JP2002338876A - Water-base coating composition and item coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-base coating composition which is excellent in stability, adhesiveness, resistances to water and chemicals, and color-developing properties and can form a coating film with an excellent glossy finish. SOLUTION: This coating composition contains (a) a polyolefin-resin- containing water-base resin composition prepared by emulisifying a polyolefin resin composition obtained by heating a mixture containing a polyolefin resin, a free-radically polymerizable monomer, and a free-radical polymerization initiator and (b) a water-base resin prepared by the emulsion polymerization of a free-radically polymerizable monomer and having a glass transition point of 60 deg.C or higher. The content of ingredient (a) and that of ingredient (b) are 50-90 wt.% and 10-50 wt., respectively, of the sum of contents of ingredients (a) and (b). The content of the polyolefin resin in the polyolefin resin composition is 5-50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a paint having excellent stability, and the resulting coating film shows good adhesion to polyolefin materials such as polyethylene and polypropylene, and plastic materials containing polyolefin and the like.
The present invention also relates to a water-based coating composition which is excellent in water resistance, chemical resistance, and coloring, and can perform excellent gloss finish.

[0002]

2. Description of the Related Art As a coating composition having good adhesion to a polyolefin-based material, a polyolefin-based resin such as a chlorinated polyolefin resin is forcibly emulsified with water and an emulsifier and subjected to solvent removal and the like. There is an aqueous resin which is later used as a paint component.

However, a coating composition using an aqueous resin obtained by forcibly emulsifying a polyolefin resin is:
There was a problem that the durability to chemicals was poor.
Therefore, even if it is possible to use as a primer coating composition, it is possible to finish with a single coating, for example, a coating treatment method represented by a conventional solvent-based lacquer type coating. It was not suitable for various uses.

Therefore, as a coating composition having excellent chemical resistance, an aqueous resin obtained by forcibly emulsifying the polyolefin resin and an acrylic aqueous resin having excellent chemical resistance such as an acrylic emulsion are mixed. Aqueous coating compositions have been proposed.

[0005] However, this aqueous coating composition uses an aqueous resin obtained by forcibly emulsifying a polyolefin resin and an emulsion having a different chemical composition such as an acrylic aqueous resin such as an acrylic emulsion. Since it is a coating composition, there is a problem that good compatibility between different polymers is often difficult to obtain. Therefore, there are problems that the mechanical strength of the formed coating film is insufficient and the adhesion to the material is insufficient.

In order to solve these problems, a resin obtained by graft-polymerizing a polyolefin resin represented by a chlorinated polyolefin resin and an acrylic resin is forcibly emulsified with water and an emulsifier, An aqueous coating composition using an aqueous resin as a coating component after removing the solvent or the like has also been proposed.

An aqueous coating composition comprising an aqueous resin obtained by forcibly emulsifying such a polyolefin resin can be applied to a coating composition for a primer which does not require a high degree of coloring. . However, this water-based paint composition can provide a paint finish with a high degree of color reproducibility, coloring (coloring properties), and glossiness, like a coating film obtained using a conventional organic solvent-based paint. Could not. Therefore, it has been extremely difficult to apply this aqueous coating composition to a coating field where these properties are required.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a coating composition which is excellent in stability and is excellent in a polyolefin material such as polyethylene and polypropylene, and a plastic material containing polyolefin and the like. An object of the present invention is to provide an aqueous coating composition which exhibits excellent adhesion, is excellent in water resistance, chemical resistance, and color development, and can perform excellent gloss finish.

[0009]

That is, the aqueous coating composition of the present invention comprises (a) a polyolefin resin obtained by heating a mixture containing a polyolefin resin, a radical polymerizable monomer and a radical polymerization initiator. A resin composition, a polyolefin-based resin-containing aqueous resin composition emulsified in water,
(B) an aqueous resin obtained by emulsion polymerization of a radical polymerizable monomer and having a glass transition temperature of 60 ° C. or higher,
The ratio of the solid content of the (a) polyolefin-based resin-containing aqueous resin composition is 50% with respect to the total amount of (a) the solid content of the polyolefin-based resin-containing aqueous resin composition and (b) the solid content of the aqueous resin. % To 90% by weight, wherein (b)
The ratio of the solid content of the aqueous resin is 10% by weight to 50% by weight based on the total amount of (a) the solid content of the polyolefin-based resin-containing aqueous resin composition and (b) the solid content of the aqueous resin,
The content of the polyolefin-based resin is 5% by weight to 50% by weight based on the polyolefin-based resin composition.

The (a) radical polymerizable monomer used in the polyolefin resin-containing aqueous resin composition has a glass transition temperature of 60 ° C. or higher of the (co) polymer of the radical polymerizable monomer. Desirably. Also,
(B) The aqueous resin emulsifies the radical polymerizable monomer in the presence of 0.3 to 20.0 parts by weight of a compound having a chain transfer action with respect to 100 parts by weight of the radical polymerizable monomer. It is preferably obtained by polymerization and has a weight average molecular weight in terms of styrene of 100,000 or less.

The aqueous coating composition of the present invention further contains a color pigment, and the color pigment is desirably dispersed in the aqueous resin (b) in advance. Also,
The coated article of the present invention is characterized by having a coating film composed of the aqueous coating composition of the present invention.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. [(A) Polyolefin-based resin-containing aqueous resin composition] The (a) polyolefin-based resin-containing aqueous resin composition of the present invention is obtained by heating a mixture containing a polyolefin-based resin, a radical polymerizable monomer, and a radical polymerization initiator. Is obtained by emulsifying a polyolefin-based resin composition obtained in water with water.

