JP2003201439A - Electrically conductive water-based coating for polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically conductive water-based coating for imparting electrical conductivity to plastic materials used for the interior/ exterior trimming of automotive body, to provide a method for coating a polyolefin plastic material with the coating to improve electrostatic coatability on the material and the relevant adhesiveness and the water resistance of the coating film. <P>SOLUTION: The electrically conductive water-based coating is obtained by including (A) an ionically conductive polymer copolymerized with a monomer component containing 5-50 wt.% of a polymerizable monomer having at least one functional group selected from quaternary ammonium salt group, tertiary sulfonium salt group and quaternary phosphonium salt group and (B) an olefin or diene polymer modified with a polymerizable unsaturated dicarboxylic acid or its anhydride, and, as necessary (C) a polyurethane resin and/or (D) a curing agent. The method for coating a polyolefin plastic material with the coating comprises coating the material with the coating followed by a topcoating. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic material used for interiors and exteriors of automobile bodies, especially in recent years.
A conductive water-based paint for imparting conductivity to a polyolefin-based plastic material that is widely used because it is advantageous for recycling, and a method for coating a polyolefin using the conductive water-based paint. And improving the adhesion and water resistance of the coating film.

[0002]

2. Description of the Related Art Since the volume specific electric resistance of a polyolefin plastic material used for the interior and exterior of an automobile body is usually 10 ¹⁰ Ω · cm or more, an electrostatic coating method is applied to this material. Therefore, it is difficult to apply the paint directly. Therefore, when the paint is electrostatically applied to these materials, a conductive primer for forming a conductive coating film is applied in advance.

Conventionally, as a conductive primer, a conductive carbon-containing coating, a coating containing a conductive filler formed by coating the surface of pigment particles such as titanium white, mica, and potassium titanate with SnO ₂ or Sb, and A paint containing an ion conductive polymer having a functional group selected from a quaternary ammonium base, a tertiary sulfonium base and a quaternary phosphonium base has been proposed.

However, the conductive carbon-containing paint forms an inexpensive and stable conductive coating film, but the coating color is limited to black or gray, so that the white color which is increasing as the color of the outer panel of the automobile. It is difficult to apply to a primer for finishing high-saturation red-yellow pearl mica color. Further, the coating material containing the conductive filler is not limited in terms of coating color, but it is expensive and S
The toxicity of b and the whisker type are regarded as problems such as safety to the human body. A coating material containing an ion conductive polymer forms a colorless and transparent coating film and is relatively inexpensive, but has a fatal defect that the water resistance of the coating film is not sufficient.

[0005]

The object of the present invention is to eliminate the above-mentioned various defects, and in particular to improve the water resistance of a coating film in a coating material containing an ion conductive polymer, As a result of earnest research, an ion conductive polymer having one or more functional groups selected from a quaternary ammonium base, a tertiary sulfonium base and a quaternary phosphonium base is modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof. The water-based paint prepared by mixing the olefin-based or diene-based polymer described above is nontoxic, safe, has excellent conductivity, is relatively inexpensive, forms a colorless and transparent coating film, and has a water resistance of the coating film. They have found that they can be improved and have completed the present invention.

That is, according to the present invention, 5 to 50 parts by weight of (A) a polymerizable monomer having at least one functional group selected from a quaternary ammonium salt group, a tertiary sulfonium salt group and a quaternary phosphonium salt group. % Of an olefin-based or diene-based polymer modified by a polymerizable unsaturated dicarboxylic acid or its anhydride, and (A) ), (B) The ratio of both components is (A) based on the total solid weight of both components.
Provided is a conductive water-based coating material for polyolefin (hereinafter, referred to as "present coating material 1"), which comprises 10 to 80% of component and 90 to 20% by weight of component (B).

Furthermore, the present invention contains (A) 5 to 50% by weight of a polymerizable monomer having at least one functional group selected from quaternary ammonium base, tertiary sulfonium base and quaternary phosphonium base. Containing an ion-conductive polymer obtained by copolymerizing a monomer component, (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof, and (C) a polyurethane resin. And the ratio of both components (A) and (B) is 10 to 80% of the component (A) and 9 of the component (B) based on the total solid content weight of the both components.
0 to 20% by weight, and the ratio of the component (C) is 1 to 1 per 100 parts by weight of the total solid content of the components (A) and (B).
Provided is a conductive water-based paint for polyolefin (hereinafter, referred to as "present paint 2"), characterized in that it is 100 parts by weight.

Furthermore, the present invention provides a conductive water-based paint for polyolefin (hereinafter referred to as "main paint 3"), characterized in that the main paint 1 or main paint 2 further contains (D) a curing agent. Include.

