JPH11131011A - Resin composition for plastic coating material and coating material composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for coating materials excellent in adhesion to polyolefin-based plastic substrates without undergoing physical or chemical pretreatments, solvent resistance, coating film hardness and storage stability and a coating material composition and a coated product using the resin composition. SOLUTION: This resin composition is obtained by heating a mixture composed of 5-80 pts.wt. chlorinated polyolefin resin having <=50 wt.% chlorine content with 95-20 pts.wt. radically polymerizable monomer together with an organic solvent and a radical polymerization initiator, thereby carrying out the solution polymerization, adding the radical polymerization initiator and a vinyl aromatic compound in an amount of 5-200 wt.% based on the radically polymerizable monomer thereto after the polymerization conversion rate of the radically polymerizable monomer attains >=70% and conducting the solution polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coatings and a coating composition using the same, especially to a plastic substrate such as a polyolefin, without applying a primer treatment to the resin composition, without having to apply a primer. The present invention relates to a coating resin composition having excellent coating film hardness and storage stability, and a coating composition using the coating resin.

[0002]

2. Description of the Related Art In recent years, in the fields of automobile interior parts, home appliances, office supplies, etc., the use of plastic instead of metal has been increasing for the purpose of weight reduction, rust prevention and other purposes. ing. Above all, the use of polyolefin resins such as polyethylene and polypropylene has been increasing due to their advantages such as moldability, light weight, low cost and recyclability.

[0003] However, polyolefin resins generally have high crystallinity and low polarity, and thus have the drawback that paints, inks, adhesives, and the like are difficult to adhere.

[0004] In order to solve such a drawback, some pretreatment is conventionally performed at the time of painting, printing and bonding. Specifically, physical treatments such as polishing, or a chemical treatment with a chromic acid mixed solution, a solvent, etc., and other treatments by plasma or corona discharge, etc., are required, but these pretreatment steps require equipment. In addition, there are problems that uniform treatment cannot be performed depending on the shape of the object to be coated and that the cost is increased.

[0005] In addition, various primers having good adhesion to a polyolefin-based substrate have been proposed, but the coating properties such as interlayer adhesion with a top coat and weather resistance are insufficient.
Poor practicality.

[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.

That is, when the chlorination rate of the chlorinated polyolefin is 50% by weight or more, the compatibility with the acrylic copolymer is improved, but the adhesion of the coating film is reduced, and when the chlorination rate is 20% by weight or less. Although the adhesion of the coating film is good, the compatibility with the acrylic copolymer is extremely poor, and practical use of both is difficult.

From these facts, it is considered appropriate that the chlorine content of the chlorinated polyolefin is in the range of 25 to 35% by weight. However, since the chlorine content is basically two components having poor compatibility, storage stability at low temperatures is low. However, problems remain in the properties and the like, and practical use is difficult.

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.

[0010] However, even in this case, depending on the vinyl-based monomer used for the grafting, there is a problem that the adhesion is reduced and separation occurs during storage.

[0011] Therefore, use of a monomer having an alicyclic structure such as isobornyl (meth) acrylate or (meth) acrylate having a hydrogenated dicyclopentadiene structure has been proposed as a vinyl monomer used for grafting. In this case, although the compatibility between the chlorinated polyolefin and the acrylic copolymer is further improved, when the formed film is hard, the solvent resistance and the coating film hardness are excellent, but the adhesion to the polyolefin material is reduced. Such a problem arises.

Further, when the film to be formed is soft, the adhesiveness to the polyolefin material is excellent, but problems such as poor solvent resistance and coating film hardness occur. It has been extremely difficult to obtain a coating composition that simultaneously satisfies the properties and hardness of the coating film.

[0013] The present invention has been made in view of such conventional problems, and has an advantage of adhering to a polyolefin-based plastic base material that has not been subjected to a physical or chemical pretreatment step, and has a stable storage property. Excellent in solvent resistance and solvent resistance,
An object of the present invention is to provide a resin composition for coatings excellent in coating film hardness, and a coating composition and a coated product using the same.