Here, the polyolefin-based resin composition comprises:
Specifically, (a1) a graft polymer of a polyolefin resin and a radical polymerizable monomer, (a2) an unreacted polyolefin resin, and (a3) a (co) polymer of a radical polymerizable monomer It contains. Further, the polyolefin-based resin composition includes these (a1) to (a).
3) Compared to a mixture obtained by simply blending the components, the compatibility is much better, and the coating film formed after applying the aqueous coating composition of the present invention has a mechanical strength and adhesion to a polyolefin material. Excellent in nature.

The polyolefin resin in the present invention refers to a resin whose main skeleton is a polyolefin polymer compound. As polyolefin resins, besides polyethylene, polypropylene, etc., modified polyolefin resins modified with maleic anhydride or the like, hydroxyl group, carboxyl group, methacryloyl group, acryloyl group, epoxy group etc. And a polyolefin-based polymer compound having the same.

[0015] Examples of the polyolefin resin in the present invention include a polyolefin resin modified with chlorine, which is generally called a chlorinated polyolefin resin. As such a chlorinated polyolefin resin, for example, Supercron 77
3H (Nippon Paper Industries, Ltd., chlorinated polyolefin resin), Supercron 822 (Nippon Paper Industries, Ltd., chlorinated polyolefin resin), Supercron 892L (Nippon Paper Industries, Ltd., chlorinated polyolefin resin), Super Clon E (chlorinated polyolefin resin, manufactured by Nippon Paper Industries Co., Ltd.), Hard Len 14LLB (Toyo Kasei Kogyo Co., Ltd.)
Made, chlorinated polyolefin resin), hard len 14ML
(Chlorinated polyolefin resin manufactured by Toyo Kasei Kogyo Co., Ltd.), Hardlen BS-40 (manufactured by Toyo Kasei Kogyo Co., Ltd.
Chlorinated polyolefin resin), Hardlen B-13 (chlorinated polyolefin resin, manufactured by Toyo Kasei Kogyo Co., Ltd.), Hardlen B-2000 (chlorinated polyolefin resin, manufactured by Toyo Kasei Kogyo Co., Ltd.), Hardlen B-4000 (Toyo) Chlorinated polyolefin resin manufactured by Kasei Kogyo Co., Ltd.). These polyolefin resins (including chlorinated polyolefin resins) may be used alone or in combination of two or more.

The content of the polyolefin resin is in the range of 5 to 50% by weight, preferably 10 to 30% by weight, based on the polyolefin resin composition. When the content of the polyolefin-based resin is less than 5% by weight, a coating film formed after applying the water-based coating composition of the present invention cannot have sufficient adhesion to the polyolefin-based material. On the other hand, if the content of the polyolefin-based resin exceeds 50% by weight, the durability of the coating film formed after applying the aqueous coating composition of the present invention, such as weather resistance and chemical resistance, is remarkably reduced. Here, the content of the polyolefin-based resin composition refers to (a1) a polyolefin-based resin contained in a graft polymer of a polyolefin-based resin and a radical polymerizable monomer, and (a2) an unreacted polyolefin-based resin. And the total amount.

As the radically polymerizable monomer in the present invention, it is possible to use a monomer which forms a (co) polymer by radical polymerization alone or in combination of several kinds. Such radically polymerizable monomers include, for example, esters of acrylic acid or methacrylic acid, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid Octyl, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc. Acrylics such as alkyl esters, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate Or alkacrylic acid esters of methacrylic acid having 2 to 18 carbon atoms such as alkoxyalkyl esters having 2 to 18 carbon atoms, allyl acrylate, and allyl methacrylate; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl Methacrylates, hydroxypropyl acrylates, hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms, such as hydroxypropyl methacrylate, allyloxyethyl acrylate,
C3-C18 alkenyloxyalkyl esters of acrylic acid or methacrylic acid such as allyloxyethyl methacrylate;

A vinyl aromatic compound, for example, styrene,
α-methylstyrene, vinyltoluene, p-chlorostyrene; olefinic compounds, for example, butadiene, isoprene, chloroprene; other, 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, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, allyl alcohol, maleic acid and the like can be exemplified. . These radical polymerizable monomers may be used alone or in combination of two or more.

The above radical polymerizable monomers can be used in any combination. The glass transition temperature of the resulting (co) polymer is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. The reason for this is that the coating film finally obtained after applying the aqueous coating composition of the present invention has excellent durability such as chemical resistance.

Here, the glass transition temperature of the (co) polymer of the radical polymerizable monomer differs depending on the molecular weight and distribution thereof, and also depending on the method of measuring the glass transition temperature of the (co) polymer. Therefore, it is difficult to describe clear numerical values and measurement methods. Thus, for example, in the case of the glass transition temperature of a copolymer composed of two types of monomers,
When the values of the known glass transition temperatures of the homopolymers of the respective monomers are Tg1 and Tg2, and the weight fractions of the respective components in the copolymer are W1 and W2, the glass obtained by the following formula is used. The transition temperature is defined as the glass transition temperature in the present invention. Glass transition temperature = W1 × Tg1 + W2 × Tg2

As the radical polymerization initiator, those used in radical polymerization carried out in a usual organic solvent can be used. Examples thereof include benzoyl peroxide, t-butylperoxy-2 Peroxides such as ethylhexanoate; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile;

Next, a method for producing the (a) polyolefin resin-containing aqueous resin composition of the present invention will be described. (A) The polyolefin-based resin-containing aqueous resin composition is prepared by heating a mixture containing a polyolefin-based resin, a radical polymerizable monomer, a radical polymerization initiator, and, if necessary, an organic solvent. The composition can be produced by obtaining a composition, emulsifying the composition by dispersing it in water, and removing the organic solvent contained in the system as necessary. When emulsifying the polyolefin-based resin composition in water, an emulsifier can be used. The polyolefin-based resin composition may be dispersed in water by applying a mechanical shearing force as needed.

