JP2000017222A - Coating resin composition and coating composition using this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating resin composition which shows a high adhesion against plastic substrates which are not subjected to a physical or chemical pretreatment, solvent resistance, coating hardness and shelf stability and has a good pigment dispersibility. SOLUTION: This composition comprises (A) a chlorinated polyolefin resin with a chlorine content of 50 wt.% or smaller, (B) a chlorinated polyolefin- containing polymer obtained by heating a mixture of a radical polymerizable monomer containing from 10 to 80 wt.% chlorinated polyolefin resin with a chlorine content of 50 wt.% or smaller and a chlorinated polyolefin resin with an organic solvent and a radical polymerization initiator and (C) an acrylic resin wherein the weight average molecular weight, calculated as polystyrene, is from 3,000 to 40,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating resin composition and a coating composition using the same, particularly to a plastic substrate such as a polyolefin, even if it is not subjected to a primer treatment, and to an adhesive property and a solvent resistance. The present invention relates to a coating resin composition having excellent performance such as excellent pigment dispersibility and a coating composition using the resin composition.

[0002]

2. Description of the Related Art As a conventional technique, for example, in the fields of automobile interior parts, home electric appliances, office supplies and the like, the use of plastic instead of metal has been increasing for the purpose of weight reduction, rust prevention and other purposes. Above all, the use of polyolefin resins such as polyethylene and polypropylene is expanding due to their characteristics such as moldability, light weight, low cost, and recyclability.

[0003]

However, in the prior art, polyolefin resins generally have high crystallinity and low polarity, and therefore have the disadvantage that paints, inks, adhesives, etc. are difficult to adhere to. I have.

[0004] In order to solve such a drawback, some pretreatment is conventionally performed at the time of painting, printing, or bonding. Specific examples include physical treatment such as polishing, chemical treatment with a chromic acid mixed solution, a solvent, and the like, and treatment with plasma and corona discharge.These pretreatment steps require equipment, Depending on the shape of the coating material, there are problems such as inability to uniformly process and cost increase.

Various primers having good adhesion to a polyolefin-based substrate have been proposed, but the coating properties such as interlayer adhesion to a top coat and weather resistance are insufficient, and the practicality is poor.

[0006] adhesion to polyolefin materials,
Solvent resistance, as a coating resin composition having improved coating properties such as hardness, a resin composition comprising a chlorinated polyolefin and an acrylic polymer is known, such a resin composition is as follows Have a serious problem.

The chlorination rate of chlorinated polyolefin is 50
When the content is more than 20% by weight, the compatibility with the acrylic copolymer is improved, but the adhesion of the coating film is reduced. When the content is less than 20% by weight, the adhesion of the coating film is good. Have extremely poor compatibility, and practical use of both is difficult.

From these facts, the chlorine content of the chlorinated polyolefin is considered appropriate in the range of 25 to 35% by weight. However, since the two components are basically incompatible with each other, the storage stability at low temperatures and the like are low. Problems remained, and it was difficult for practical use.

On the other hand, as a method for further improving the compatibility between a chlorinated polyolefin and an acrylic copolymer and at the same time improving the adhesion to a polyolefin-based material, a resin obtained by grafting a vinyl-based polymer to a chlorinated polyolefin is used. Has been proposed. In this case, a resin having excellent coating film hardness and solvent resistance as well as improved adhesion to the polyolefin material can be obtained, but when coloring with a pigment, a favorable hue is obtained because of poor pigment dispersibility. There was a problem that the coating film after coating was not provided with sufficient glossiness.

The present invention solves such a problem,
In addition to exhibiting good adhesion to polyolefin-based plastic substrates that have not been subjected to physical and chemical pretreatment steps, they have excellent solvent resistance, coating film hardness, storage stability, and pigment dispersibility. It is a main object to provide a good resin composition, and a coating composition and a coated product using the same.

[0011]

Means for Solving the Problems In order to solve the above-mentioned problems, in the first invention, (A) a chlorinated polyolefin resin having a chlorine content of 50% by weight or less, and (B) a chlorine content of 50% by weight. % Or less of chlorinated polyolefin resin
A chlorinated polyolefin-containing polymer obtained by heating a mixture of a radically polymerizable monomer containing 80% by weight and a chlorinated polyolefin resin together with an organic solvent and a radical polymerization initiator; and (C) a weight average molecular weight in terms of polystyrene of 3, An acrylic resin having a molecular weight of 000 to 40,000 is provided.

