JP3479208B2 - Resin composition for plastic paint and paint composition using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coating and a coating composition using the same, particularly adhesiveness and solvent resistance even if a plastic substrate such as polyolefin is not treated with a primer. The present invention relates to a coating resin composition excellent in coating film hardness and storage stability, and a coating composition using the coating resin.

[0002]

2. Description of the Related Art Recently, in the fields of automobile interior parts, home 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. ing. Above all, the use amount of polyolefin resins such as polyethylene and polypropylene is expanding due to advantages such as moldability, light weight, low cost and recyclability.

However, since polyolefin resins generally have high crystallinity and small polarity, they have a drawback that paints, inks, adhesives and the like are difficult to adhere to them.

In order to solve such a defect, conventionally, some kind of pretreatment is performed at the time of painting, printing and bonding. Specific examples include physical treatment such as polishing, chemical treatment with chromic acid mixture, solvent, etc., and treatment with plasma or corona discharge. These pretreatment steps require equipment. However, depending on the shape of the object to be coated, there are problems that it cannot be uniformly processed, and the cost is increased.

Further, various primers having good adhesion to polyolefin-based substrates have been proposed, but the coating properties such as interlayer adhesion to the top coat and weather resistance are insufficient,
Practicality is poor.

Adhesion to polyolefin materials,
As a resin composition for coatings having improved coating performance such as solvent resistance and hardness, a resin composition comprising a chlorinated polyolefin and an acrylic polymer is known, and such a resin composition is as follows. Have a problem.

That is, when the chlorination ratio 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 lowered, and when it is 20% by weight or less. The adhesion of the coating film is good, but the compatibility with the acrylic copolymer is extremely poor, and both are difficult to practically use.

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, but since it is basically two components with poor compatibility, it is stable in storage at low temperatures. There are still problems with sex, and practical use is difficult.

On the other hand, as a method for further improving the compatibility between the chlorinated polyolefin and the acrylic copolymer and at the same time improving the adhesion to the polyolefin material, a resin obtained by grafting the vinyl polymer onto the chlorinated polyolefin is used. Is proposed.

However, even in this case, depending on the vinyl-based monomer used for grafting, there are problems that the adhesiveness is lowered and separation occurs during storage.

Therefore, use of a monomer having an alicyclic structure found in isobornyl (meth) acrylate and (meth) acrylate having a hydrogenated dicyclopentadiene structure as a vinyl-based monomer used for grafting has been proposed. 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 occurs.

Further, when the formed film is soft, the adhesion to the polyolefin material is excellent, but the solvent resistance and the coating film hardness are inferior. It has been extremely difficult to obtain a coating composition that simultaneously satisfies the properties, coating film hardness, and the like.

The present invention has been made by paying attention to such conventional problems, and it is possible to obtain the adhesiveness and the storage stability to a polyolefin-based plastic substrate which is not subjected to a physical or chemical pretreatment step. Excellent in solvent resistance,
The main object of the present invention is to provide a coating resin composition excellent in coating film hardness, a coating composition using the same, and a coated article.

Chlorinated poly having a chlorine content of 50% by weight or less
5 to 80 parts by weight of olefin resin and radically polymerizable monomer
-Mixed with 95 to 20 parts by weight of organic solvent and radical
Solution polymerization by heating with a polymerization initiator,
Polymerization conversion rate of the radically polymerizable monomer is 70% or more
After reaching the free radical polymerization initiator and vinyl aromatic compound
Resin composition for plastic coatings in which solution polymerization is performed by adding
Wherein the vinyl aromatic compound is the radical
Characterized by 5 to 200% by weight based on the compatible monomer
A resin composition for plastic paint. It is intended to provide. "