Here, the polyolefin resin composition comprises:
It can be obtained by the same method and under the same conditions as in the radical polymerization reaction prescription in an organic solvent used for the production of ordinary acrylic resins and vinyl resins. As an example of such a radical polymerization reaction recipe, a method in which a mixture of the above components is heated while stirring at a temperature of about 60 to 180 ° C. in a nitrogen atmosphere can be shown. The reaction time is usually 1 to 1
It is about 0 hours. In addition, as the organic solvent to be added as needed, ether solvents, ester solvents, hydrocarbon solvents, and the like, which are used in ordinary organic solvent-based paints, can be used.

Examples of the emulsifier include known nonionics,
Anionic or cationic emulsifiers can be used, and polymer-type or reactive emulsifiers can also be used. The type and amount of the emulsifier to be used affect the stability at the time of formulation of the emulsion and the durability such as the chemical resistance of the coating film finally obtained after the aqueous coating composition of the present invention is subjected to the coating treatment. . Therefore, it is necessary to select an appropriate emulsifier according to the polyolefin-based resin composition.

Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether emulsifier, polyoxyethylene octylphenyl ether emulsifier, polyoxyethylene 2-hexylhexyl ether emulsifier, and polyoxyethylene lauryl ether emulsifier. Emulsifier, polyoxyethylene tridecyl ether emulsifier, polyoxyethylene castor oil ether emulsifier, polyoxyethylene cetyl ether emulsifier, polyoxyethylene stearyl ether emulsifier, polyoxyethylene alkylene alkyl emulsifier, polyoxyalkylene glycol emulsifier , Polyoxyethylene oleate emulsifier, polyoxyethylene alkylamine emulsifier, polyoxyethylene sorbitan alkyl emulsifier, polyoxyethylene Emissions polycyclic phenyl ether emulsifiers, polyoxyalkylene polycyclic phenyl ether emulsifiers, polyoxyalkylene nonyl phenyl ether emulsifier and the like; as anionic emulsifier, dodecylbenzene sulfonate NH ₄ salt, dodecylbenzenesulfonic acid Na
Salt, Ca salt of dodecylbenzenesulfonic acid, sodium salt of alkylenedisulfonic acid salt, emulsifier of alkylidiphenyl ether disulfonate, emulsifier of dialkyl succinate sulfonate, emulsifier of monoalkyl succinate sulfonate, polyoxyethylene nonylphenyl Ether sulfate emulsifier, polyoxyethylene alkyl ether sulfate emulsifier, polyoxyethylene allyl ether sulfate emulsifier, polyoxyethylene nonyl phenyl ether phosphate emulsifier, polyoxyethylene alkyl ether phosphate Emulsifiers and the like; and other examples include cationic emulsifiers, zwitterionic emulsifiers, and polymer and reactive emulsifiers.

(A) As an emulsifying formulation for obtaining a polyolefin resin-containing aqueous resin composition, generally, a polymer compound dissolved in an organic solvent-based solvent or a polymer compound having a relatively low melting point The formulation used for emulsification can be used. Such prescriptions include:
For example, a resin in a molten state, a phase inversion emulsification method in which emulsification is performed by stirring with an emulsifier and water, or a resin compound dissolved in water with a hydrocarbon-based organic solvent or the like is added to the emulsifier. An emulsification formulation such as removing an organic solvent component from the emulsion by heating and azeotropic distillation after obtaining the emulsion by performing strong stirring together with the emulsion can be exemplified.

[(B) Aqueous resin] (b) in the present invention
The aqueous resin is obtained by emulsion polymerization of a radical polymerizable monomer, and has a glass transition temperature of 60 ° C. or higher. (B) The radical polymerizable monomer that can be used for the aqueous resin is a radical polymerizable monomer that can generally perform emulsion polymerization, and forms a (co) polymer by emulsion polymerization alone or by several types. Is a radical polymerizable monomer.

Examples of such radical polymerizable monomers include 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, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate,
C1-C18 alkyl esters of acrylic acid or methacrylic acid such as octyl methacrylate and lauryl methacrylate, methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, methoxybutyl acrylate, ethoxybutyl acrylate, methacrylic C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid, such as ethoxybutyl acid; and C2-C8 alkenyl esters of acrylic acid or methacrylic acid, such as allyl acrylate and allyl methacrylate; hydroxyethyl acrylate; hydroxyethyl methacrylate Or acrylic acid such as hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. Hydroxyalkyl esters having 2 to 8 carbon atoms of acrylic acid, allyl oxyethyl acrylate, alkenyloxyalkyl esters having 3 to 18 carbon atoms of acrylic acid or methacrylic acid and allyl methacrylate;

Vinyl aromatic compounds, for example, styrene,
α-methylstyrene, vinyltoluene, p-chlorostyrene; polyolefin-based compounds such as butadiene,
Isoprene, chloroprene; other, 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 can be exemplified. These radical polymerizable monomers may be used alone or in combination of two or more.

The radical polymerizable monomers can be used in any combination, but (b) the glass transition of the aqueous resin obtained by emulsion polymerization of the radical polymerizable monomers singly or in combination. The temperature is at least 60 ° C, more preferably at least 80 ° C. The reason for this is that (b) when an aqueous resin having a glass transition temperature of 60 ° C. or lower is used as the aqueous resin, the coating film obtained after coating the coating composition of the present invention has high durability such as chemical resistance. This is because the properties are significantly reduced.