[0012] To solve the above-described problem, a second
According to the invention, the component (A) having a solid content of 20 to 70% by weight,
(A) + (B) + (C) having a total of 100% by weight of solids containing the above-mentioned component (B) and 10-60% by weight of the above-mentioned component (C). And a resin composition for coatings characterized by the following.

[0013] In order to solve the above-described problems, a third
According to the invention, the component (B) is a chlorinated polyolefin-containing polymer containing at least 5% by weight or more of a propylene oxide prepolymer in the coating resin composition according to any one of claims 1 and 2. It is intended to provide a resin composition for a paint characterized by the above.

In order to solve the above-described problem, a fourth
The invention according to any one of claims 1 to 3, wherein the component (C) is an acrylic resin containing at least 5% by weight or more of a propylene oxide prepolymer. It is intended to provide a resin composition for paints to be used.

[0015] In order to solve the above-mentioned problem, the fifth
According to the invention, in the coating resin composition according to any one of claims 1 to 4, the component (C) has an organic acid as a functional group, and has an acid value of 2 to 30 mgKOH / g. An object of the present invention is to provide a resin composition for a paint characterized by the following.

In order to solve the above-mentioned problem, a sixth
According to the invention, in the resin composition for a coating material according to any one of claims 1 to 5, the component (C) has an amino group as a functional group, and has an amine value of 0.5 to 20 mgKOH /
g. A resin composition for coatings characterized by being g.

In order to solve the above-mentioned problem, a seventh
In the invention of (1), the color pigment is dispersed in the resin composition for a coating material according to any one of (1) to (6), using the component (C) described in any one of (1) to (4). And obtaining a resin composition in which a color pigment is dispersed,
A coating composition comprising the component (A) and the component (B) according to any one of claims 3 to 3.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for a coating material of the present invention basically comprises a component (A) for achieving adhesion to a coating material, chemical resistance and coating film hardness, and a pigment dispersing property. An excellent component (C) and a component (B) which achieves adhesion to coating materials and compatibilization of the components (A) and (C),
The above problem is solved by using specific (A), (B) and (C).

The component (A) of the resin composition of the present invention is a chlorinated polyolefin resin. The chlorinated polyolefin resin has a chlorine content of 50% by weight or less, such as polyethylene resin, polypropylene resin, and ethylene-propylene copolymer. Coalesce, ethylene-vinyl acetate copolymer, and their carboxylic acids or their anhydride-modified polymers, etc.
The unsaturated carboxylic acid or anhydride thereof for the polymer modification treatment includes crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and the like.

The chlorinated polyolefin resin preferably has a chlorine content of 50% by weight or less. The reason is that
If the chlorine content is 50% by weight or more, the adhesion to the polyolefin resin base material to be coated decreases, which is not preferable.

Various chlorinated polyolefin resins described above are commercially available, for example, Supercron 773.
H (chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., 45% solution in toluene), Supercron 822 (chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., 20% solution in toluene) Supercron 892L (manufactured by Nippon Paper Co., Ltd.) Chlorinated polyolefin, toluene 20% solution), Supercron 832L (Nippon Paper Industries Co., Ltd. chlorinated polyolefin, toluene 30% solution), Supercron E (Nippon Paper Industries Co., Ltd., chlorinated polyolefin, toluene 20% solution) ), Hard Len 14LLB (a chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., 30% solution in toluene), Hard Len 14ML (a chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., a 30% solution in toluene), Hard Wren BS-40
(Chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., toluene 50% solution), Hardlen B-13 (Toyo Kasei Kogyo Co., Ltd., chlorinated polyolefin, toluene 30% solution), Hardlen B-4000 (Toyo Kasei Kogyo Co., Ltd.) Various chlorinated polyolefin resins, such as chlorinated polyolefins manufactured by K.K. and a 30% solution of toluene, can be exemplified.

Component (B) of the coating composition according to the present invention
Is a chlorinated polyolefin resin obtained by heating a mixture of a radically polymerizable monomer containing 10 to 80% by weight of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less and an organic solvent and a radical polymerization initiator. It is a polymer.

Examples of the chlorinated polyolefin resin used for the component (B) include polyethylene resins having a chlorine content of 50% by weight or less, polypropylene resins, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and carboxylic acids thereof. An acid or its anhydride modified polymer. The unsaturated carboxylic acid or anhydride thereof for the polymer modification treatment includes crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and the like.