[0014]

Means for Solving the Problems In order to solve the above-mentioned problems, the invention according to claim 1 is a method for converting a mixture of a radically polymerizable monomer containing a chlorinated polyolefin resin and a chlorinated polyolefin resin into an organic compound. Solution polymerization is performed by heating with a solvent and a radical polymerization initiator, and after the polymerization conversion of the radical polymerizable monomer reaches a predetermined value or more, a vinyl aromatic compound is added to the radical polymerization initiator and the radical polymerizable monomer. The present invention provides a resin composition for a plastic coating, characterized in that solution polymerization is carried out by performing a solution polymerization.

In order to solve the above-mentioned problems, the invention according to claim 2 is directed to claim 1 wherein the chlorinated polyolefin resin has a chlorine content of 50% by weight or less, and
80 parts by weight, and 95 to 20 radical polymerizable monomers.
It is intended to provide a resin composition for a plastic paint, which is in a range of parts by weight.

In order to solve the above-mentioned problems, the invention according to claim 3 is the invention according to claim 1 or 2, wherein the polymerization conversion rate of the radical polymerizable monomer is 70% or more. It is intended to provide a resin composition for plastic paint characterized by the above.

In order to solve the above-mentioned problem, the invention according to claim 4 is directed to a method according to any one of claims 1 to 3, wherein the vinyl aromatic compound is added to the radical polymerizable monomer by 5%. It is intended to provide a resin composition for a plastic coating, characterized in that the content is from 200 to 200% by weight.

In order to solve the above-mentioned problems, the invention according to claim 5 is directed to a method according to any one of claims 1 to 4, wherein the radically polymerizable monomer is methacrylic acid ester, acrylic acid ester or methacrylic acid. An object of the present invention is to provide a resin composition for a plastic paint, which is a mixture of an acid ester and an acrylic ester, and wherein the vinyl aromatic compound is styrene.

In order to solve the above-mentioned problem, the invention according to claim 6 is a mixture of a radical polymerizable monomer containing a chlorinated polyolefin resin and a chlorinated polyolefin resin, wherein the radical polymerizable monomer is Contains a radically polymerizable polystyrene having a radically polymerizable double bond at a terminal, and is obtained by heating a mixture of the chlorinated polyolefin resin and a radically polymerizable monomer together with an organic solvent and a radical polymerization initiator. It is intended to provide a resin composition for a plastic coating characterized by the following.

In order to solve the above-mentioned problems, the invention according to claim 7 is directed to claim 6, wherein the chlorinated polyolefin resin has a chlorine content of 50% by weight or less,
An object of the present invention is to provide a resin composition for a plastic paint, which is in a range of 80 parts by weight.

In order to solve the above-mentioned problem, the invention according to claim 8 is the invention according to claim 6 or 7, wherein the radically polymerizable polystyrene has a number average molecular weight of 1000 or more, It is intended to provide a resin composition for plastic coatings, which is in the range of 5 to 70% by weight.

In order to solve the above-mentioned problem, the invention according to claim 9 is directed to a method according to any one of claims 6 to 8, wherein the mixture of the chlorinated polyolefin resin and the radical polymerizable monomer is 95%. It is intended to provide a resin composition for a plastic paint, which is within a range of from 20 to 20 parts by weight.

[0023] In order to solve the above-mentioned problems, the invention according to claim 10 is characterized in that in any one of claims 1 to 9, the resin composition for a plastic paint is used. A coating composition is provided.

In order to solve the above-mentioned problems, the invention according to claim 11 is the invention according to any one of claims 1 to 10, wherein the content of the chlorinated polyolefin resin is in the range of 5 to 80%. And a coating composition characterized by using the resin composition for plastic coating according to (1).