Means for Solving the Problems In order to solve the above problems, the invention according to claim 2 provides the radically polymerizable monomer according to claim 1, wherein the radically polymerizable monomer is a methacrylic acid ester or an acrylic acid ester or methacrylic acid. A resin composition for a plastic coating, which is a mixture of an ester and an acrylic ester, and the vinyl aromatic compound is styrene and a styrene derivative . Is provided.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention contains a chlorinated polyolefin resin. With this chlorinated polyolefin resin, the chlorine content is 50 wt% or less polyethylene resin, polypropylene resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and carboxylic acids of those resins and copolymers or Examples include polymers modified with acid anhydrides. The unsaturated carboxylic acid or its acid anhydride 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 used in the resin composition of the present invention is preferably 50% by weight or less. When the chlorine content is 50% by weight or more, the adhesion to the polyolefin resin base material that is the object to be coated is reduced, which is not preferable.

Various chlorinated polyolefin resins are commercially available, for example, Super Clone 773H (Nippon Paper Industries (
Co., Ltd. chlorinated polyolefin, toluene 45% solution), Super Clone 822 (Nippon Paper Industries Co., Ltd. chlorinated polyolefin, toluene 20% solution) Super Cron 892L (Nippon Paper Co., Ltd. chlorinated polyolefin, toluene 20% solution) ), Supercron 832L (Chlorinated polyolefin manufactured by Nippon Paper Industries Co., Ltd., 30% toluene solution), Supercron E
(Nippon Paper Industries Co., Ltd. chlorinated polyolefin, toluene 20
% Solution), HARDREN 14LLB (chlorinated polyolefin manufactured by Toyo Kasei Co., Ltd., 30% toluene solution), HARDREN
14ML (Toyo Kasei Kogyo Co., Ltd. chlorinated polyolefin, toluene 30% solution), Hardlen BS-40 (Toyo Kasei (
Co., Ltd. chlorinated polyolefin, toluene 50% solution), HARDREN B-13 (Toyo Kasei Co., Ltd. chlorinated polyolefin, toluene 30% solution), HARDREN B-4000 (Toyo Kasei Co., Ltd.) chlorinated polyolefin , 30% toluene solution) and various chlorinated polyolefin resins.

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

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

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

Acrylic acid such as alkoxyalkyl ester of methacrylic acid having 2 to 18 carbon atoms, allyl acrylate, allyl methacrylate, or alkenyl ester of methacrylic acid having 2 to 8 carbon atoms, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate , Acrylic acid such as hydroxybutyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate, or acrylic acid such as methacrylic acid having 2 to 8 carbon atoms, acrylic acid such as allyloxyethyl acrylate, and allyloxyethyl methacrylate, or carbon of methacrylic acid. Also included are alkenyloxyalkyl esters of the number 3-18.

Examples of the radically polymerizable monomer include vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene, and polyolefin compounds such as butadiene.
There are also isoprene and chloroprene, and in addition to them, caprolactone-modified acrylic acid ester compound, caprolactone-modified methacrylic acid ester, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, N Examples thereof include methylol methacrylamide, N-methylol acrylamide butyl ether, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol and maleic acid.

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

As the organic solvent, ether-based solvents, ester-based solvents, hydrocarbon-based solvents can be used, and the heating temperature and the polymerization time depend on the radical polymerization initiator and the radical polymerizable monomer used, but in general, It can be obtained by the same method and conditions as the 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 this resin composition is 5 to 80% by weight, preferably 1
It is 0 to 50% by weight. When the content of the chlorinated polyolefin resin is 5% by weight or less, the adhesiveness to the polyolefin material when used as a paint cannot be sufficiently obtained, which is not preferable. 80% chlorinated polyolefin resin content
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 aspect, after the polymerization conversion rate of the radical-polymerizable monomer reaches 70% or more, the radical-polymerization initiator and the radical-polymerizable monomer are continuously added in an amount of 5 to 200% by weight. It can be obtained by adding the vinyl aromatic compound of 1) and continuing the solution polymerization.