The chlorine content of the chlorinated polyolefin resin is preferably 50% by weight or less. The reason for this is that when the chlorine content is 50% by weight or more, the adhesion to the polyolefin-based resin base material to be coated decreases.

Various chlorinated polyolefin resins are commercially available, such as Supercron 773H (a chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., a 45% solution in toluene), and Supercron 822 (a chlorinated polyolefin manufactured by Nippon Paper Co., Ltd.) Polyolefin, 20% solution in toluene) Supercron 892L (chlorinated polyolefin, 20% solution in toluene manufactured by Nippon Paper Industries), Supercron 832L
(A chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., a 30% solution in toluene), Supercron E (a chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., a 20% solution in toluene), and a hardlene 14LLB (manufactured by Toyo Kasei Kogyo Co., Ltd.) Chlorinated polyolefin, toluene 30% solution), hard len 14ML
(Chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., 30% solution in toluene), Hardlen BS-40 (Chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., 50% solution in toluene), Hardlen B-13 (Toyo Kasei Kogyo Co., Ltd.) Various chlorinated polyolefin resins, such as chlorinated polyolefin and toluene 30% solution manufactured by K.K., and Hardlen B-4000 (chlorinated polyolefin and toluene 30% solution manufactured by Toyo Kasei Kogyo Co., Ltd.) can be exemplified.

The content of the chlorinated polyolefin resin of the component (B) is preferably from 10 to 80% by weight.
Since the action of the component (B) in the coating composition is to compatibilize the component (A) and the component (C) and to impart adhesion to the coating material, the content of the chlorinated polyolefin resin of the component (B) is 10%. If the content is less than 10% by weight, it is not preferable because the adhesion is reduced and the effect as a compatibilizing component is reduced. Further, when the content of the chlorinated polyolefin resin of the component (B) is 80% by weight or more, the effect as a compatibilizing component is undesirably reduced.

The component (B) is obtained by polymerizing a radical polymerizable monomer in the presence of the chlorinated polyolefin resin. As the radical polymerizable monomer, an ester of acrylic acid or methacrylic acid, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid Acrylic acid such as lauryl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, or alkyl ester of methacrylic acid having 1 to 18 carbon atoms Acrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, or methacrylic acid Acrylic acid such as alkoxyalkyl ester having 2 to 18 carbon atoms of allyl acid, allyl acrylate, allyl methacrylate or the like, or alkenyl ester of methacrylic acid having 2 to 8 carbon atoms, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl Acrylic acid such as methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or hydroxyalkyl ester of methacrylic acid having 2 to 8 carbon atoms, allyloxyethyl acrylate, acrylic acid such as allyloxyethyl methacrylate, or 3 to 3 carbon atoms of methacrylic acid 18 alkenyloxyalkyl esters and the like.

Further, a vinyl aromatic compound can also be used. Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene. In addition, a polyolefin-based compound can also be used. Examples of the polyolefin-based compound include butadiene, isoprene, and chloroprene. In addition, caprolactone-modified acrylate compound, caprolactone-modified methacrylate, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N -Methylol acrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, maleic acid and the like.

Further, as a monomer component of the component (B), a radical polymerizable monomer having a propylene oxide prepolymer component is used as a part of the radical polymerizable monomer component, whereby the component (A) And the component (C) can be improved in compatibility.

The radical polymerizable monomer containing propylene oxide refers to propylene oxide in an amount of 1 mole relative to 1 mole of a monoalcohol compound having a radical polymerizable group.
It is a compound to which about 100 mol has been added. The addition number of propylene oxide is preferably within 100 moles. this is,
This is because no improvement in compatibility with the polymer (B) is observed even when 100 mol or more is added. The monoalcohol compound having a radical polymerizable group described herein includes, for example, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate Butyl and the like can be exemplified.

Various types of the radical polymerizable compound to which the propylene oxide is added are commercially available, for example, Blemmer PP-800 (manufactured by NOF Corporation), Blemmer P
P-1000 (manufactured by NOF Corporation), Blemmer 70P
EP-350B (manufactured by NOF Corporation) and the like can be exemplified.

When the propylene oxide or the radical polymerizable compound to which both propylene oxide and ethylene oxide are added is used as the radical polymerizable monomer used for the component (B), the content is 5% by weight or more. If the content is 5% by weight or less, the effect of improving the compatibility is small, so that it is not preferable.