Here, the glass transition temperature of the aqueous resin (b) varies greatly depending on the molecular weight and the distribution thereof, and also on the method of measuring the glass transition temperature of the aqueous resin (b). Is difficult to describe. Therefore, the glass transition temperature of (b) the glass transition temperature of the aqueous resin is defined as the glass transition temperature obtained from the description of the glass transition temperature described above. That is, in the case of the glass transition temperature of a copolymer composed of two types of monomers, the values of the glass transition temperatures known as a homopolymer composed of each monomer are defined as Tg1 and Tg2, respectively. The weight fraction of the component
And W2, the glass transition temperature obtained by the following equation is defined as the glass transition temperature in the present invention. Glass transition temperature = W1 × Tg1 + W2 × Tg2

Next, the method for producing the aqueous resin (b) in the present invention will be described. (B) The aqueous resin can be obtained by the same method and under the same conditions as those used in the general emulsion polymerization of a radical polymerizable compound. As an example of such an emulsion polymerization formulation, for example, a reaction vessel containing an appropriate amount of ion-exchanged water is heated to 50 ° C. or higher and 100 ° C.
Emulsion polymerization in which a pre-emulsion composed of a mixture of a separately prepared radical polymerizable monomer, a water-soluble radical polymerization initiator, ion-exchange water and an emulsifier is dropped into the reaction vessel over several hours while maintaining the temperature below. Method and a part of the pre-emulsion is added to a reaction vessel together with ion-exchanged water in advance, and seed particles in emulsion polymerization are obtained by raising the temperature,
Thereafter, a method of dropping the remaining pre-emulsified product over several hours can be exemplified.

Examples of the water-soluble radical polymerization initiator include water-soluble radical polymerization initiators such as ammonium peroxodisulfate and potassium peroxodisulfate. In some cases, the water-insoluble radical polymerization initiator may be used alone or in combination with the water-soluble radical polymerization initiator.

As the emulsifier required for the emulsion polymerization, those generally used in emulsion polymerization of radically polymerizable monomers can be used. For example, a known nonionic, anionic or cationic emulsifier can be used, and a polymer type emulsifier or a reactive emulsifier can also be used. The type and amount of the emulsifier to be used affect the stability at the time of formulation of the emulsion and the durability such as the chemical resistance of the coating film finally obtained after the aqueous coating composition of the present invention is subjected to the coating treatment. Therefore, an appropriate choice is needed.

Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether emulsifier, polyoxyethylene octylphenyl ether emulsifier, polyoxyethylene 2-hexylhexyl ether emulsifier, and polyoxyethylene lauryl. Ether type emulsifier, polyoxyethylene tridecyl ether type emulsifier, polyoxyethylene castor oil ether type emulsifier, polyoxyethylene cetyl ether type emulsifier,
Polyoxyethylene stearyl ether emulsifier, polyoxyethylene alkylene alkyl emulsifier, polyoxyalkylene glycol emulsifier, polyoxyethylene oleate emulsifier, polyoxyethylene alkylamine emulsifier, polyoxyethylene sorbitan alkyl emulsifier, polyoxyethylene Polycyclic phenyl ether type emulsifier, polyoxyalkylene polycyclic phenyl ether type emulsifier, polyoxyalkylene nonyl phenyl ether type emulsifier, etc .; dodecylbenzenesulfonic acid NH ₄ salt, dodecylbenzenesulfonic acid N as anionic emulsifier
a salt, dodecylbenzenesulfonic acid Ca salt, alkylenedisulfonic acid Na salt emulsifier, alkylidiphenyl ether disulfonate emulsifier, dialkyl succinate sulfonate emulsifier, monoalkyl succinate sulfonate emulsifier, polyoxyethylene nonyl Phenyl ether sulfate ester emulsifier, polyoxyethylene alkyl ether sulfate ester emulsifier, polyoxyethylene allyl ether sulfate ester emulsifier, polyoxyethylene nonyl phenyl ether phosphate ester emulsifier, polyoxyethylene alkyl ether phosphate Other examples include cationic emulsifiers, zwitterionic emulsifiers, and high molecular weight and reactive emulsifiers.

In the formulation of the aqueous resin (b) in the present invention, it is preferable to use a compound having a chain transfer effect, which is used as a chain transfer agent in a general radical polymerization reaction. The reasons are as follows. The polymer compound obtained by emulsion polymerization generally has a large molecular weight. Therefore, when the aqueous coating composition of the present invention uses a high-molecular-weight aqueous resin, the aqueous coating composition of the present invention uses an organic solvent or the like as a film-forming aid for the purpose of forming a good coating film after the coating treatment. Even if it is added to the product, the action of the film-forming aid is not sufficiently exhibited,
The flatness of the coating film after the coating treatment may be insufficient. As a result, in the appearance of the article after the article is coated with the aqueous coating composition of the present invention, a good appearance such as excellent glossiness may not be obtained. By adding a compound having a chain transfer effect, the molecular weight of (b) the aqueous resin can be suppressed to a low level, and the article has excellent glossiness in appearance after the aqueous coating composition of the present invention is applied to the article. Good appearance such as is obtained.

As the chain transfer agent, a mercaptan-based compound, a chlorine-based compound, a compound which exhibits a strong chain transfer action in a radical polymerization reaction, or the like can be used. The amount used is preferably 0.3 parts by weight to 20.0 parts by weight, more preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the radical polymerizable monomer used in the formulation of the aqueous resin (b). Part by weight is more preferable, and 1 to 5 parts by weight is further preferable. If the amount of the chain transfer agent is less than 0.3 parts by weight, the above-mentioned effects appearing in the water-based coating composition of the present invention are small, which is not preferable. On the other hand, when the amount of the chain transfer agent exceeds 20.0 parts by weight, the molecular weight of the formed polymer becomes too small, or the remaining chain transfer agent acts as an impurity, and the physical properties of the formed coating film deteriorate. And unfavorable effects such as the generation of unpleasant odor are not preferred.