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

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

The amount of the vinyl aromatic compound monomer added is 5 to 200% by weight based on the radical polymerizable monomer used in the polymerization initiation stage. Preferably 20-100% by weight
Is. If the amount is 5% by weight or less, sufficient solvent resistance cannot be obtained when used in a paint, which is not preferable. When it is more than 200% by weight, the adhesiveness to the polyolefin material is lowered, which is not preferable.

Further, the vinyl aromatic compound has a polymerization conversion ratio of the radically polymerizable monomer used at the initial stage of polymerization of 70% or less.
Add it when it reaches over%. It is not preferable to add the vinyl aromatic compound when the conversion is 70% or less, because the adhesion to the polyolefin-based material decreases.

Furthermore, a chlorinated polyolefin resin containing methacrylic acid ester, or acrylic acid ester or a mixture of methacrylic acid ester and acrylic acid ester as a radically polymerizable monomer, and styrene as a vinyl aromatic compound is contained. It may be a resin composition.

Next, in the resin composition according to the second embodiment of the present invention, as a polymerization method for obtaining a resin composition in which 5 to 80 parts by weight of the chlorinated polyolefin resin having a chlorine content of 50% by weight or less and styrene are grafted Heating a mixture of radically polymerizable monomers containing 5 to 70% by weight of radically polymerizable polystyrene having a number average molecular weight of 1000 or more having a radically polymerizable double bond at the end together with an organic solvent and a radical polymerization initiator. It is a resin composition containing a chlorinated polyolefin resin obtained by.

Examples of the radical-polymerizable monomer include esters 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 thereof 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, allyl methacrylate, or the like, alkenyl ester of acrylic acid or methacrylic acid having 2 to 8 carbon atoms, hydroxyethyl acrylate, hydroxy Acrylic acid such as ethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or acrylic acid such as methacrylic acid having 2 to 8 hydroxyalkyl ester, allyloxyethyl acrylate, and allyloxyethyl methacrylate. Alternatively, an alkenyloxyalkyl ester of methacrylic acid having 3 to 18 carbon atoms can also be used.

Further, as the radical-polymerizable monomer, there are vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene, and also polyolefin compounds such as butadiene, isoprene and chloroprene.

In addition, caprolactone-modified acrylic acid ester compound, caprolactone-modified methacrylic acid ester, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, acrylamide, N-methylol acrylamide, N-methylol Examples thereof include 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.

The number average molecular weight having a radically polymerizable double bond at the terminal is preferably 1000 or more. When the number average molecular weight is 1000 or less, the coating film hardness is not improved, which is not preferable.

Radical-polymerizable polystyrene having a radical-polymerizable double bond at the end is generally commercially available, and macromonomer AS-6 (terminal methacryloyl group polystyrene; number average molecular weight 6000 Toa Gosei Co., Ltd.) can be exemplified. .

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

The resin composition for coating material of the present invention can be obtained by the same method and conditions as in the radical polymerization reaction of a usual acrylic resin or vinyl resin.

As an example of such a synthesis reaction, a method of dissolving each monomer component in an organic solvent and heating it in a nitrogen atmosphere in the presence of a radical polymerization initiator at a temperature of about 60 to 180 ° C. with stirring is shown. be able to. The reaction time is
Usually, it should be about 1 to 10 hours.

Further, as the organic solvent, an ether solvent, an ester solvent, or a hydrocarbon solvent 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, Examples thereof include azo compounds such as azobisdimethylvaleronitrile.

Next, the 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 fibrin resin, an isocyanate resin, etc., but their amount is preferably not more than 30% by weight in order to maintain the effects of the present invention.

Further, in the resin composition for coating material of the present invention, if necessary, a known coating surface adjusting agent, fluidity adjusting agent,
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.

This coating composition is usually 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, dioxane or ethylene glycol. It can be coated by a general coating method such as spray coating, roll coating or brush coating after diluting with an ether solvent such as diethyl ether or the like or with a mixed solvent.