The component (B) can be obtained by performing radical polymerization in the presence of the chlorinated polyolefin resin in the same manner and under the same conditions as those for a conventional radical polymerization reaction of an acrylic resin or a vinyl resin. As an example of such a synthesis reaction, each monomer component is dissolved in an organic solvent, and is dissolved in a nitrogen atmosphere in the presence of a radical polymerization initiator.
A method of heating with stirring at a temperature of about 0 ° C. can be shown. The reaction time may be generally about 1 to 10 hours.

As the organic solvent, ether solvents, ester solvents, and hydrocarbon solvents can be used. As the radical polymerization initiator, those commonly used can be used, and examples thereof include benzoyl peroxide, t-
Examples thereof include peroxides such as butylperoxy-2-ethylhexanoate and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile.

The component (C) used in the coating resin composition of the present invention is an acrylic resin having a weight average molecular weight in terms of polystyrene of 3,000 to 40,000. The effect of component (C) in the coating composition is pigment dispersion.
Component (C) preferably has a weight average molecular weight of 3,000 to 40,000 in terms of polystyrene. More preferably, it is 5000-15000. If the weight-average molecular weight in terms of polystyrene is 3000 or less, a coating film using the coating resin composition of the present invention contains a large amount of low molecular weight components, so that durability such as solvent resistance decreases, which is not preferable. The weight average molecular weight in terms of polystyrene is 4
If it is 0000 or more, it is not preferable because the pigment dispersion characteristics deteriorate.

As the radical polymerizable monomer used for the component (C), an ester of acrylic acid or methacrylic acid,
For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Acrylic acid such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, or an alkyl ester of methacrylic acid having 1 to 18 carbon atoms, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, methacrylic acid Acrylic acid such as methoxyethyl, ethoxybutyl acrylate, ethoxybutyl methacrylate, or methacrylic acid having 2 to 18 carbon atoms, alkoxyalkyl ester, allyl acrylate, Acrylic acid such as methacrylate,
Or alkenyl esters of methacrylic acid having 2 to 8 carbon atoms, such as acrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate, or 2 to 8 carbon atoms of methacrylic acid Hydroxyalkyl ester, allyloxyethyl acrylate,
Examples thereof include acrylic acid such as allyloxyethyl methacrylate or alkenyloxyalkyl ester of methacrylic acid having 3 to 18 carbon atoms.

Further, vinyl aromatic compounds, for example,
Styrene, α-methylstyrene, vinyltoluene, p-
Chlorstyrene can be mentioned, and polyolefin-based compounds such as butadiene, isoprene and chloroprene can also be used.In addition, caprolactone-modified acrylate compounds, caprolactone-modified methacrylate esters, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone , Vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methylol acrylamide butyl ether,
Examples thereof include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, and maleic acid.

Further, by using a radical polymerizable monomer having a propylene oxide prepolymer component as a monomer component of the component (C) for a part of the radical polymerizable monomer component, the component (A) The compatibility with the component (B) can be improved.

The radically polymerizable monomer containing propylene oxide is defined as “one mole of a monoalcohol compound having a radically polymerizable group and one mole of propylene oxide.
It is a compound to which about 100 mol has been added. The addition number of propylene oxide is preferably within 100 moles. this is,
This is because no improvement in compatibility between the component (A) and the component (B) is observed even when 100 mol or more is added. The monoalcohol compound having a radical polymerizable group described here is
Examples include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like.

Various radical polymerizable compounds to which the propylene oxide has been added are commercially available, for example, Blemmer PP-800 (manufactured by NOF Corporation), Blemmer P
P-1000 (manufactured by NOF Corporation), Blemmer 70P
EP-350B (manufactured by NOF Corporation) and the like can be exemplified.

When the above-mentioned propylene oxide or a radically polymerizable compound to which both propylene oxide and ethylene oxide are added is used as the radically polymerizable monomer used for the component (C), the content is 5% by weight or more. If the content is 5% by weight or less, the effect of improving the compatibility is small, so that it is not preferable.

The component (C) preferably has an acid such as a carboxyl group for the purpose of improving the dispersibility of the color pigment. The acid value is 2 to 30 mgKOH / g
It is preferred that More preferably, 2 to 10 mgK
OH / g. If it is 2 mgKOH / g or less, the effect of dispersing the pigment is small, which is not preferable. If it is 30 mgKOH / g or more, the pigment dispersibility decreases and the solution viscosity of the polymer increases, which is not preferable.