In the present invention, the molecular weight of the aqueous resin (b) is 10 as a weight average molecular weight in terms of styrene.
It is preferably not more than 0000, more preferably not more than 50,000, and still more preferably 3 or less.
It is less than 000. When the weight average molecular weight in terms of styrene exceeds 100,000, as described above, an organic solvent or the like is used for the purpose of forming a good coating film after the water-based coating composition of the present invention is applied. Even if it is added as a film-forming aid, the effect of the film-forming aid is not sufficiently exerted, so that the flatness of the coating film after the coating treatment becomes insufficient, so that the glossiness after the coating treatment on the article, etc. Appearance is deteriorated.

[Aqueous coating composition] The aqueous coating composition of the present invention contains (a) the aqueous resin composition containing a polyolefin resin described above and (b) the aqueous resin. In the aqueous coating composition of the present invention, (a) the solid content of the polyolefin-based resin-containing aqueous resin composition is determined by: (a) the solid content of the polyolefin-based resin-containing aqueous resin composition; and (b) the solid content of the aqueous resin. 5
0% to 90% by weight, and the proportion of (b) the solid content of the aqueous resin is defined as the total amount of (a) the solid content of the polyolefin resin-containing aqueous resin composition and (b) the solid content of the aqueous resin. On the other hand, it is 10% by weight to 50% by weight.

When (a) the solid content of the polyolefin-based resin-containing aqueous resin composition is less than 50% by weight, that is, (b) when the solid content of the aqueous resin is more than 50% by weight, (a)
Due to the shortage of the polyolefin-based resin-containing aqueous resin composition, the adhesion of the coating film formed after applying the aqueous coating composition of the present invention to the polyolefin-based material cannot be sufficiently obtained. On the other hand, when (a) the solid content of the polyolefin-based resin-containing aqueous resin composition exceeds 90% by weight, that is, when (b) the solid content of the aqueous resin is less than 10% by weight, (b) the aqueous resin is insufficient. In addition, the flatness of the coating film after the water-based coating composition of the present invention has been coated becomes insufficient, and thus the appearance such as glossiness after the coating processing of the article is reduced. In the case where (b) an organic or inorganic color pigment is dispersed by using an aqueous resin, it is possible to impart high coloring power and hiding power to the aqueous coating composition of the present invention. It becomes necessary to disperse an excessive amount of the color pigment in the aqueous resin. For this reason, the fine dispersibility of the pigment deteriorates, and problems such as the hue, color development, hiding power, and the like inherent to the pigment cannot be obtained.

When the aqueous coating composition of the present invention is used in an article as a clear coat paint for gloss finishing,
Gives a painted product with excellent glossiness. In addition, a water-based paint can be obtained by dispersing a color pigment therein, and a water-based paint composition having excellent coloring properties can be obtained. As the color pigment, an organic or inorganic color pigment which is usually used as a color pigment for a paint can be used.

It is preferable that the coloring pigment is previously dispersed in the aqueous resin (b). in this case,
(B) A colored pigment or the like is dispersed in the aqueous resin to obtain a colored (b) aqueous resin composition, and (a) a polyolefin-based resin-containing aqueous resin composition is added to the composition. An aqueous coating composition is obtained. Such a colored aqueous coating composition forms a coating film with extremely high uniformity, flatness and good coloring by forming a coating film using a part of a film-forming aid such as an organic solvent. It is possible to

It is also possible to disperse the color pigment in the (a) polyolefin resin-containing aqueous resin composition. However, in this case, since the coloring pigment does not sufficiently adapt to the resin particles, not only may there be a problem in the coloring property and the concealing property, but also the adhesion of the formed coating film to the material and the mechanical strength of the coating film. Further, there is a possibility that a problem such as a decrease in durability against chemicals or the like may occur, which is not preferable.

In the aqueous coating composition of the present invention, a pigment is dispersed by using a water-soluble pigment-dispersing resin composition as used in general aqueous coating compositions. It is also possible to add pigment pastes. However, in general, the chemical properties of the water-soluble pigment-dispersing resin composition and the polyolefin-based resin-containing aqueous resin composition are significantly different from each other, so that the compatibility of the respective compounds is not always good. As a result, there is a possibility that a problem may occur with respect to the coloring property and concealing property of the paint, or a problem may occur such that the adhesion of the formed coating film to the material, the mechanical strength of the coating film, and the durability to chemicals and the like are reduced. It is not preferable because there is.

The above-mentioned film-forming aid is used in an aqueous paint or the like using an aqueous emulsion type emulsified resin in order to smoothly form a coating film by fusing resin fine particles.
It is a compound such as an organic solvent added to the water-based paint as needed. As such a film forming aid, for example, an ether solvent, an ester solvent, and a hydrocarbon solvent can be used. Preferred are glycol ether-based, propylene glycol-based, and dialkyl glycol ether-based organic solvents, for example, methyl glycol, methyl diglycol, methyl triglycol, methyl polyglycol, methyl propylene glycol, methyl propylene diglycol, propyl propylene glycol, Propyl propylene diglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, butyl propylene glycol, butyl propylene diglycol, phenyl propylene diglycol, methyl propylene glycol acetate, dimethyl glycol, dimethyl diglycol, diethyl di Glycol, dibutyldiglycol, dimethyltriglycol, etc. Can Shimesuru.

The above-mentioned film-forming aid affects the state of formation of the coating film depending on the kind and the amount of the addition. Since the mechanical strength of the coating film and the durability of the coating film to chemicals and the like are reduced, it is necessary to appropriately select the type and amount of the coating film.

The aqueous coating composition of the present invention is an aqueous coating composition containing the above-mentioned specific components. If necessary, a known coating surface adjuster, fluidity adjuster, ultraviolet absorber, light stabilizer Agents, curing catalysts, extender pigments, coloring pigments, metal pigments, mica powder pigments, dyes, organic solvents, and the like.