Further, the present invention is a coating method of polyolefin (hereinafter referred to as "this method") characterized in that the above-mentioned main coating material 1, 2 or 3 is applied to a polyolefin plastic material, and then a top coating material is applied. Also includes.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The "present paints 1, 2 and 3" and the "present method" will be described in detail below.

The present coating material 1: (A) quaternary ammonium salt base,
5 to 5 polymerizable monomers having one or more functional groups selected from tertiary sulfonium base and quaternary phosphonium base are used.
An ion-conductive polymer obtained by copolymerizing 0% by weight of a monomer component and (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof, and The ratio of both components (A) and (B) is from 10 to 80 based on the total solid weight of both components.
%, The component (B) is 90 to 20% by weight, which is a conductive aqueous coating material for polyolefin. By using the component (A) and the component (B) together,
As compared with the component (A) alone, the water resistance could be significantly improved without lowering the conductivity of the coating film.

Component (A) is a quaternary ammonium base, 3
A polymerizable monomer having at least one functional group selected from a quaternary sulfonium base and a quaternary phosphonium base is added in an amount of 5 to 50.
It is an ion conductive polymer obtained by copolymerizing a monomer component contained in a weight percentage.

Specifically, a monomer having at least one functional group selected from a quaternary ammonium base, a tertiary sulfonium base and a quaternary phosphonium base in the same molecule and a polymerizable double bond (hereinafter, It can be obtained by copolymerizing “a functional monomer”) with another monomer having a polymerizable double bond.

The functional monomer has at least one functional group selected from a quaternary ammonium base, a tertiary sulfonium base and a quaternary phosphonium base and a polymerizable double bond in the same molecule. It is a monomer to have, and it is preferable that these functional groups and polymerizable double bonds are bonded to both ends of the molecule.

Examples of the quaternary ammonium salt group-containing monomer include compounds represented by the following formula (1).
Examples thereof include quaternary dimethylaminoethyl acrylate, quaternary dimethylaminoethyl methacrylate, quaternary diethylaminoethyl acrylate, quaternary diethylaminoethyl methacrylate and quaternary dimethylaminostyrene.

Formula (1): CH ₂ ═CH (or CH ₃ ) C (O) O—R ₁ N ⁺ (R
₂ ) (R ₃ ) R ₄ X ⁻ (wherein R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, and X ⁻ is a sulfonate ion or a phosphonate. ion, _BF ⁴ -, As
F ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , Br ⁻ , I ⁻ , Cl ⁻ , RC
OO ⁻ (R is an alkyl group having 1 to 20 carbon atoms), C ₆ H ₆
〇 ^-, ClO ₄ ^- and is)

Examples of the tertiary sulfonium base-containing monomer include compounds represented by the following formula (2).
Examples thereof include tertiary chloride of 4- (dimethylsulfonio) phenyl methacrylate.

Formula (2): CH ₂ ═CH (or CH ₃ ) C (O) O—R ₄ S ⁺ (R
₅ ) (R ₆ ) X ⁻ (wherein, R ₅ and R ₆ are alkyl groups having 1 to 20 carbon atoms,
Phenyl group, a benzyl group, X ^- is as defined above)

Examples of the quaternary phosphonium base-containing monomer include compounds represented by the following formula (3).
Examples thereof include quaternary chloride of orthophosphoric acid hydroxyethyl methacrylate monoester and triphenylphosphonioethyl methacrylate quaternary chloride.

Formula (3): CH ₂ = CH (or CH ₃ ) C (O) O-R ₇ P ⁺ (R
₈ ) (R ₉ ) R ₁₀ X ⁻ (in the formula, R ₇ , R ₈ , R ₉ and R ₁₀ are the same as the above-mentioned alkyl groups having 1 to 20 carbon atoms, phenyl groups, benzyl groups and X ⁻ )

The other monomer is a compound having at least one polymerizable double bond in one molecule which can be copolymerized with the above functional monomer, and examples thereof include the compounds shown below.

1) Methyl (meth) acrylate, (meth)
Ethyl acrylate, n-propyl (meth) acrylate,
Isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Lauryl acid, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and the like, alkyl or cycloalkyl esters of acrylic or methacrylic acid having 1 to 24 carbon atoms: methoxybutyl (meth) acrylate,
C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxyethyl (meth) acrylate and ethoxybutyl (meth) acrylate.