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

【Example】

Example 1 A 1-liter four-necked round-bottomed flask equipped with a nitrogen introducing tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer was charged with Super Clone E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co.
Toluene 20% solution) 110 g, methyl methacrylate 100
g, 75 g of isobutyl methacrylate, 75 g of normal butyl methacrylate, and 377 g of toluene were charged, and the mixture was heated and stirred while blowing nitrogen gas. Flask temperature is 105
Cdox B-75AW (Kayaku Akzo Co., Ltd.)
Made by benzoyl peroxide, 75% water wet product) 10% by weight
5 g of a toluene solution was added.

Keeping the temperature inside the flask at 105 ° C., 45 minutes and 90 minutes after the initial addition of Cadox B-75AW,
While adding 5 g of 10% toluene solution of Cadox B-75AW and keeping the temperature at 105 ° C., heating and stirring were continued for another 45 minutes. At this point, the rate of addition of acrylic monomer to the polymer at the beginning of the flask was 80% or more, so 75 g of styrene and Cadox B-75AW 10% toluene solution
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 Cadox B-75AW 10% toluene solution was added, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C. Then, cool to room temperature to terminate the reaction,
Next, 30 g of toluene was added to obtain a resin composition for paint of Example 1.

This example contains 8.1% by solid content of the chlorinated polyolefin resin as a component of the coating resin composition at the time of initial charging and 6.3% as a whole of the resin composition,
Polymerization conversion rate of radically polymerizable monomers initially charged 80
This is an example in which 30% by weight of styrene as a vinyl aromatic monomer was added to the radically polymerizable monomer initially charged at the time when the amount reached at least 100% to perform polymerization.

Example 2 A 1-liter four-necked round-bottomed flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer was charged with Super Clone E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd.).
Toluene 20% solution) 150 g, methyl methacrylate 90 g,
75 g of isobutyl methacrylate, 75 g of normal butyl methacrylate, 60 g of AS-6 (radical-polymerizable polystyrene manufactured by Toagosei Co., Ltd., number average molecular weight of 6000) and 310 g of toluene were charged, and the mixture was heated and stirred while blowing 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 inside the flask was kept at 105 ° C., and 45 minutes and 90 minutes after the addition of Cadox B-75AW, 135
Minutes, 180 minutes, 225 minutes later Cadox B-75AW
5 g of a 10% toluene solution was added. After continuing heating and stirring for another 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 resin composition for coating material of Example 2.

In this example, 9.1% chlorinated polyolefin resin as a solid content was contained as a component of the coating resin composition, and 20% by weight of the radical-polymerizable monomer was radical-polymerizable polystyrene.

[Comparative example]

Comparative Example 1 Using the same apparatus as in Example 1, Super Clone E (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 the mixture was heated and stirred while blowing nitrogen gas. When the temperature in the flask reached 105 ° C., 5 g of 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., 75% water wet product) was added.

While keeping the temperature in the flask at 105 ° C., 45 minutes after and 90 minutes after the addition of Cadox B-75AW, 5 g of 10% toluene solution of Cadox B-75AW was added and the temperature was kept at 105 ° C. The heating and stirring were continued for another 45 minutes. At this point, the rate of addition of the acrylic monomer initially added to the flask to the polymer was 80% or more, so 7.5 g of styrene and 5 g of a 10% solution of Cadox B-75AW in toluene were added, and the temperature was adjusted to 105%. The heating and stirring were continued while maintaining the temperature at ℃. 45 and 90 minutes after the addition of styrene, 5 g of Cadox B-75AW 10% toluene solution was added, and while maintaining the temperature at 105 ° C, continue heating and stirring for 120 minutes, then cool to room temperature. The reaction was terminated, and 30 g of toluene was added to obtain a resin composition for coating material of Comparative Example 1.