In order to solve the above-mentioned problem, the invention according to claim 12 is directed to a resin composition for a plastic paint according to any one of claims 1 to 11, wherein
% Or more, and 30% or less of another resin composition.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention contains a chlorinated polyolefin resin. The chlorinated polyolefin resin is a polyethylene resin having a chlorine content of 50% by weight or less, a polypropylene resin, an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, and a carboxylic acid or a carboxylic acid of the resin or the copolymer. Polymers modified with acid anhydrides and the like. The unsaturated carboxylic acid or acid anhydride for the polymer modification treatment includes crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and the like.

The chlorinated polyolefin resin used in the resin composition of the present invention preferably has a chlorine content of 50% by weight or less. 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 are commercially available, for example, Supercron 773H (Nippon Paper Industries, Ltd.)
Chlorinated polyolefin manufactured by Nippon Paper Co., Ltd., 45% solution in toluene, Supercron 822 (Nippon Paper Industries Co., Ltd., chlorinated polyolefin, 20% solution in toluene) Supercron 892L (Nippon Paper Industries Co., Ltd., chlorinated polyolefin, 20% solution in toluene) ), Supercron 832L (chlorinated polyolefin from Nippon Paper Industries, 30% toluene solution), Supercron E
(Nippon Paper Industries chlorinated polyolefin, toluene 20
% Solution), Hardlen 14LLB (chlorinated polyolefin, toluene 30% solution manufactured by Toyo Kasei Kogyo Co., Ltd.), Hardlen
14ML (Toyo Kasei Kogyo Co., Ltd. chlorinated polyolefin, toluene 30% solution), Hardlen BS-40 (Toyo Kasei Kogyo (
Chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., 50% solution in toluene; Hardlen B-13 (chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., 30% solution in toluene); Hardlen B-4000 (chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd.) , A 30% solution of toluene).

The resin composition according to the first embodiment for carrying out the present invention comprises a radical polymerizable monomer containing 5 to 80% by weight of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less and a chlorinated monomer. Solution polymerization is performed by heating a mixture of the polyolefin resin together with an organic solvent and a radical polymerization initiator.

As the radical polymerizable monomer,
Esters 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, There are acrylic acids such as propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and lauryl methacrylate.

[0031] There are also alkyl esters of methacrylic acid having 1 to 18 carbon atoms, and acrylic acids such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate. .

Acrylic acid such as methacrylic acid having 2 to 18 carbon atoms such as alkoxyalkyl ester, allyl acrylate and allyl methacrylate, or methacrylic acid having 2 to 8 carbon atoms alkenyl ester, hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxybutyl acrylate Acrylic acid such as hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or methacrylic acid having 2 to 8 carbon atoms, alkyl acid such as allyloxyethyl acrylate, allyloxyethyl methacrylate, or carbon of methacrylic acid Alkenyloxyalkyl esters of the formulas 3 to 18 are also included.

Examples of the radical polymerizable monomer include vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene, and polyolefin-based compounds such as butadiene,
There are also isoprene and chloroprene.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-methylolacrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, maleic acid, and the like.

As the radical polymerization initiator, commonly used radical polymerization initiators can be used. Examples thereof include benzoyl peroxide and t-butylperoxy-2-amine.
Examples include peroxides such as ethylhexanoate, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile.

As the organic solvent, ether solvents, ester solvents, and hydrocarbon solvents can be used. The heating temperature and the polymerization time depend on the radical polymerization initiator and the radical polymerizable monomer used. It can be obtained by the same method and under the same conditions as those for a radical polymerization reaction of an ordinary acrylic resin or vinyl resin. As an example, a method of heating for 1 to 10 hours while stirring at a temperature of about 60 to 180 ° C. in a nitrogen atmosphere can be shown.

The content of the chlorinated polyolefin resin in the resin composition is 5 to 80% by weight, preferably 1 to 80% by weight.
0 to 50% by weight. When the content of the chlorinated polyolefin resin is 5% by weight or less, it is not preferable because sufficient adhesion to the polyolefin material when used as a coating material cannot be obtained. 80 content of chlorinated polyolefin resin
If it is more than 10% by weight, sufficient coating film hardness, weather resistance, chemical resistance,
It is not preferable because characteristics such as weather resistance cannot be obtained.