2) C2 to C8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate;
Polyethylene glycol, polypropylene glycol,
Monoesters of polyether polyols such as polybutylene glycol and unsaturated carboxylic acids such as acrylic acid or methacrylic acid; polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and 2-hydroxyethyl (meth) acrylate Monoether with a hydroxyl group-containing unsaturated monomer; α, β-unsaturated carboxylic acid and cardura E1
0 (manufactured by Shell Chemical Co., Ltd.), an adduct with a monoepoxy compound such as α-olefin epoxide; glycidyl (meth)
Addition products of acrylates with monobasic acids such as acetic acid, propionic acid, pt-butylbenzoic acid, and fatty acids; unsaturated compounds containing an acid anhydride group such as maleic anhydride and itaconic anhydride, and ethylene glycol, hexanediol , Mono- or di-esterified products with glycols such as neopentyl glycol; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 3-
Chlorine-containing hydroxy group-containing monomer such as chloro-2-hydroxypropyl (meth) acrylate, allyl alcohol
A hydroxyl group-containing polymerizable monomer such as ruthenium.

3) Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, etc. The carboxyl group-containing polymerizable monomer.

4) Glycidyl group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether.

5) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
1,4-butanediol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, glycerol ant Roxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxyme) 2) Polymerization of two or more in one molecule such as ethanetri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, and divinylbenzene. Polyvinyl polymerizable monomer having a polyunsaturated bond.

6) Aromatic polymerizable monomers such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene.

7) Nitrogen-containing alkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and Nt-butylaminoethyl (meth) acrylate; acrylamide , Methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N
-Methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide And other polymerizable amides; 2
-Vinyl pyridine, 1-vinyl-2-pyrrolidone, 4-
Aromatic nitrogen-containing monomers such as vinylpyridine, polymerizable nitriles such as acrylonitrile and methacrylonitrile; nitrogen-containing polymerizable monomers such as allylamine.

The component (A) is the above-mentioned "functional monomer".
It can be obtained by copolymerizing the monomer with another monomer, and this copolymerization reaction is preferably performed by a known solution polymerization method or the like. The ratio of the functional monomer to the other monomer in the copolymerization reaction is 5 to 50% by weight, particularly 2 to 50% by weight, based on the total weight of both monomers.
0-40% by weight, the ratio with other monomers is 95-50
It is preferably within the range of 80% by weight, particularly 80 to 60% by weight. The weight average molecular weight of the component (A) obtained by this copolymerization reaction is 2000 to 100,000, and particularly 5,000 to 5
The range of 0000 is preferable. If the content of the functional monomer is less than 5% by weight, the electrical conductivity of the coating film of the present coating composition 1 is lowered, while if it is more than 50% by weight, the water resistance of the coating film is reduced, which is not preferable.

The component (B) is an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or its anhydride. Specifically, the component (B) can be prepared by graft-polymerizing a polymerizable unsaturated dicarboxylic acid or an anhydride thereof onto an olefin-based or diene-based polymer by a known method.

As the olefin-based or diene-based polymer before graft polymerization, for example, (co) polymerization of at least one olefin-based or diene-based monomer selected from ethylene, propylene, butadiene, isoprene and butadiene is carried out. And a polymer obtained by copolymerizing these olefin-based or diene-based monomers with other monomers (for example, styrene, acrylonitrile, etc.). Specifically, polypropylene, ethylene / propylene copolymer, ethylene / propylene / butadiene copolymer, polybutadiene, styrene / butadiene block copolymer and hydrogenated product thereof, polyisoprene, isoprene / styrene block copolymer and its Examples include hydrogenated products. The weight average molecular weight of these olefin-based or diene-based polymers is preferably 30,000 to 150,000, and particularly preferably 50,000 to 120,000.

The polymerizable unsaturated dicarboxylic acid or its anhydride used for modifying the olefin or diene polymer is 1
A compound having one polymerizable unsaturated bond and two or more carboxyl groups or its acid anhydride group in the molecule, such as maleic acid and its anhydride, itaconic acid and its anhydride, citraconic acid and its anhydride. And the like, and one or more selected from these can be preferably used.

The graft polymerization reaction of the polymerizable unsaturated dicarboxylic acid or its anhydride onto the olefin-based or diene-based polymer can be carried out by a known method. The ratio of the polymerizable unsaturated dicarboxylic acid or the anhydride thereof is such that the saponification value of the resulting modified olefin-based or diene-based polymer is 1
0-60mgKOH / g, especially 20-50mgKOH / g
The degree of inclusion within the range of g is preferable.

The olefin-based or diene-based polymer contained in the component (B) may be chlorinated, and this chlorination can be carried out before or after the graft polymerization.
The degree of chlorination is preferably within the range of 0 to 30% by weight, particularly 15 to 25% by weight based on the olefin-based or diene-based polymer before graft polymerization.