The component (C) preferably has an amino group for the purpose of improving the dispersibility of the color pigment. The amine value is preferably 0.5 to 20 mgKOH / g. A concentration of 0.5 mgKOH / g or less is not preferred because the effect of improving the pigment dispersibility is small. 20mgK
OH / g or more is not preferred because pigment dispersibility decreases.

The component (C) can be obtained by the same method and under the same conditions as those used for a conventional radical polymerization reaction of an acrylic resin or a vinyl resin. And heating with stirring at a temperature of about 60 to 180 ° C. in a nitrogen atmosphere in the presence of a radical polymerization initiator. The reaction time may be generally about 1 to 10 hours. As the organic solvent, ether solvents, ester solvents, and hydrocarbon solvents can be used.

As the radical polymerization initiator, those commonly used can be used. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate; Examples include azo compounds such as bisisobutyronitrile and azobisdimethylvaleronitrile.

The resin composition for a coating material of the present invention comprises a component (A), a component (B) and a component (C). The solids content of component (A) is in the range of 20% to 70% by weight. The content of the component (B) in the solid content is 10% by weight to 60% by weight. The content of the component (C) in the solid content is 10% by weight to 60% by weight. The sum of each component,
The sum of the solid contents in (A) + (B) + (C) is 100
% By weight.

When the content of the component (A) in the solid content is 20% by weight or less, it is not preferable because the adhesion is reduced. When the content of the component (A) in the solid content is 70% by weight or more, the coloring power is lowered because the content of the components (B) and (C) is lowered, which is not preferable.

When the content of the component (B) in the solid content is 10% by weight or less, the adhesion is reduced and the components (A) and (C)
Is not preferred because the compatibilizing action of the compound becomes small, and problems such as separation of each component occur. When the content of the component (B) in the solid content is 60% by weight or more, the component (A)
Since the content of (C) decreases, the coloring power and the adhesive force decrease, which is not preferable.

When the content of the component (C) in the solid content is 10% by weight or less, the coloring power is undesirably reduced. When the content of the component (C) in the solid content is 60% by weight or more, the content of the components (A) and (B) is reduced, so that the adhesive force is reduced.

As the color pigment used in the coating resin composition of the present invention, generally used inorganic color pigments and organic color pigments can be used. Further, the resin composition for coating of the present invention, if necessary, for example, a polyester resin, an alkyd resin, an epoxy resin, an acrylic resin, a urethane resin, a cellulose resin, an isocyanate resin, and the like can be mixed. Preferably, their amount does not exceed 30% by weight to maintain the effect of the present invention. Further, the coating resin composition of the present invention, if necessary,
Known coating surface modifier, fluidity modifier, ultraviolet absorber, light stabilizer, curing catalyst, extender pigment, metal pigment, mica powder pigment,
A coating composition can be prepared by adding a dye, an organic solvent, and the like.

The coating composition is usually made of an organic solvent, for example, a hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate or butyl acetate,
It can be diluted with a single or mixed solvent such as an ether-based solvent such as dioxane and ethylene glycol diethyl ether and applied by a general coating method such as spray coating, roll coating, brush coating and the like.

[0052]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 [Synthesis of B1 Equivalent to Component (B)] Supercron was placed in a 2 liter round bottom four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device. 892 L (chlorinated polyolefin resin, Nippon Paper Industries Co., Ltd., toluene 20% solution) 1400 g, methyl methacrylate 138.
6 g, 138.6 g of butyl methacrylate, and 2.8 g of methacrylic acid were charged and stirred while heating while blowing nitrogen gas. When the temperature in the flask reached 90 ° C., 3 g of a 50% by weight Kayaester O (manufactured by Kayaku Akzo Co., Ltd.) toluene solution was added.

The temperature in the flask was kept at 90 ° C., 90 minutes and 180 minutes after the initial addition of Kayaester O, 3 g of a 50% toluene solution of Kayaester O was added, and the temperature in the flask was further increased for 180 minutes. After maintaining at 90 ° C., the reaction was terminated by cooling to room temperature, and toluene 1
80 g was added to obtain a chlorinated polyolefin-containing polymer B1. Note that B1 contains a chlorinated polyolefin resin having a solid content of 50%.

[Synthesis of C1 Corresponding to Component (C)] 320 g of toluene was placed in a 1-liter round bottom four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device.
And heated to 110 ° C.

Separately Prepared Methyl Methacrylate 14
4.0 g, butyl methacrylate 336.0 g, ABN-
E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) 24.
A mixture of 0 g was added to the flask over 2 hours using a dropping funnel.