The coated product of the present invention has a coating film composed of the aqueous coating composition of the present invention, and is obtained by coating various materials with the aqueous coating composition of the present invention. The aqueous coating composition of the present invention can be generally diluted with water or an organic solvent alone or a mixed solution, and applied by a coating method such as spray coating, roll coating, and brush coating. The water-based coating composition of the present invention is not limited to application to only polyolefin-based materials, and includes ABS resin,
It can also be used for molded plastic products such as PC resin and nylon, and metal products such as stainless steel and chrome plating. The aqueous coating composition of the present invention can be dried at room temperature,
Baking and drying at a low temperature of 0 ° C. or less is possible.

[0049]

The present invention will be described below with reference to examples, but the present invention is not limited by these examples. Example 1 (1) Synthesis of Polyolefin-Based Resin Composition Hardlen B-2000 (Toyo) 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. 240 g of chlorinated polyolefin resin, organic solvent dilution containing 30% by weight of chlorinated polyolefin resin, 163.3 g of methyl methacrylate, tertiary butyl methacrylate 2 manufactured by Kasei Kogyo Co., Ltd.
40.7 g, methacrylic acid 4.0 g, toluene 952.
0 g was added and heated to 90 ° C. The temperature in the flask is 90
° C, Kayaester O
2.0 g of a peroxide compound (manufactured by Kayaku Akzo Co., Ltd.) was added. Thereafter, stirring was continued while the temperature in the flask was maintained at 90 ° C., and after one hour of addition of peroxide, Kayaester O (manufactured by Kayaku Akzo Co., Ltd.) 1 hour, 2 hours, and 3 hours later, respectively. , Peroxide compound). Thereafter, the temperature in the flask was further reduced to 9 for 3 hours.
After maintaining at 0 ° C., the temperature in the flask was cooled to room temperature to terminate the reaction, and a polyolefin resin composition used in Example 1 was obtained.

(2) Formulation of (a) Polyolefin Resin-Containing Aqueous Resin Composition Resin solution comprising 50% by weight of polyolefin resin composition obtained in (1) and 50% by weight of toluene
g, Newcol 740SF (manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier) (3.0 g) and ion-exchanged water (297 g) were mixed sufficiently using a high-speed stirrer to obtain an emulsion. Used in Example 1 by heating the emulsion and performing azeotropic distillation to remove the organic solvent component contained in the emulsion and continuing the distillation until the solid content becomes 30% by weight. (A) A polyolefin resin-containing aqueous resin composition was obtained.

(3) (b) Synthesis of Aqueous Resin 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, 250.0 g of ion-exchanged water, 5.0 g of Cole 707SF (an anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.) was added. Separately from this, 43.0 g of methyl methacrylate, 100.0 g of tertiary butyl methacrylate, 2.10 g of methacrylic acid.
0 g, Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd.)
Anionic emulsifier) 10.0 g, ammonium persulfate 1
A mixture of 15.0 g of a 0% aqueous solution and 75.0 g of ion-exchanged water was vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion. 12.5g of this pre-emulsion
Was added to the flask, and then the temperature in the flask was increased to 80 ° C. while stirring and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours. After completion of the dropping of the pre-emulsion, the temperature in the flask was maintained at 80 ° C. for 3 hours, and then cooled to room temperature to obtain the aqueous resin (b) used in Example 1.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) the aqueous resin composition containing polyolefin resin obtained in (2) and 27 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene The aqueous coating composition of Example 1 was obtained by mixing 10 parts by weight of diglycol and stirring the mixture until it became uniform.

In this example, 70% by weight of a polyolefin-based resin-containing aqueous resin composition obtained by emulsifying a polyolefin-based resin composition obtained from 15% by weight of a polyolefin-based resin and 85% by weight of a radical polymerizable monomer mixture was used. % (Solid content) and a radical polymerizable monomer mixture, obtained by emulsion polymerization, having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 240,000. It is an example of an aqueous resin composition comprising% by weight (solid content). The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 2 (1) Synthesis of Polyolefin Resin Composition Using the same apparatus as in Example 1 (1), Hardlen B-2 was used.
480 g (manufactured by Toyo Kasei Kogyo Co., Ltd., chlorinated polyolefin resin, organic solvent dilution containing 30% by weight of chlorinated polyolefin resin), methyl methacrylate 1
34.4 g, tertiary butyl methacrylate 198.
2 g, 3.4 g of methacrylic acid, and 784.0 g of toluene were added, and the mixture was heated to 90 ° C. When the temperature in the flask reached 90 ° C., 2.0 g of Kayaester O (a peroxide-based compound manufactured by Kayaku Akzo Co., Ltd.) was added while stirring was continued. Thereafter, stirring was continued while maintaining the temperature in the flask at 90 ° C., and one hour after the peroxide was first added, 2 hours later
After a lapse of 3 hours, 2.0 g of Kayaester O (a peroxide-based compound manufactured by Kayaku Akzo Co., Ltd.) was added.
Thereafter, the temperature in the flask was further increased to 90 ° C. for 3 hours.
After keeping the temperature in the flask, the temperature in the flask was cooled to room temperature to terminate the reaction, and a polyolefin-based resin composition used in Example 2 was obtained.

(2) Formulation of (a) polyolefin resin-containing aqueous resin composition (a) Polyolefin resin used in Example 2 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) The resulting aqueous resin composition was obtained. (3) (b) Synthesis of aqueous resin Using the same apparatus and formulation as in Example 1 (3), an aqueous resin (b) used in Example 2 was obtained.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2) and 27 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene The aqueous coating composition of Example 2 was obtained by mixing 10 parts by weight of diglycol and stirring the mixture until it became uniform.