Further, in order to facilitate the water-solubilization or water-dispersion of the component (B), it is preferable to neutralize a part or all of the carboxyl contained in the molecule with an amine compound. As amine compounds, tertiary amines such as triethylamine, tributylamine, dimethylethanolamine and triethanolamine; 2 such as diethylamine, dibutylamine, diethanolamine and morpholine
Primary amine; 1 such as propylamine and ethanolamine
Examples include primary amines. It is also possible to use a surfactant together with these amine compounds for water-solubilization or water-dispersion.

The coating composition 1 can be obtained by mixing the above-mentioned components (A) and (B) with water, and the ratio of both components is (A) based on the total solid content weight of both components. ) Component is 10 to 80%, particularly preferably 20 to
70% by weight, component (B) is 90 to 20% by weight, particularly preferably 80 to 30% by weight.

In addition to these components (A) and (B), the coating composition 1 further comprises solid color pigments, metallic pigments, light interference pigments, extender pigments, anti-settling agents, organic solvents, coating additives. And the like can be appropriately mixed.

Main coating 2: (A) quaternary ammonium salt base,
5 to 5 polymerizable monomers having one or more functional groups selected from tertiary sulfonium base and quaternary phosphonium base are used.
Ion conductive polymer obtained by copolymerizing 0% by weight of a monomer component, (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof, and (C) polyurethane Contains a resin, and (A),
(B) The ratio of both components is 10 to 80% of the component (A) and 90 to 20 of the component (B) based on the total solid content weight of the both components.
% By weight, and the ratio of (C) component is (A) component and (B)
It is 1-100 weight part per 100 weight part of total solids with a component, It is an electroconductive aqueous coating material for polyolefins characterized by the above-mentioned.

By adding a polyurethane resin (C) in addition to the components (A) and (B), the performance of the coating film formed, such as the adhesion to the coated surface and the top coating film, is improved. be able to.

Containing 5 to 50% by weight of (A) a polymerizable monomer having at least one functional group selected from quaternary ammonium salt group, tertiary sulfonium salt group and quaternary phosphonium salt group used in the present coating composition 2. As the ionic conductive polymer formed by copolymerizing the monomer component and (B) the olefin-based or diene-based polymer modified with the polymerizable unsaturated dicarboxylic acid or the anhydride thereof, Since the explained component (A) and component (B) can be used in the same manner,
The description will not be repeated.

The component (C) is a polyurethane resin, and a hydrophilic polyurethane resin which can be dissolved or dispersed in water can be preferably used.

Examples of such hydrophilic polyurethane resin include (i) aliphatic and / or alicyclic diisocyanate,
(Ii) a diol having a number average molecular weight of 500 to 5000, (i
ii) a low molecular weight polyhydroxyl compound and (iv) a urethane prepolymer obtained by reacting a one-shot or a multi-stage method with dimethylolalkanoic acid can be obtained by neutralizing or elongating while emulsifying while neutralizing the urethane prepolymer, In particular, an aqueous dispersion of a self-emulsifying urethane resin having an average particle diameter of about 0.001 to 1.0 μm obtained by distilling off part or all of the organic solvent used in the manufacturing process is preferable.

(I) Aliphatic diisocyanates and alicyclic diisocyanates include aliphatic diisocyanates having 2 to 12 carbon atoms, such as hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate and lysine diisocyanate; 18 cycloaliphatic diisocyanates, for example 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4
Examples include ′ -dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate; modified products of these diisocyanates (carbodiimide, uretdione, uretoimine, etc.) and the like.

(Ii) As the diol having a number average molecular weight of 500 to 5000, preferably 1000 to 3000, for example, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ether (tetrahydrofuran, etc.) is polymerized. Or a polyether diol obtained by copolymerization (block or random), specifically, polyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, poly Octamethylene ether glycol, etc .;
Dicarboxylic acids (adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol, neopentyl glycol, bishydroxymethylcyclohexane, etc.)
A polycondensed polyester diol with, specifically,
Examples thereof include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, and polyneopentyl / hexyl adipate. In addition, polylactone diols such as polycaprolactone diol, poly-
3-Methylvalerolactone diol; polycarbonate diol and the like can be applied.

(Iii) The low molecular weight polyhydroxyl compound is a compound having a number average molecular weight of less than 500,
For example, glycols and their alkylene oxide low-molar adducts (molecular weight less than 500) listed as the raw materials for the above polyester diols; trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and their alkylene oxide low-molar adducts (molecular weight 50
Less than 0); and mixtures of two or more thereof. The amount of the low molecular weight polyhydroxyl compound is as described in (ii) above.
0.1 to 20% by weight, preferably 0.
It is 5 to 10% by weight.