In the resin composition according to the first embodiment, after the polymerization conversion of the radically polymerizable monomer reaches 70% or more, the radical polymerization initiator and the radically polymerizable monomer are successively added in an amount of 5 to 200% by weight. By adding a vinyl aromatic compound of the formula (1) and continuing the solution polymerization.

As the radical polymerization initiator, those commonly used can be used. Examples of the radical polymerization initiator include benzoyl peroxide and t-butylperoxy-2-amine.
Examples include peroxides such as ethylhexanoate, azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, and preferably radical radical initiators based on peroxides such as benzoyl peroxide. It is.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, and the like.

The addition amount of the vinyl aromatic compound monomer is 5 to 200% by weight based on the radical polymerizable monomer used in the polymerization initiation stage. Preferably 20 to 100% by weight
It is. If the content is less than 5% by weight, sufficient solvent resistance cannot be obtained when used in a paint, which is not preferable. If the content is more than 200% by weight, the adhesion to the polyolefin-based material is undesirably reduced.

Further, the vinyl aromatic compound has a polymerization conversion of the radical polymerizable monomer used in the initial stage of polymerization of 70.
Add when it reaches at least%. If the vinyl aromatic compound is added at a conversion point of 70% or less, it is not preferable because the adhesion to the polyolefin-based material is reduced.

Further, a chlorinated polyolefin resin containing methacrylate, or acrylate or a mixture of methacrylate and acrylate as the radical polymerizable monomer, and styrene as a vinyl aromatic compound is further contained. It may be a resin composition.

Next, in the resin composition according to the second embodiment of the present invention, a polymerization method for obtaining 5-80 parts by weight of the chlorinated polyolefin resin having a chlorine content of 50% by weight or less and a resin composition obtained by grafting styrene is used. Heating a mixture of radically polymerizable monomers containing 5 to 70% by weight of radically polymerizable polystyrene having a number average molecular weight of 1,000 or more having a radically polymerizable double bond at the terminal together with an organic solvent and a radical polymerization initiator. Is a resin composition containing a chlorinated polyolefin resin obtained by the above method.

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 Lauryl,
Examples include acrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, and lauryl methacrylate.

Further, an alkyl ester of methacrylic acid having 1 to 18 carbon atoms, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate,
Acrylic acid such as ethoxybutyl methacrylate, or an alkoxyalkyl ester of methacrylic acid having 2 to 18 carbon atoms, allyl acrylate, alkenyl ester of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as allyl methacrylate, hydroxyethyl acrylate, hydroxy Acrylic acid such as ethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or acrylic acid such as hydroxyalkyl ester of methacrylic acid having 2 to 8 carbon atoms, allyloxyethyl acrylate, allyloxyethyl methacrylate Alternatively, an alkenyloxyalkyl ester of methacrylic acid having 3 to 18 carbon atoms may be used.

Further, examples of the radical polymerizable monomer include vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene, and also include polyolefin-based compounds such as 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-methylolacrylamide, N-methylol Examples thereof include methacrylamide, N-methylolacrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, and maleic acid.

The number average molecular weight having a radical polymerizable double bond at the terminal is preferably 1,000 or more. When the number average molecular weight is 1000 or less, no improvement in the hardness of the coating film is observed, which is not preferable.

A radically polymerizable polystyrene having a radically polymerizable double bond at a terminal is generally commercially available, and examples thereof include a macromonomer AS-6 (terminal methacryloyl group polystyrene; number average molecular weight 6000 Toagosei Co., Ltd.). .

The content of the radically polymerizable polystyrene in the radically polymerizable monomer is 5 to 70% by weight, preferably 10 to 70% by weight.
~ 50% by weight. If the content is less than 5% by weight, sufficient solvent resistance cannot be obtained when used in a paint, which is not preferable. 70
If the content is more than 10% by weight, the adhesion to the polyolefin-based material is undesirably reduced.