In this example, the polyolefin resin composition obtained from 30% by weight of the polyolefin resin and 70% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition % (Solid content) and a radical polymerizable monomer mixture, obtained by emulsion polymerization, having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 240,000. It is an example of an aqueous resin composition comprising% by weight (solid content). The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 3 (1) Synthesis of Polyolefin Resin Composition Using the same apparatus as in Example 1 (1), Hardlen B-2 was used.
240 g (manufactured by Toyo Kasei Kogyo Co., Ltd., chlorinated polyolefin resin, diluted organic solvent containing 30% by weight of chlorinated polyolefin resin), methyl methacrylate 1
63.2 g, normal butyl methacrylate 102.0
g, 138.8 g of normal butyl acrylate, 4.0 g of methacrylic acid, and 784.0 g of toluene, and the mixture was heated to 90 ° C. When the temperature in the flask reaches 90 ° C., Kayaester O (Kakuyaku Akzo Co., Ltd.) is maintained while stirring is continued.
2.0 g of peroxide compound). Thereafter, stirring was continued while the temperature in the flask was maintained at 90 ° C., and after one hour of addition of the peroxide, one hour, two hours, and three hours later, Kayaester O (Kakuyaku Akzo Co., Ltd.) Made,
2.0 g of a peroxide compound) was added. Then, after maintaining the temperature in the flask at 90 ° C. for further 3 hours,
The temperature in the flask was cooled to room temperature to terminate the reaction, and a polyolefin-based resin composition used in Example 3 was obtained.

(2) (a) Formulation of polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin used in Example 3 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) The resulting aqueous resin composition was obtained. (3) (b) Synthesis of Aqueous Resin (b) Aqueous resin used in Example 3 was obtained using the same apparatus and formulation as in Example 1 (3).

(4) Preparation of aqueous coating composition 63 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2) and (b) 27 parts by weight of aqueous resin obtained in (3), and butyl propylene The mixture was mixed with 10 parts by weight of diglycol, and the mixture was stirred until it became uniform to obtain an aqueous coating composition of Example 3.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture, obtained by emulsion polymerization, having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 240,000. It is an example of an aqueous resin composition comprising% by weight (solid content). The glass transition temperature of the copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 30 ° C.

Example 4 (1) Synthesis of Polyolefin Resin Composition Example 4 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Example 4 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1 (3), 250.0 g of ion-exchanged water and Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic (Emulsifier) 5.0 g. Separately, 48.0 g of methyl methacrylate, 100.0 g of tert-butyl methacrylate, 2.0 g of methacrylic acid, 10.0 g of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier), 10.0 g of ammonium persulfate A mixture of 15.0 g of a 1% aqueous solution, 1.5 g of normal dodecyl mercaptan, and 75.0 g of ion-exchanged water was vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion. After 12.5 g of this pre-emulsion was added into the flask, the temperature in the flask was increased to 80 ° C. while stirring and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours. After completion of the dropping of the pre-emulsion, the temperature in the flask was maintained at 80 ° C. for 3 hours, and then cooled to room temperature to obtain an aqueous resin (b) used in Example 4.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2) and (b) 27 parts by weight of aqueous resin obtained in (3), and butyl propylene The aqueous coating composition of Example 4 was obtained by mixing 10 parts by weight of diglycol and stirring the mixture until it became uniform.

In this example, 70% by weight of a polyolefin resin-containing aqueous resin composition (a) in which a polyolefin resin composition obtained from 15% by weight of a polyolefin resin and 85% by weight of a radical polymerizable monomer mixture were emulsified. % (Solid content), and a mixture of a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent in an amount of 1.0 part by weight, based on 100 parts by weight of the radical polymerizable monomer mixture, by emulsion polymerization. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 30,000. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 5 (1) Synthesis of Polyolefin Resin Composition Example 5 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Example 5 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1 (3), 250.0 g of ion-exchanged water and Newcol 707SF (Nippon Emulsifier Co., Ltd. (Emulsifier) 5.0 g. Separately, 48.0 g of methyl methacrylate, 100.0 g of tertiary butyl methacrylate, 2.0 g of methacrylic acid, 10.0 g of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier), 10.0 g of ammonium persulfate A mixture of 15.0 g of a 1% aqueous solution, 4.5 g of normal dodecyl mercaptan, and 75.0 g of ion-exchanged water was vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion. After 12.5 g of this pre-emulsion was added into the flask, the temperature in the flask was increased to 80 ° C. while stirring and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours. After the completion of the dropping of the pre-emulsion, the temperature in the flask was kept at 80 ° C. for 3 hours and then cooled to room temperature to obtain the aqueous resin (b) used in Example 5.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2) and (b) 27 parts by weight of aqueous resin obtained in (3), and butyl propylene The mixture was mixed with 10 parts by weight of diglycol and stirred until they became uniform to obtain an aqueous coating composition of Example 5.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition % (Solid content), a radical polymerizable monomer mixture, and 3.0 parts by weight of normal dodecyl mercaptan as a chain transfer agent, based on 100 parts by weight of the radical polymerizable monomer mixture, and emulsion polymerization. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 10,000. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 6 (1) Synthesis of Polyolefin Resin Composition Example 6 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Example 6 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of aqueous resin Using the same apparatus as in Example 1 (3), 250.0 g of ion-exchanged water and Newcol 707SF (Nippon Emulsifier Co., Ltd. (Emulsifier) 5.0 g. Separately, 48.0 g of methyl methacrylate, 100.0 g of tert-butyl methacrylate, 2.0 g of methacrylic acid, 10.0 g of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier), 10.0 g of ammonium persulfate % Of an aqueous solution, 15.0 g of normal dodecyl mercaptan, and 75.0 g of ion-exchanged water were vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion. 12.5g of this pre-emulsion
Was added to the flask, and while stirring, the temperature in the flask was raised to 80 ° C. and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours. After completion of dropping of the pre-emulsion, the temperature in the flask was kept at 80 ° C. for 3 hours, and then cooled to room temperature to obtain an aqueous resin (b) used in Example 6.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2) and (b) 27 parts by weight of aqueous resin obtained in (3), and butyl propylene The aqueous coating composition of Example 6 was obtained by mixing 10 parts by weight of diglycol and stirring the mixture until it became uniform.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition % (Solid content), a radical polymerizable monomer mixture, and normal dodecyl mercaptan as a chain transfer agent, 10.0 parts by weight based on 100 parts by weight of the radical polymerizable monomer mixture, and emulsion polymerization. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 4,000. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 7 (1) Synthesis of Polyolefin Resin Composition Example 7 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Example 7 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1 (3), 250.0 g of ion-exchanged water and Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic (Emulsifier) 5.0 g. Separately, 48.0 g of methyl methacrylate, 100.0 g of tertiary butyl methacrylate, 2.0 g of methacrylic acid, 10.0 g of Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier), 10.0 g of ammonium persulfate % Of an aqueous solution, 45.0 g of normal dodecyl mercaptan, and 75.0 g of ion-exchanged water were vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion. 12.5g of this pre-emulsion
Was added to the flask, and while stirring, the temperature in the flask was raised to 80 ° C. and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours. After completion of the dropping of the pre-emulsion, the temperature in the flask was kept at 80 ° C. for 3 hours, and then cooled to room temperature to obtain the aqueous resin (b) used in Example 7.