(Iv) As dimethylolalkanoic acid,
Examples thereof include dimethylol acetic acid, dimethylol propionic acid, and dimethylol butyric acid. The content of dimethylolalkanoic acid is such that the content as a carboxyl group (—COOH) is 0.5 to 5% by weight, preferably 1 to 3% by weight in the urethane prepolymer obtained by reacting (i) to (iv). A suitable amount is%.

These (i) to (iv) are a part of the carboxyl groups introduced by dimethylolalkanoic acid contained in the urethane prepolymer obtained by the reaction by a known method by a one-shot method or a multi-step method, or It is preferable to neutralize all with an amine compound in order to facilitate water-solubilization or water-dispersion of the component (C). As amine compounds, triethylamine, tributylamine, dimethylethanolamine, triethanolamine, etc. 3
Examples include secondary amines such as diethylamine, dibutylamine, diethanolamine and morpholine; primary amines such as propylamine and ethanolamine. The neutralization amount of the amine is usually 0.5 to 1 equivalent, preferably 0.7 to 1 equivalent based on 1 equivalent of the carboxyl group of dimethylolalkanoic acid.

As the component (C) used in the present coating composition 2, it is preferable to use one having specific physical properties. That is, a single coating film of this component (C) is poured with acetic acid.
Tensile strength of the sample after soaking in water adjusted to H4.0 (temperature 80 ° C) for 2 hours, drying at 130 ° C for 1 hour, and then standing for 200 hours in a humidity oven at 70 ° C and 95% humidity It is preferable to use a material in which the rate of change in elongation is within a reduction rate of 25% as compared with those before the test and no reduction in whitening is visually observed. Commercially available polyurethane resins having such characteristics include, for example,
"Takelac w610" (Takeda Pharmaceutical Co., Ltd., trade name), "Neolets R960" (Zenecare Resin Co., Ltd.)
Trade name), "U-Coat UWS-145" (manufactured by Sanyo Chemical Industry Co., Ltd., trade name) and the like.

The main coating material 2 is composed of the above-mentioned components (A) and (B).
It is a conductive water-based coating material for polyolefin containing the component and the component (C), which can be obtained by mixing these with water. The composition ratio of each of these components is
The component (A) is 10 to 80%, particularly preferably 20 to 70, based on the total solid weight of the components (A) and (B).
%, The component (B) is 90 to 20% by weight, particularly preferably 80 to 30% by weight, and the component (C) is 1 to 100 parts by weight of the total solid content of the components (A) and (B). 10
0 parts by weight, particularly preferably 20 to 90 parts by weight.

In addition to these components, the present paint 2 may further contain solid color pigments, metallic pigments, light interference pigments, extender pigments, anti-settling agents, organic solvents, paint additives and the like. .

The present coating composition 3 comprises (A) 5 parts of a polymerizable monomer having at least one functional group selected from quaternary ammonium base, tertiary sulfonium base and quaternary phosphonium base.
A polymer containing an ion-conductive polymer obtained by copolymerizing a monomer component containing 50 to 50% by weight and (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof. Conductive water for polyolefin, characterized in that the coating material 1 or the main coating material 2 in which the component (A) and the component (B) contain a component (C) polyurethane resin, and a component (D) a curing agent. It is paint.

The component (D) is the component (A),
A curing agent used for three-dimensionally cross-linking and curing the coating film of the present paint 1 and the present paint 2 by a crosslinking reaction with one or more selected from the components (B) and (C). is there. Thus, the coating film formed by the main coating material 3 which has been crosslinked and cured has excellent conductivity and water resistance, and can also have improved water resistance, chemical resistance and the like.

A crosslinkable functional group such as a hydroxyl group and a carboxyl group can be introduced into the component (A), and the components (B) and (C) have a carboxyl group in the molecule. A compound capable of reacting with the group can be used as the component (D).

As the component (D), for example, one or more selected from melamine resin, epoxy resin, carbodiimide resin and the like can be preferably used.

The melamine resin is effective for cross-linking and curing the component (A) containing a hydroxyl group, and specifically, a methylolated melamine resin obtained by reacting melamine with formaldehyde, and further having 1 to 10 carbon atoms. A portion obtained by reacting a monoalcohol or a full-etherified melamine resin can be used. As these melamine resins, those having an imino group can also be used. These may be either hydrophobic or hydrophilic, but in particular, the number average molecular weight of 3 which is etherified with methanol and has a low degree of condensation is 3
000 or less, especially 100 to 1500 hydrophilic melamine resin is suitable. Examples of commercially available products of such hydrophilic melamine resin include "Cymel 303" and "Cymel 325".
(Both products are manufactured by Cytec Co., Ltd., etc.).