The resin composition for a coating material of the present invention can be obtained by the same method 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, a method is shown in which each monomer component is dissolved in an organic solvent and heated with stirring at a temperature of about 60 to 180 ° C. in a nitrogen atmosphere in the presence of a radical polymerization initiator. be able to. The reaction time is
Usually, it should be 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 usually used may be used, and examples thereof include benzoyl peroxide, peroxides such as t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, An azo compound such as azobisdimethylvaleronitrile can be used.

Next, a coating composition according to the present invention is a coating composition using the resin composition containing the chlorinated polyolefin resin described above. The coating resin composition of the present invention, if necessary, for example, polyester resin, alkyd resin, epoxy resin, acrylic resin, urethane resin,
It can be mixed with a cellulose resin, an isocyanate resin or the like, but the amount thereof is preferably not more than 30% by weight in order to maintain the effect of the present invention.

Further, the coating resin composition of the present invention may contain, if necessary, a known coating surface adjuster, a fluidity adjuster,
A coating composition can be prepared by adding an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metal pigment, a mica powder pigment, 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 and xylene, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate and butyl acetate, dioxane, and ethylene glycol. It can be diluted by a single or mixed solvent such as an ether-based solvent such as diethyl ether and applied by a general coating method such as spray coating, roll coating, brush coating and the like.

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

【Example】

Example 1 Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Co., Ltd.) was placed in a one-liter four-necked round-bottomed flask equipped with a nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer.
110 g of toluene 20% solution), methyl methacrylate 100
g, isobutyl methacrylate (75 g), normal butyl methacrylate (75 g), and toluene (377 g) were charged and heated and stirred while blowing in nitrogen gas. The temperature in the flask is 105
When the temperature reaches ℃ Cadox B-75AW (Kakuyaku Akzo Co., Ltd.)
Benzoyl peroxide, 75% water wet product) 10% by weight
5 g of a toluene solution were added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes and 90 minutes after the initial addition of Cadox B-75AW,
Each of them was added with 5 g of a 10% toluene solution of Kadox B-75AW, and the mixture was further heated and stirred for 45 minutes while maintaining the temperature at 105 ° C. At this time, the addition ratio of the acrylic monomer added to the flask in the initial stage to the polymer was 80% or more, so 75 g of styrene and 10% toluene solution of Cadox B-75AW were used.
5 g was added, and heating and stirring were continued while maintaining the temperature at 105 ° C. 45 minutes and 90 minutes after the addition of styrene, 5 g of a 10% toluene solution of Cadox B-75AW was added, and the mixture was heated and stirred for 120 minutes while maintaining the temperature at 105 ° C. Then, the reaction is terminated by cooling to room temperature,
Next, 30 g of toluene was added to obtain a resin composition for coating of Example 1.

This example contains a chlorinated polyolefin resin of 8.1% solids at the time of initial charging as a component of the resin composition for coatings and 6.3% of the resin composition as a whole,
Polymerization conversion rate of the initially charged radical polymerizable monomer is 80
%, The polymerization was conducted by adding styrene as a vinyl aromatic monomer and adding 30% by weight to the initially charged radically polymerizable monomer.

Example 2 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 was charged with Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Co., Ltd.).
150 g of 20% toluene solution), 90 g of methyl methacrylate,
75 g of isobutyl methacrylate, 75 g of normal butyl methacrylate, 60 g of AS-6 (radical polymerizable polystyrene having a number average molecular weight of 6000, manufactured by Toagosei Co., Ltd.) and 310 g of toluene were charged and heated and stirred while blowing in nitrogen gas. When the temperature in the flask reaches 105 ° C, Cadox B-75AW
(Benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., 75%
5 g of a 10% by weight toluene solution was added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes, 90 minutes, and 135 minutes after the initial addition of Cadox B-75AW.
Minutes, 180 minutes and 225 minutes, respectively, Kadox B-75AW
5 g of a 10% toluene solution were added. After heating and stirring for further 120 minutes while maintaining the temperature at 105 ° C., the reaction was terminated by cooling to room temperature, and 35 g of toluene was added to obtain a coating resin composition of Example 2.

