the hydroxyl group containing polyester resin obtained is 20mgKOH/g, hydroxyl value be 60mgKOH/g, number-average molecular weight is 1,700。

The making of coating composition

Embodiment 1

Chlorine-free vistanex dispersion liquid (A-1) 35 parts (solid constituent) is coordinated according to conventional method, waterborne polyurethane resin dispersion liquid (B-1) 20 parts (solid constituent), there is the blocked polyisocyanate compound solution (C-1) 20 parts (solid constituent) of nonionic hydrophilic group, hydroxy acryl acid resin solution (E-1) 10 parts (solid constituent), hydroxyl group containing polyester resin (F-1) 15 parts (solid constituent), conductive pigment (D-1) (" Ketjen black EC600J ", Lyons AudioCodes helps Co., Ltd.'s system, trade name, conductive carbon black pigment) 5 parts, " JR-806 " (Tayca company system, trade name, titanium white) 100 parts and mix dispersion, making solid constituent with deionized water dilution is 20%, thus obtaining water-based paint compositions (1)。

Embodiment 2～14 and comparative example 1～7

In embodiment 1, cooperation composition is set as shown in table 2, in addition, obtains each water-based paint compositions (2)～(21) by the operation identical with embodiment 1。

It addition, the cooperation of table 2 represents with solids content, (note 2) in table 2 is as shown in following。

(note 2) watersoluble chlorinated polyolefin (A-3) (aqueous dispersion by the maleic acid modified acid number obtained is 35mgKOH/g and maleic acid modified chlorinated polypropylene that chlorine containing ratio is 22%)

The making of test coated plate

As metal parts, it is 20 μm that cold-rolled steel sheet (450mm × 300mm × 0.8mm) substrates coated heat curable epoxy resin cation electrodeposition coating composition (trade name " ELECRONGT-10 ", Northwest paint company system) processed at zinc phosphate makes thickness, and at 170 DEG C, heating makes it solidify in 30 minutes。

As plastic components, prepare " TSOP-1 (TC-6) " (trade name, Polygem company of Japan system, 350mm × 10mm × 2mm)。

Then, ungrease treatment is carried out with the surface of the gauze wiping metal parts containing petroleum benzin and plastic components。By adjacent to the steel plate as above obtained and polypropylene board configuration, as bread board。

In above-mentioned bread board, coating composition (1)～(21) of the above-mentioned making of spraying coating make dry film thickness be 10 μm, after at room temperature arranging 3 minutes, it is 15 μm that electrostatic applications makes dry thickness as " WBC-713T#1F7 " (trade name, Northwest paint company system, acrylic melamine resin system water-ba sed top coat base coating coating, silver color are tinted) of painted two road primers。Then, it is 30 μm that electrostatic applications makes dry film thickness as " SOFLEX#500CLEAR " (Northwest coating (strain) system, trade name, the acrylic acid urethane system organic solvent type clear dope) of clear dope, after at room temperature placing 5 minutes, the baking oven of 95 DEG C heats 30 minutes, obtains being formed with the test coated plate of multilayer film。This multilayer film is utilized to carry out the various film performances test of the following stated。

Film performance is tested

Polishability: polishability is evaluated by following flatness and distinctiveness。

Flatness: use the W1 value recorded by " WaveScanDOI " (trade name, BYKGardner company system) to be evaluated。W1 value is more little, represents that the flatness in painting face is more high。

Distinctiveness: use the W4 value recorded by " WaveScanDOI " (trade name, BYKGardner company system) to be evaluated。W4 value is more little, represents that the distinctiveness in painting face is more high。

Chipping resistance: (at slungshot testing machine in the test piece holding station of trade name " Q-G-R gravel meter " (QPanel company system), bread board is set, is made granite stones and the 100g bread board collision of granularity 6 at-20 DEG C by the compression air of 480～520kPa from the place of distance test (DT) plate 30cm with the angle of 90 degree。Then, by the bread board washing obtained, dry, be coated with face adhesive fabric adhesive tape (Nichiban Co., Ltd. system)。Then, peel off above-mentioned adhesive tape, be evaluated based on the area (referred to as peeling off area) that electro-deposition face and underlying component are exposed。