The epoxy resin is a resin having two or more epoxy groups in one molecule and is effective in crosslinking and curing the (A) component, (B) component and (C) component containing a carboxyl group. . Specifically, a copolymer of an epoxy group-containing polymerizable monomer and a vinyl polymerizable monomer can be mentioned. Examples of the epoxy group-containing polymerizable monomer include glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, and methylglycidyl methacrylate. The vinyl-based polymerizable monomer is
Other than the epoxy group-containing polymerizable monomer, for example,
Examples include (meth) acrylic acid alkyl ester, acrylonitrile, styrene, vinyl acetate, vinyl chloride and the like. The copolymerization reaction with these monomers can be carried out by a known method, and the resulting polymer has an epoxy equivalent of 20.
~ 2800, especially 30-700, number average molecular weight 300
The range of 0 to 100,000, particularly 4000 to 50,000 is preferable. Further, a glycidyl etherified epoxy resin of bisphenol, a hydrogenated product thereof, a glycidyl etherified epoxy resin of an aliphatic polyhydric alcohol, a glycidyl ester type epoxy resin, an alicyclic epoxy resin and the like can also be used as a crosslinking agent. The molecular weight of these epoxy resins is preferably in the range of 500 to 20000, particularly 800 to 5000.

The carbodiimide resin can be obtained, for example, by subjecting the isocyanate groups of a polyisocyanate compound to a carbon dioxide deoxidation reaction, and as commercially available products, "carbodilite E-01" and "carbodilite E-02" ( The Nisshinbo Co., Ltd. product name etc. are mentioned.

The present paint 3 is a conductive water-based paint for polyolefin containing the above-mentioned components (A), (B), (C) and (D) curing agent. By mixing these with water, Obtainable.

The constituent ratios of these components in the paint 3 can be arbitrarily selected according to the purpose. For example, the ratio of the component (A) to the component (B) is such that the component (A) is 10 to 80% by weight, particularly preferably 20 to 70% by weight, based on the total solid content weight of these two components, (B). 90 to 20% by weight of ingredients,
It is particularly preferably 80 to 30% by weight, and the ratio of the component (C) is 1 to 100 parts by weight, and particularly preferably 20 to 9 per 100 parts by weight of the total solid content of the components (A) and (B).
0 parts by weight. The component (D) is 1 to 10 per 100 parts by weight of the total solid content of the components (A) and (B).
0 parts by weight, particularly preferably 20 to 90 parts by weight.

In addition to these components, the present paint 3 may further contain solid color pigments, metallic pigments, light interference pigments, extender pigments, antisettling agents, organic solvents, paint additives and the like. .

The paints 1, 2 and 3 are plastic materials used for interiors and exteriors of automobile bodies, especially polyolefin-based plastic materials often used because of their excellent recyclability, such as polypropylene resin and ethylene.・ Conductivity for imparting conductivity to the surface of automobile parts such as bumpers, fenders, door under parts, etc. formed by molding and processing propylene resin, ethylene propylene diene resin, ethylene olefin resin, etc. Effective as a water-based paint (primer).

The viscosity of the paints 1, 2 and 3 was adjusted to 10 to 30 seconds / Ford cup # 4/20 ° C., and the above plastic automobile parts were spray-painted, airless spray paint, brush paint, dip paint, etc. Can be applied by the method of. The coating thickness is 1-30 based on the cured coating
μm, particularly 5 to 20 μm is preferable. With respect to the coating films thus coated, the coating films of the main coatings 1 and 2 are dried at room temperature and by heating (room temperature to about 140 ° C.) to form a dry coating film. Since the film contains a curing agent, when it is heated to 60 to 140 ° C., a three-dimensionally cross-linked cured film is formed.

The present method relates to a method for coating a polyolefin, which comprises coating the above-mentioned main paint 1, 2 or 3 on a polyolefin plastic material and then applying a top coat paint.

The polyolefin-based plastic material and the main coating material 1, 2 or 3 in the present method have already been described above, and those selected from these can be preferably used in the present method. That is, since the surface of the polyolefin plastic material coated with the main coating materials 1, 2 and 3 as described above has conductivity, the top coating material can be electrostatically coated on the surface.

As the top coating material, one known per se can be used. Specific examples include acrylic resin / melamine resin-based, acrylic resin / (block) polyisocyanate compound-based clear coatings, solid color coatings, metallic coatings, and light interference coatings. The form of these top coating materials is not particularly limited, and examples thereof include organic solvent type, aqueous solution type, water dispersion type, and high solid type. The coating film is dried and cured at room temperature, heating, irradiation with active energy rays, etc. be able to. Top coat is a single layer or 2
It is a multi-layer coating film of more than one layer.