This comparative example contains 8.1% by solid content of chlorinated polyolefin resin as a component of the coating resin composition at the initial charging time and 6.3% as a whole of the resin composition,
Polymerization conversion rate of radically polymerizable monomers initially charged 80
This is an example in which styrene as a vinyl aromatic monomer was added at 3% by weight to the radically polymerizable monomer initially charged at the time when the amount reached to the level of not less than%.

Comparative Example 2 Using the same apparatus as in Example 1, Super Clone E (chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%) was used.
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 10% by weight toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., 75% water wet product) was added.

The temperature inside the flask was kept at 105 ° C., and 45 minutes after and 90 minutes after the addition of Cadox B-75AW at the beginning, 5 g of a 10% solution of Cadox B-75AW in toluene was added to bring the temperature to 105 ° C. While stirring, heating and stirring were continued for another 45 minutes. At this point, the rate of addition of acrylic monomer added to the flask in the initial stage to the polymer was 80% or more, so 250 g of styrene and 5 g of toluene solution of Cadox B-75AW10% were added, and the temperature was changed to 105 ° C. The heating and stirring was continued while maintaining the temperature at. 45 minutes after adding styrene, and 90
After 10 minutes each Cadox B-75AW 10% toluene solution 5
g, and while maintaining the temperature at 105 ° C, continue heating and stirring for another 120 minutes, then cool to room temperature to end the reaction,
Toluene (30 g) was added to obtain a coating resin composition of Comparative Example 2.

This comparative example contains 16.7% by solid content of chlorinated polyolefin resin as a component of the coating resin composition at the time of initial charging and 5.4% of the resin composition as a whole,
Polymerization conversion rate of radically polymerizable monomers initially charged 80
This is an example in which styrene as a vinyl aromatic monomer was polymerized by adding 250% by weight to the radically polymerizable monomer initially charged at the time when the amount reached to 100% or more.

Comparative Example 3 Using the same apparatus as in Example 1, Super Clone E (a chlorinated polyolefin resin manufactured by Nippon Paper Industries Co., Ltd., toluene 20%) was used.
Solution) 40 g, methyl methacrylate 100 g, isobutyl methacrylate 75 g, normal butyl methacrylate 75 g, and toluene 402 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 wt% toluene solution of Cadox B-75AW (benzoyl peroxide manufactured by Kayaku Akzo Co., Ltd., 75% water wet product) was added.

The temperature inside the flask was kept at 105 ° C., and after 45 minutes and 90 minutes after the initial addition of Cadox B-75AW, 5 g of a 10% solution of Cadox B-75AW in toluene was added to bring the temperature to 105 ° C. While stirring, heating and stirring was continued for another 45 minutes. At this point, the addition rate 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 5 g of a 10% solution of Cadox B-75AW in toluene were added and the temperature was changed to 105 ° C. The heating and stirring was continued while maintaining the temperature at. 45 and 90 minutes after the addition of styrene, 5 g of Cadox B-75AW 10% toluene solution was added, and the mixture was heated and stirred for another 120 minutes while maintaining the temperature at 105 ° C, then cooled to room temperature. To end the reaction and
30 g was added to obtain a resin composition for a coating material of Comparative Example 3.

This comparative example contains chlorinated polyolefin resin as a component of the coating resin composition at a solid content of 3.1% at the initial charging time and the resin composition as a whole is 2.4%,
Polymerization conversion rate of radically polymerizable monomers initially charged 80
This is an example in which 30% by weight of styrene as a vinyl aromatic monomer was added to the radically polymerizable monomer initially charged at the time when the amount reached at least 100% to perform polymerization.

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

Keeping the temperature inside the flask at 105 ° C., add 45 g of styrene after 45 minutes from the beginning when Cadox B-75AW was added.
And Cadox B-75AW 10% toluene solution 5g,
The heating and stirring were continued while maintaining the temperature at 105 ° C. Immediately before the addition of styrene at this point, the polymerization conversion rate of the radically polymerizable monomer initially added was 40%. 45 minutes, 90 minutes, and 135 minutes after the addition of styrene, 5 g of a toluene solution containing 10% of Cadox B-75AW was added, and heating and stirring were continued for another 120 minutes while maintaining the temperature at 105 ° C.
After that, the reaction is terminated by cooling to room temperature and 30 g of toluene
Was added to obtain a coating resin composition of Comparative Example 4.