S: peel off the area ratio relative to test coated plate area lower than 5%

A: peeling off area relative to the ratio of test coated plate area is 5%～10%

C: peeling off area relative to the ratio of test coated plate area is 10%

Water-fast tack: bread board impregnated 240 hours in the warm water of 40 DEG C, pull out, at 20 DEG C after dry 12 hours, cuts into clathrate to arrive bottom with cutter by the multilayer film of each bread board, makes the gridiron pattern 100 of 2mm × 2mm size。Then, the adhesive tape of laminating bonding in its surface, at 20 DEG C, quickly peel off the Restzustand of adhesive tape " Invest, Then Investigate " gridiron pattern film, according to following benchmark evaluation resistance to water。

S: gridiron pattern film remains 100, the edge in cutter cutting does not produce the less crimping of film

A: gridiron pattern film remains 100, the edge in cutter cutting produces the less crimping of film

B: gridiron pattern film remains 90～99

C: the residual number of gridiron pattern film is less than 89。

Gasohol resistance: illustrate according to parts。

The situation of plastic components: each test coating material impregnated at 20 DEG C in the experimental liquid of gasoline/methanol=90/10 weight ratio, observes the painting surface state of the expansion through 30 minutes time, peeling, evaluates under following benchmark。

S: entirely without abnormal,

The expansion of below A:3mm, peeling,

The expansion of B:3～5mm, peeling,

The expansion of more than C:5mm, peeling,

The situation of metal parts: each test coating material impregnated at 40 DEG C in the experimental liquid of gasoline/methanol=90/10 weight ratio, is observed the painting surface state of the expansion through 60 minutes time, peeling, is evaluated by the benchmark same with the situation of plastics。

[table 2]

Table 2

[table 3]

Table 2 (Continued)

[table 4]

Table 2 (Continued)

Claims

1. a water-based paint compositions, it contains chlorine-free polyolefin-based resins (A), waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D), it is characterized in that, the acid number of waterborne polyurethane resin (B) is 1mgKOH/g～30mgKOH/g, and at the temperature of 20 DEG C time to film forming be 5 minutes～20 minutes。

2. water-based paint compositions according to claim 1, wherein, there is the blocked polyisocyanate compound (C) of nonionic hydrophilic group for having the blocked polyisocyanate compound of at least one blocked isocyanate base in the blocked isocyanate base shown in the blocked isocyanate base shown in following formula (I), following formula (II) and the blocked isocyanate base shown in following formula (III)

[chemical formula 1]

In formula (I), R¹、R²、R⁴And R⁵Represent the alkyl of carbon number 1～12, R independently³Represent the straight-chain of carbon number 1～12 or the alkylidene of branched,

[chemical formula 2]

In formula (II), R²、R³、R⁴And R⁵With above-mentioned R²、R³、R⁴And R⁵It is identical,

[chemical formula 3]

In formula (III), R²、R³、R⁴And R⁵With above-mentioned R²、R³、R⁴And R⁵Identical, R⁶Represent the alkyl of carbon number 1～12。

3. water-based paint compositions according to claim 1, wherein, described water-based paint compositions is possibly together with the acrylic resin of hydroxyl。

4. water-based paint compositions according to claim 1, wherein, with the total resin solid content quality in water-based paint compositions for benchmark, the conductive pigment (D) of chlorine-free polyolefin-based resins (A) containing 10 mass %～60 mass %, the waterborne polyurethane resin (B) of 10 mass %～50 mass %, the blocked isocyanate compounds (C) with nonionic hydrophilic group of 5 mass %～40 mass % and 0.5 mass %～40 mass %。

5. a coating film-forming methods, it is as the water-based paint compositions according to any one of coating Claims 1 to 4 on the metal parts of coated article and plastic components。

6. comprising article for film, described film is by obtaining as the water-based paint compositions according to any one of coating Claims 1 to 4 on the metal parts of coated article and plastic components。