By this method, in the polyolefin-based plastic material coated with the main coating material 1, 2 or 3 and the top coating material, the electrostatic coating property of the top coating material is good and the finished appearance such as the smoothness of the top coating surface is excellent. In addition, the adhesion between the polyolefin plastic material, the coating film of the present paint 1, 2 or 3 and the top coating film is good, and the water resistance is also excellent.

[0067]

EFFECTS OF THE INVENTION The paints 1, 2 and 3 contain (A) a polymerizable monomer having at least one functional group selected from quaternary ammonium base, tertiary sulfonium base and quaternary phosphonium base. An ion-conductive polymer obtained by copolymerizing a monomer component contained in an amount of ˜50 wt% and (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof ( This paint 1), and if necessary, (C) polyurethane resin (this paint 2), (D)
A conductive water-based paint for polyolefins, characterized in that it contains a curing agent (present paint 3). The surface resistance of the coating film formed by these main paints is 60% humidity,
Since it has a conductivity of 10 ⁸ Ω / □ or less,
The top coating can be easily applied to the coating surface by the electrostatic method, and the water resistance is good, and the smoothness of the coating surface after the top coating is excellent.

Furthermore, since the coating films formed by the present coating materials 1, 2 and 3 are colorless and transparent, it is possible to color them in a desired color tone, and it is possible to use a top coating material of any color tone. became.

Further, the coating films of the present coating materials 1, 2 and 3 also have the effect that they have good adhesion to the polyolefin to be coated and the top coating film. In addition, tin oxide,
It is cheaper, safer, and less toxic than conventional paints containing an Sb-coated conductive agent and the like, which is advantageous in terms of commerciality and economy in industrial use.

[0070]

EXAMPLES Examples and comparative examples relating to the present invention will be described below. All parts and% are based on weight, and the film thickness of the coating film is that of the dried and cured coating film.

1. Preparation of sample (A) Component (A-1): quaternary chloride of methyl methacrylate / n-butyl acrylate / hydroxyethyl acrylate / dimethylaminoethyl methacrylate = 40/20/1
An ion conductive resin (weight average molecular weight 23000) obtained by copolymerizing a monomer component composed of 5/25 (weight ratio).

(A-2): Copolymerization of a monomer component consisting of methyl methacrylate / ethyl acrylate / 4- (dimethylsulfonio) phenyl methacrylate tertiary chloride = 40/25/35 (weight ratio) Ion conductive resin (weight average molecular weight 18,000).

(A-3): A monomer component consisting of quaternary chloride of methyl methacrylate / ethyl acrylate / hydroxyethyl acrylate / triphenylphosphonioethyl methacrylate = 40/20/10/30 (weight ratio) is used together. Ion conductive resin formed by polymerization (weight average molecular weight 21,000).

(A-4): (For comparison) Methyl methacrylate / n-butyl acrylate / hydroxyethyl acrylate / quaternary chloride of dimethylaminoethyl methacrylate = 5/20/15/60 (weight ratio) An ion conductive resin (weight average molecular weight 23000) obtained by copolymerizing body components.

(A-5): (For comparison) "Aquapass 5%
Aqueous solution "(trade name, manufactured by Mitsubishi Rayon Co., Ltd., aqueous solution of polyaniline-based conductive resin).

Component (B) (B-1): 500 parts of maleated chlorinated polypropylene having a weight average molecular weight of 80,000 (chlorine content 22%, maleic acid modification 2.0%, saponification number 30 mgKOH / g),
A mixture (50 ° C.) consisting of 150 parts of n-heptane and 50 parts of N-methyl-vinylpyrrolidone, 12 parts of dimethylethanolamine and Neugen EA-140 (nonionic surfactant, manufactured by Dai-Ichi Kogyo Co., Ltd., product) Name) 5 parts and after stirring for 1 hour at the same temperature, deionized water 2000
Parts were gradually charged, and the mixture was further stirred for 1 hour. Next, the pressure was reduced at a temperature of 70 ° C., and a total of 600 parts of n-heptane and water was distilled off to obtain a polyolefin emulsion having a solid content rate of 23.6%. The average particle size of the resin particles was 1.8 μm.

Component (C) (C-1): “Takelac W610” (trade name, aqueous polyurethane resin manufactured by Takeda Pharmaceutical Co., Ltd.).

Component (D) (D-1): “Cymel 325” (Cytec Corporation)
(Product name, water-soluble melamine resin).

(D-2): "Carbodilite E-01"
(Nisshinbo Co., Ltd., trade name, aqueous carbodiimide resin).