This example is an example in which a chlorinated polyolefin resin having a solid content of 9.1% is contained as a component of a resin composition for a paint, and 20% by weight of a radically polymerizable monomer is a radically polymerizable polystyrene.

[Comparative example]

Comparative Example 1 Using the same apparatus as in Example 1, Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%
Solution) 110 g, methyl methacrylate 100 g, isobutyl methacrylate 75 g, normal butyl methacrylate 75 g,
377 g of toluene was charged and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of a 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., wetted with 75% water) was added.

The temperature in the flask was maintained at 105 ° C., and 45 and 90 minutes after the initial addition of Cadox B-75AW, 5 g of a 10% toluene solution of Cadox B-75AW was added, and the temperature was maintained at 105 ° C. The heating and stirring were continued for another 45 minutes. At this time, since the addition ratio of the acrylic monomer initially added to the flask to the polymer was 80% or more, 7.5 g of styrene and 5 g of a 10% toluene solution of cadox B-75AW were added, and the temperature was increased to 105%. The heating and stirring were continued while maintaining the temperature at ° C. After 45 minutes and 90 minutes after the addition of styrene, 5 g of a 10% toluene solution of Kadox B-75AW was added, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C, and then cooled to room temperature. Then, the reaction was completed, and 30 g of toluene was added to obtain a coating resin composition of Comparative Example 1.

This comparative example contains a chlorinated polyolefin resin having a solid content of 8.1% at the time of initial charging as a component of the coating resin composition and 6.3% of the resin composition as a whole,
Polymerization conversion rate of the initially charged radical polymerizable monomer is 80
In this example, styrene as a vinyl aromatic monomer was added at 3% by weight, and 3% by weight was added to the radically polymerizable monomer initially charged.

Comparative Example 2 Using the same apparatus as in Example 1, Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%
Solution) 100 g, methyl methacrylate 40 g, isobutyl methacrylate 30 g, normal butyl methacrylate 30 g, and toluene 410 g were charged, and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of a 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., wetted with 75% water) was added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes and 90 minutes after the initial addition of Cadox B-75AW, 5 g of a 10% toluene solution of Cadox B-75AW was added, and the temperature was raised to 105 ° C. While keeping the temperature, the mixture was heated and stirred for another 45 minutes. At this time, the addition ratio of the acrylic monomer initially added into the flask to the polymer was 80% or more, so 250 g of styrene and 5 g of a 10% toluene solution of Cadox B-75AW were added, and the temperature was increased to 105 ° C. , And heating and stirring were continued. 45 minutes after the addition of styrene, and 90 minutes
After 5 minutes, each of the Cadox B-75AW 10% toluene solution 5
g, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C, and then cooled to room temperature to terminate the reaction.
30 g of toluene was added to obtain a coating resin composition of Comparative Example 2.

This comparative example contains a chlorinated polyolefin resin of 16.7% in solid content at the time of initial preparation as a component of the resin composition for coating, and 5.4% in total of the resin composition,
Polymerization conversion rate of the initially charged radical polymerizable monomer is 80
%, The polymerization was conducted by adding styrene as a vinyl aromatic monomer and adding 250% by weight to the radically polymerizable monomer initially charged.

Comparative Example 3 Using the same apparatus as in Example 1, Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Co., Ltd., toluene 20%
Solution), 40 g of methyl methacrylate, 100 g of methyl methacrylate, 75 g of isobutyl methacrylate, 75 g of normal butyl methacrylate, and 402 g of toluene, and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of a 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide, manufactured by Kayaku Akzo Co., Ltd., wetted with 75% water) was added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes and 90 minutes after the initial addition of Cadox B-75AW, 5 g of a 10% toluene solution of Cadox B-75AW was added, and the temperature was raised to 105 ° C. The heating and stirring were continued for another 45 minutes while keeping the temperature. At this time, the addition ratio of the acrylic monomer initially added to the flask to the polymer was 80% or more, so 75 g of styrene and 5 g of a 10% solution of Cadox B-75AW in toluene were added, and the temperature was increased to 105 ° C. , And heating and stirring were continued. After 45 minutes and 90 minutes after the addition of styrene, 5 g of a 10% toluene solution of Cadox B-75AW was added, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C, and then cooled to room temperature. To end the reaction
30 g was added to obtain a coating resin composition of Comparative Example 3.