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

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

The temperature inside the flask was kept at 105 ° C., and 45 minutes and 90 minutes after the initial addition of Cadox B-75AW, 135
Minutes, 180 minutes, 225 minutes later Cadox B-75AW
5 g of a 10% toluene solution was added. Heating and stirring was continued for another 120 minutes while maintaining the temperature at 105 ° C., then the reaction was terminated by cooling to room temperature, and 35 g of toluene was added to Comparative Example 5.
To obtain a resin composition for paint.

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

[Coating film evaluation method]

(A) Paint Preparation and Coating Drying A polypropylene molding material was diluted with the coating resin composition obtained in the above Examples and Comparative Examples with a mixed solvent of 50 parts by weight of toluene and 50 parts by weight of xylene, and air sprayed. The coating was applied uniformly so that the dry film thickness was 10 μm. After the air spraying was completed, the mixture was allowed to stand for 5 minutes and dried in a box-type drying oven at 80 ° C for 30 minutes. By leaving it for another 3 days at room temperature, the drying process was completed and various tests were conducted. The test results are shown in Table 1.

(B) Coating film test items and evaluation method Adhesion test: 1 mm × 1 mm × 100 cuts in a grid pattern and judged by the number of remaining grid patterns after the cellophane tape peeling test. Moisture resistance adhesion test: After leaving it in 50 ℃, 95RH% for 240 hours,
1 mm x 1 mm x 100 cuts, judged by the number of remaining crosses after cellophane tape peeling test. Oil resistance test: 2 g of beef tallow (made by Nakarai Task Co., Ltd.) per 100 cm2 is coated with cotton cloth, wrapped with aluminum foil, left at 80 ℃ for 1h, and then coated with neutral detergent. After washing and natural drying, a cellophane tape peeling test was performed to make a judgment. Cosmetic resistance test: 1g of hair liquid per 100 cm2 (Brass hair liquid manufactured by Shiseido Co., Ltd.) is applied, a cotton cloth is placed on it, and it is wrapped with aluminum foil.
After leaving it to stand, wash the coated surface with a neutral detergent, let it air-dry, and then judge by performing a cellophane tape peeling test.

(C) Test Evaluation Judgment Criteria ◎: Very good ○: Good △: somewhat inferior but usable range ×: defective

[0072]

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,
It has become possible to provide a coating resin composition having excellent coating film hardness and storage stability, a coating composition using the same, and a coated article.

[Table 1]

Front page continued (51) Int.Cl. ⁷ identification code FI C08F 212: 08) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 1/00-10/00 C09D 101/00-201 / 10 C08F 251/00-283/00 C08F 283/02-289/00 C08F 291/00-297/08 C08F 283/01 C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/00 -2/60

Claims (2)

(57) [Claims] 1. A chlorinated poly having a chlorine content of 50% by weight or less.
5 to 80 parts by weight of olefin resin and radically polymerizable monomer
-Mixed with 95 to 20 parts by weight of organic solvent and radical
Solution polymerization by heating with a polymerization initiator,
Polymerization conversion rate of the radically polymerizable monomer is 70% or more
After reaching the free radical polymerization initiator and vinyl aromatic compound
Resin composition for plastic coatings in which solution polymerization is performed by adding
It is those, the vinyl aromatic compound wherein the radical polymerizable monomer
Plus 5 to 200% by weight
Resin composition for tick paint. " 2. The method of claim 1, the radical polymerizable monomer is a mixture of methacrylic acid esters or acrylic acid esters or methacrylic acid esters and acrylic acid ester, and the vinyl aromatic compound is styrene
A resin composition for a plastic coating, which is a len and a styrene derivative .