Others (E-1): methyl methacrylate / butyl acrylate / 2-ethylhexyl methacrylate / hydroxyethyl acrylate / acrylic acid = 40/20/20/5
A water-soluble acrylic resin (weight average molecular weight 12000) obtained by copolymerizing a monomer component of / 5 (weight ratio).

Titanium white pigment: "Taipaque CR-93"
(Product name of Ishihara Sangyo Co., Ltd.) 2. Examples and Comparative Examples Using the above components, the respective components were mixed in the ratios (weight and solid content ratios) shown in Table 1 to obtain main paints 1, 2, 3 and a comparative paint.

These conductive water-based paints were applied to the surface of the polyolefin material (“TX-933” manufactured by Nippon Polychem Co., Ltd., trade name) by air spray coating. The coating film thickness was 10 to 15 μm, and the coating film was allowed to stand at room temperature for 3 minutes and then forcedly dried at 80 ° C. for 10 minutes.

On the coated surface, "Soflex # 420 Silver" (manufactured by Kansai Paint Co., Ltd., trade name, polyester urethane-based one-component organic solvent-based metallic coating) as a top coating has a film thickness of 15 to 20 μm. Electrostatic coating like this, leave it at room temperature for 3 minutes, and then touch "Soflex # 52
0 clear "(Kansai Paint Co., Ltd., trade name, acrylic urethane two-component organic solvent-based clear paint) with a film thickness of 25-
It was electrostatically coated to a thickness of 30 μm, left at room temperature for 5 minutes, and then heated at 100 ° C. for 30 minutes to cure the coating film.

The performance test of the multilayer coating film thus formed was conducted, and the results are also shown in Table 1. The test method is as follows.

Appearance: The presence or absence of abnormalities such as spots, dents, blisters, and coloring on the coated surface was visually evaluated. ○ indicates that these abnormalities were not observed at all, Δ indicates that these abnormalities were slightly observed, and × indicates that these abnormalities were significantly observed.

Surface electric resistance value: This is the result of measuring the surface electric resistance value of the coated surface by TREK's trade name "MODEL 150" after coating this coating material and drying the coating film at 80 ° C for 10 minutes. If the measured value is less than 10 ⁹ Ω / □, the electrostatic coating is appropriate.

Adhesiveness: 100 pieces of 2 mm wide burdock stitches were cut by a cutter so as to reach the substrate, adhesive cellophane tape was adhered to the surface thereof, and the number of burdock stitch coating films left after sudden peeling at 20 ° C. Was observed.

Water resistance test: After being immersed in warm water of 40 ° C. for 10 days, the appearance (whether whitening, blistering, etc. were generated) immediately after pulling up and the adhesion (the same as above) were evaluated. Appearance ○
Indicates that whitening and blistering did not occur, Δ indicates that whitening and blistering occurred a little, and X indicates that whitening and blistering occurred frequently. The evaluation of adhesion is the same as above.

[0089]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J038 CA101 CA102 CB141 CB142                       CC091 CC092 CG011 CG012                       CG031 CG032 CG141 CG142                       CH031 CH032 CH041 CH042                       CH111 CH112 CH121 CH122                       CH201 CH202 CH261 CH262                       CP031 CP032 CP081 CP082                       DA162 DG002 GA06 GA08                       GA13 GA14 KA08 NA04 PA03                       PA19 PB03 PB07 PC08

Claims (4)

[Claims] 1. A monomer containing 5 to 50% by weight of (A) a polymerizable monomer having at least one functional group selected from quaternary ammonium base, tertiary sulfonium base and quaternary phosphonium base. An ion-conductive polymer obtained by copolymerizing components and (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof, and both (A) and (B) The ratio of the components is 10 to 80% of the component (A) based on the total solid content weight of the both components, (B)
A conductive water-based coating material for polyolefin, characterized in that its content is 90 to 20% by weight. 2. A monomer containing 5 to 50% by weight of (A) a polymerizable monomer having at least one functional group selected from a quaternary ammonium base, a tertiary sulfonium base and a quaternary phosphonium base. An ion conductive polymer obtained by copolymerizing components, (B) an olefin-based or diene-based polymer modified with a polymerizable unsaturated dicarboxylic acid or an anhydride thereof, and (C)
Contains polyurethane resin, and the ratio of both components (A) and (B) is 10 to 80% of component (A) and 90 to 20% by weight of component (B) based on the total solid weight of both components. The ratio of the component (C) is 1 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (A) and (B), and the conductive water-based coating material for polyolefin. 3. The water-based paint according to claim 1 or 2, further comprising (D)
A conductive water-based paint for polyolefins, characterized by containing a curing agent. 4. A method for coating a polyolefin, which comprises coating the polyolefin-based plastic material with the water-based coating composition according to claim 1, 2 or 3, and then coating a top coating composition.