This comparative example contains a chlorinated polyolefin resin having a solid content of 3.1% at the time of initial preparation as a component of the coating resin composition and 2.4% of the resin composition as a whole,
Polymerization conversion rate of the initially charged radical polymerizable monomer is 80
%, The polymerization was conducted by adding styrene as a vinyl aromatic monomer and adding 30% by weight to the initially charged radically polymerizable monomer.

Comparative Example 4 Using the same apparatus as in Example 1, Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%
Solution), 40 g of methyl methacrylate, 100 g of methyl methacrylate, 75 g of isobutyl methacrylate, 75 g of normal butyl methacrylate, and 402 g of toluene, and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of a 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., wetted with 75% water) was added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes after the initial addition of Cadox B-75AW, 75 g of styrene
And 5 g of a 10% toluene solution of Cadox B-75AW,
The heating and stirring were continued while maintaining the temperature at 105 ° C. At this point, the polymerization conversion of the initially added radically polymerizable monomer immediately before the addition of styrene was 40%. After 45 minutes, 90 minutes, and 135 minutes after the addition of styrene, 5 g of a 10% toluene solution of Kadox B-75AW was added, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C.
Then, the reaction was terminated by cooling to room temperature, and toluene 30 g
Was added to obtain a coating resin composition of Comparative Example 4.

This comparative example contains a chlorinated polyolefin resin having a solid content of 8.1% at the time of initial charging as a component of the coating resin composition and 6.3% of the resin composition as a whole,
Polymerization conversion rate of the initially charged radical polymerizable monomer of 40
% Of styrene as a vinyl aromatic monomer and 30% of the radically polymerizable monomer initially charged.
This is an example in which polymerization is performed by adding weight%.

Comparative Example 5 Using the same apparatus as in Example 2, Supercron E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%
Solution) 150 g, methyl methacrylate 90 g, isobutyl methacrylate 75 g, normal butyl methacrylate 75 g, AS
6 g (radical polymerizable polystyrene, number average molecular weight: 6000, manufactured by Toa Gosei Co., Ltd.), 54 g of styrene monomer and 310 g of toluene were charged and heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of a 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide, manufactured by Kayaku Akzo Co., Ltd., wetted with 75% water) was added.

The temperature in the flask was maintained at 105 ° C., and 45 minutes, 90 minutes, and 135 minutes after the initial addition of Cadox B-75AW.
Minutes, 180 minutes and 225 minutes, respectively, Kadox B-75AW
5 g of a 10% toluene solution were added. The heating and stirring were continued for another 120 minutes while maintaining the temperature at 105 ° C., and then the reaction was terminated by cooling to room temperature, and 35 g of toluene was added, and Comparative Example 5 was added.
Was obtained.

This comparative example is an example in which a chlorinated polyolefin resin having a solid content of 9.1% is contained as a component of a coating resin composition, and 2% by weight of a radically polymerizable monomer is a radically polymerizable polystyrene.