After the addition, 1.0 g of ABN-E was added every 20 minutes for 100 minutes for a total of 5 times.
The reaction was terminated while maintaining the temperature in the flask at 110 ° C. for 0 minutes to obtain an acrylic resin C1. C1 is an acrylic resin having a weight average molecular weight in terms of polystyrene of 15,000.

[Preparation of black enamel paint]
0 g, 2 g of FW-200 (carbon black pigment manufactured by Degussa Co., Ltd.) and 28 g of toluene were mixed with 300 g of iron beads having a diameter of 3 mm, and dispersed with a paint shaker for 4 hours to obtain a black paste. Next, 100 g of the black paste using the above-described C1 and Supercron 822
(Chlorinated polyolefin resin manufactured by Nippon Paper Industries) 10
0 g and 127 g of the above-mentioned component B1 were added and stirred to obtain a black enamel coating composition of Example 1. The composition of this example is such that the solid content of the component (A) is 20% by weight, the solid content of the component (B) is 38% by weight, and the solid content of the component (C) is 42% by weight.

Example 2 [Synthesis of B2 Equivalent to Component (B)] A 2-liter four-necked round bottom flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer was charged with Supercron. 892 L (chlorinated polyolefin resin, Nippon Paper Industries Co., Ltd., toluene 20% solution) 1400 g, methyl methacrylate 96.6
g, butyl methacrylate 124.6 g, Blemmer PP
−100056.0 g (radical polymerization type propylene oxide prepolymer manufactured by NOF Corporation) and 2.8 g of methacrylic acid were charged, and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 90 ° C., 3 g of a 50% by weight toluene solution of Kayaester O (manufactured by Kayaku Akzo) was added.

The temperature in the flask is maintained at 90 ° C., and 90 g and 180 minutes after the initial addition of Kayaester O, 3 g of a 50% toluene solution of Kayaester O is added. Further, the temperature in the flask is set to 90 ° C. for 180 minutes.
After cooling to room temperature to terminate the reaction, 180 g of toluene was added and the chlorinated polyolefin-containing polymer B2 was added.
I got

B2 contains 50% solids chlorinated polyolefin resin and 10% solids propylene oxide.

[Preparation of black enamel paint]
0 g, 2 g of FW-200 (carbon black pigment manufactured by Degussa Co., Ltd.) and 28 g of toluene were mixed with 300 g of iron beads having a diameter of 3 mm, and dispersed with a paint shaker for 4 hours to obtain a black paste. Next, 100 g of the black paste using the aforementioned C1 and 100 g of Supercron 822 (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd.)
And 127 g of the above-mentioned B1 were added and stirred to obtain a black enamel coating composition of Example 2. The composition of this example is such that the solid content of the component (A) is 20% by weight, the solid content of the component (B) is 38% by weight, and the solid content of the component (C) is 42% by weight.

Example 3 Synthesis of C2 Equivalent to Component (C) 320 g of toluene was placed in a 1-liter round-bottom four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device. Preparation 1
Heated to 10 ° C.

Separately Prepared Methyl Methacrylate 14
4.0 g, butyl methacrylate 288.0 g, Blenmer PP-1000 (radical polymerizable propylene oxide prepolymer manufactured by NOF Corporation) 48.0 g, ABN-
E (azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) 24.0
g of the mixture was added to the flask using a dropping funnel over 2 hours.

After the addition, 1.0 g of ABN-E was added every 20 minutes for 100 minutes, and a total of 10 times was added.
The reaction was terminated by maintaining the temperature in the flask at 110 ° C. for 0 minutes to obtain an acrylic resin C1.

C2 has a weight-average molecular weight in terms of polystyrene of 15,000 and a solid content of 10.0% by weight.
Is an acrylic resin containing a propylene oxide prepolymer.

[Preparation of black enamel paint]
0 g, 2 g of FW-200 (carbon black pigment manufactured by Degussa Co., Ltd.) and 28 g of toluene were mixed with 300 g of iron beads having a diameter of 3 mm, and dispersed with a paint shaker for 4 hours to obtain a black paste. Next, 100 g of the above-mentioned black paste using C2 and 100 g of Supercron 822 (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd.)
And 127 g of the above-mentioned B1 were added and stirred to obtain a black enamel coating composition of Example 3. The composition of the present example is composed of the component A
A solid content of 20% by weight, a solid content of the component (B) 38% by weight,
The solid content of the component (C) is 42% by weight.