[Coating film evaluation method]

(A) Preparation and drying of paint The resin composition for paint obtained in the above Examples and Comparative Examples was diluted with a mixed solvent consisting of 50 parts by weight of toluene and 50 parts by weight of xylene on a polypropylene molding material and air-sprayed. The coating was uniformly applied so that the dry film thickness was 10 μm. After the completion of the air spray, the mixture was allowed to stand still for 5 minutes, and dried in a box-type drying oven at 80 ° C for 30 minutes. After leaving it at room temperature for 3 days, the drying process was completed 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 Cut in grids, judged by the number of grids remaining after cellophane tape peeling test. Moisture resistance adhesion test: After leaving at 50 ° C and 95RH% for 240 hours,
1 mm x 1 mm x 100 Cut in grids, judged by the number of crosses remaining after the cellophane tape peeling test. Oil resistance test: 2 g of tallow per 100 cm ² (manufactured by Nacalai Task Co., Ltd.) is applied, a cotton cloth is placed on the cloth, wrapped in aluminum foil, left at 80 ° C. for 1 hour, and then coated with a neutral detergent. After washing and air drying, a cellophane tape peeling test was performed to determine. Cosmetic resistance test: 1 g of hair liquid per 100 cm ² (Bravas hair liquid manufactured by Shiseido Co., Ltd.) was applied, a cotton cloth was placed, and then wrapped in aluminum foil, and the temperature was 80 ° C. × 1 h.
The coated surface was washed with a neutral detergent and air-dried. Then, a cellophane tape peeling test was performed to judge.

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

[0082]

As described above, in the present invention, adhesion to a polyolefin-based plastic substrate not subjected to a physical or chemical pretreatment step, solvent resistance,
A coating resin composition having excellent coating film hardness and storage stability, and a coating composition and a coated product using the same can be provided.

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 212: 08)

Claims (12)

[Claims] A mixture of a radically polymerizable monomer containing a chlorinated polyolefin resin and a chlorinated polyolefin resin is solution-polymerized by heating together with an organic solvent and a radical polymerization initiator, and the polymerization conversion rate of the radically polymerizable monomer is increased. After reaching a predetermined value, a vinyl aromatic compound is added to the radical polymerization initiator and the radical polymerizable monomer to carry out solution polymerization, wherein the resin composition is used for a plastic paint. 2. The method according to claim 1, wherein the chlorinated polyolefin resin has a chlorine content of 50% by weight or less and 5 to 80 parts by weight, and the radically polymerizable monomer is in a range of 95 to 20 parts by weight. Characteristic resin composition for plastic coating. 3. The resin composition for a plastic paint according to claim 1, wherein the polymerization conversion of the radically polymerizable monomer is 70% or more. 4. The resin composition for a plastic paint according to claim 1, wherein the amount of the vinyl aromatic compound is 5 to 200% by weight based on the radically polymerizable monomer. 5. The radically polymerizable monomer according to claim 1, wherein the radically polymerizable monomer is a methacrylate ester, an acrylate ester, or a mixture of a methacrylate ester and an acrylate ester, and the vinyl aromatic compound Is a resin composition for a plastic paint, characterized by being styrene. 6. A mixture of a radically polymerizable monomer containing a chlorinated polyolefin resin and a chlorinated polyolefin resin, wherein the radically polymerizable monomer contains a radically polymerizable polystyrene having a radically polymerizable double bond at a terminal. And a resin composition for a plastic coating obtained by heating a mixture of the chlorinated polyolefin resin and a radical polymerizable monomer together with an organic solvent and a radical polymerization initiator. 7. The resin composition for a plastic paint according to claim 6, wherein the chlorinated polyolefin resin has a chlorine content of 50% by weight or less and is in a range of 5 to 80 parts by weight. 8. The radical-polymerizable polystyrene according to claim 6, wherein the number-average molecular weight is 10 or more.
A resin composition for a plastic paint, which is not less than 00 and in the range of 5 to 70% by weight. 9. The resin for a plastic paint according to claim 6, wherein the mixture of the chlorinated polyolefin resin and the radical polymerizable monomer is in a range of 95 to 20 parts by weight. Composition. 10. The coating composition according to claim 1, wherein the resin composition for a plastic coating is used. 11. The method according to claim 1, wherein the content of the chlorinated polyolefin resin is 5%.
A paint composition characterized by using a resin composition for plastic paint in the range of up to 80%. 12. The coating composition according to claim 1, wherein the content of the resin composition for plastic coating is at least 70%, and the content of the other resin composition is at most 30%.