Example 4 Synthesis of C3 Corresponding to Component (C) 320 g of toluene was placed in a 1-liter round-bottom four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer. Preparation 1
Heated to 10 ° C.

Separately Prepared Methyl Methacrylate 14
4.0 g, butyl methacrylate 326.4 g, methacrylic acid 9.6 g, ABN-E (Nippon Hydrazine Industry Co., Ltd.)
Azo compound) was added to the flask over 2 hours using a dropping funnel.

After completion of the addition, 1.0 g of ABN-E was added every 20 minutes for 100 minutes, for a total of 5 times.
The reaction was terminated while maintaining the temperature in the flask at 110 ° C. for 0 minutes to obtain an acrylic resin C1.

C3 is an acrylic resin having a weight average molecular weight in terms of polystyrene of 15,000 and an acid value of 13 mgKOH / g.

[Preparation of black enamel paint]
0 g, 2 g of FW-200 (carbon black pigment manufactured by Degussa Co., Ltd.) and 28 g of toluene were mixed with 300 g of iron beads having a diameter of 3 mm, and dispersed with a paint shaker for 4 hours to obtain a black paste. Next, 100 g of the black paste using the above-mentioned C3 and Supercron 822
(Chlorinated polyolefin resin manufactured by Nippon Paper Industries) 10
0 g and 127 g of the aforementioned B1 were added and stirred to obtain a black enamel coating composition of Example 4. The composition of the present example is such that the solid content of the component (A) is 20% by weight and the solid content of the component (B) is 38%.
% By weight, and the solid content of the component (C) was 42% by weight.

Example 5 Synthesis of C4 Corresponding to Component (C) 320 g of toluene was placed in a 1-liter round-bottom four-necked flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device. Preparation 1
Heated to 10 ° C.

Separately Prepared Methyl Methacrylate 14
A mixture of 4.0 g, 326.4 g of butyl methacrylate, 9.6 g of dimethylaminoethyl methacrylate, and 24.0 g of ABN-E (an azo compound manufactured by Nippon Hydrazine Industry Co., Ltd.) was used over 2 hours using a dropping funnel. Added into flask.

After the addition was completed, 1.0 g of ABN-E was added every 20 minutes for 100 minutes for a total of 5 times.
The reaction was terminated while maintaining the temperature in the flask at 110 ° C. for 0 minutes to obtain an acrylic resin C1.

C4 has a weight average molecular weight in terms of polystyrene of 15,000 and an amine value of 7 mgKOH / g.
Acrylic resin.

[Preparation of black enamel paint]
0 g, 2 g of FW-200 (carbon black pigment manufactured by Degussa Co., Ltd.) and 28 g of toluene were mixed with 300 g of iron beads having a diameter of 3 mm, and dispersed with a paint shaker for 4 hours to obtain a black paste. Next, 100 g of the black paste using the above-mentioned C4 and Supercron 822
(Chlorinated polyolefin resin manufactured by Nippon Paper Industries) 10
0 g and 127 g of the aforementioned B1 were added and stirred to obtain a black enamel coating composition of Example 5. The composition of the present example is such that the solid content of the component (A) is 20% by weight and the solid content of the component (B) is 38%.
% By weight, and a solid content of 42% by weight of the component (C).

Comparative Example 1: [Preparation of Black Enamel Paint] 100 g of a black paste using C1 and Supercron 822 (Nippon Paper Industries Co., Ltd.)
Chlorinated polyolefin resin) (30 g) and 173 g of B1 described above were added and stirred to obtain a black enamel coating composition of Comparative Example 1. The composition of this comparative example has a solid content of 6 of the component (A).
% By weight, the solid content of the component (B) 52% by weight, and the solid content of the component (C) 42% by weight.

Comparative Example 2 [Preparation of Black Enamel Paint] 100 g of a black paste using the above C1 and Supercron 822 (Nippon Paper Industries Co., Ltd.)
260g chlorinated polyolefin resin) and B1
Was added and stirred to obtain a black enamel coating composition of Comparative Example 2. The composition of this comparative example is the solid content of component (A) 5
2% by weight, 6% by weight of the solid content of the component (B), and 42% by weight of the solid content of the component (C).

Comparative Example 3 [Preparation of Black Enamel Paint] 12.5 g of the black paste using C1 described above, 200 g of Supercron 822 (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd.) and 183 g of the aforementioned B1 were added and stirred. Thus, a black enamel coating composition of Comparative Example 3 was obtained. The composition of this comparative example is such that the solid content of the component (A) is 40% by weight, the solid content of the component (B) is 55% by weight, and the solid content of the component (C) is 5% by weight.

[Coating film evaluation method] (A) Paint preparation and coating drying-Mixing the black enamel coating compositions obtained in the above Examples and Comparative Examples with 50 parts by weight of toluene and 50 parts by weight of xylene on a polypropylene molding material. After diluting with a solvent, coating was performed uniformly by air spray coating so that the dry film thickness became 20 μm.

After the completion of the air spray, let stand for 5 minutes,
Drying was performed for 30 minutes in a box-type drying oven at 80 ° C.
Further, the drying process was completed by standing at room temperature for 3 days, and various tests were performed. Table 1 shows the test results.

(B) Coating film test items and evaluation method Adhesion test: 1 mm × 1 mm × 100 cross cuts, the number of cross cuts remaining after cellophane tape peeling test. Water resistance adhesion test: 1 mm x 1 mm x 100 pieces after immersion in hot water at 40 ° C for 240 hours. Pigment dispersion state: The pigment dispersion state was relatively visually evaluated. Opacity: Opacity at a dry film thickness of 20 μm was relatively evaluated using an opacity test sheet certified by the Japan Paint Inspection Association. Storage stability: The test paint was sealed in a glass container, and the storage stability of the paint after being stored at 40 ° C. for 60 days was relatively evaluated.

(C) Evaluation criteria for test evaluation ：: extremely good ：: good △: slightly poor, but usable range ×: poor

[0085]

As described above, according to the present invention, adhesion to a polyolefin-based plastic substrate not subjected to a physical or chemical pretreatment step, solvent resistance, coating film hardness, storage stability It is possible to provide a coating resin composition having excellent pigment dispersibility and excellent pigment dispersibility.

The coating composition using the coating resin composition of the present invention has adhesion, storage stability, coating film hardness, etc., which are equal to or higher than those of conventional coating compositions used for polyolefin plastics. And at the same time, it has made it possible to provide a coating composition having the coloring property required for automotive exterior coatings, which has heretofore been difficult. Table 1

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J038 CA021 CA081 CB051 CB171 CC021 CC081 CC101 CE011 CF021 CF031 CG001 CG021 CG031 CG061 CG071 CG081 CG141 CG161 CH021 CH031 CH041 CH121 CH131 CH06 CH06 KA01 GA06 NA25 NA26

Claims (7)

[Claims] 1. A chlorinated polyolefin resin having a chlorine content of 50% by weight or less, and (B) a chlorine content of 50% by weight.
A chlorinated polyolefin-containing polymer obtained by heating a mixture of a radically polymerizable monomer containing 10 to 80% by weight of the following chlorinated polyolefin resin and a chlorinated polyolefin resin together with an organic solvent and a radical polymerization initiator;
(C) the weight average molecular weight in terms of polystyrene is 3,
A resin composition for a paint, comprising an acrylic resin having a molecular weight of 000 to 40,000. 2. The coating resin composition according to claim 1, wherein
20 to 70% by weight of the component (A) as a solid content,
0 to 60% by weight of the component (B) and 10 to 60% by weight
(A) + (B) + (C), wherein the total solid content of (A) + (B) + (C) is 100% by weight. 3. The coating resin composition according to claim 1, wherein the component (B) is at least 5%.
A resin composition for coatings, characterized in that it is a chlorinated polyolefin-containing polymer containing at least 1% by weight of a propylene oxide prepolymer. 4. The coating resin composition according to claim 1, wherein the component (C) is an acrylic resin containing at least 5% by weight or more of a propylene oxide prepolymer. Paint resin composition. 5. The coating resin composition according to claim 1, wherein the component (C) has an organic acid as a functional group, and has an acid value of 2 to 30 mgKOH / g. A resin composition for coatings, characterized by comprising: 6. The coating resin composition according to claim 1, wherein the component (C) has an amino group as a functional group, and has an amine value of 0.5 to 20 mg KOH.
/ G of the coating resin composition. 7. The coating resin composition according to any one of claims 1 to 6, wherein the component (C) according to any one of claims 1, 2, and 4 to 6 is used, and a coloring pigment is used. A coating composition comprising a resin composition in which a color pigment is dispersed by dispersion, and then the component (A) and the component (B) according to any one of claims 1 to 3 are added. .