(4) Preparation of aqueous coating composition 63 parts by weight of (a) aqueous resin composition containing polyolefin resin obtained in (2) and 27 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene The mixture was mixed with 10 parts by weight of diglycol, and the mixture was stirred until it became uniform to obtain an aqueous coating composition of Example 7.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content), and a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent, obtained by emulsion polymerization using 30.0 parts by weight in combination with 100 parts by weight of the radical polymerizable monomer mixture. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 1,500. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Comparative Example 1 (1) Synthesis of Polyolefin Resin Composition Using the same apparatus as in Example 1 (1), Hardlen B-2 was used.
48 g of 000 (manufactured by Toyo Kasei Kogyo Co., Ltd., chlorinated polyolefin resin, diluted organic solvent containing 30% by weight of chlorinated polyolefin resin), methyl methacrylate 18
6.2 g, tertiary butyl methacrylate 274.7
g, 4.7 g of methacrylic acid and 1086.4 g of toluene were added and heated to 90 ° C. When the temperature in the flask reached 90 ° C., 2.0 g of Kayaester O (a peroxide-based compound manufactured by Kayaku Akzo Co., Ltd.) was added while stirring was continued. Thereafter, stirring was continued while maintaining the temperature in the flask at 90 ° C., and one hour after the peroxide was first added, 2 hours later
After a lapse of 3 hours, 2.0 g of Kayaester O (a peroxide-based compound manufactured by Kayaku Akzo Co., Ltd.) was added.
Thereafter, the temperature in the flask was further increased to 90 ° C. for 3 hours.
After keeping the temperature in the flask, the temperature in the flask was cooled to room temperature to terminate the reaction, and a polyolefin-based resin composition used in Comparative Example 1 was obtained.

(2) Formulation of Polyolefin Resin-Containing Aqueous Resin Composition The polyolefin resin-containing aqueous resin composition used in Comparative Example 1 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) was prepared. Obtained. (3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1 and using the formulation of Example 4, (b) an aqueous resin used in Comparative Example 1 was obtained.

(4) Preparation of aqueous coating composition 63 parts by weight of polyolefin resin-containing aqueous resin composition obtained in (2), 27 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene diglycol 10 Mix with parts by weight,
The mixture was stirred until it became uniform to obtain an aqueous coating composition of Comparative Example 1.

In this comparative example, a polyolefin-based resin-containing aqueous resin composition obtained by emulsifying a polyolefin-based resin composition obtained from 3% by weight of a polyolefin-based resin and 97% by weight of a radical polymerizable monomer mixture was used. Minutes)
And a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent are obtained by emulsion polymerization using 1.0 part by weight in combination with 100 parts by weight of the radical polymerizable monomer mixture, and the glass transition temperature is obtained. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a weight average molecular weight of 30,000 in terms of styrene at 105 ° C. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Comparative Example 2 (1) Synthesis of Polyolefin Resin Composition Using the same apparatus as in Example 1 (1), Hardlen B-2 was used.
000 (manufactured by Toyo Kasei Kogyo Co., Ltd., chlorinated polyolefin resin, diluted organic solvent containing 30% by weight of chlorinated polyolefin resin) 1120.0 g, methyl methacrylate 57.5 g, tertiary butyl methacrylate 8
5.0 g, methacrylic acid 1.5 g, toluene 336.0
g and heated to 90 ° C. The temperature in the flask is 90 ° C
Is reached, Kayaester O is added while stirring is continued.
2.0 g of a peroxide compound (manufactured by Kayaku Akzo Co., Ltd.) was added. Thereafter, stirring was continued while maintaining the temperature in the flask at 90 ° C., and after 1 hour, 2 hours, and 3 hours after the peroxide was first added, each of the Kayaester O was added.
2.0 g of a peroxide compound (manufactured by Kayaku Akzo Co., Ltd.) was added. Then, after maintaining the temperature in the flask at 90 ° C. for further 3 hours, the temperature in the flask was cooled to room temperature to terminate the reaction, and a polyolefin resin composition used in Comparative Example 2 was obtained.

(2) Formulation of Polyolefin-Based Resin-Containing Aqueous Resin Composition The polyolefin-based resin-containing aqueous resin composition used in Comparative Example 2 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) was prepared. Obtained. (3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1, using the formulation of Example 4, (b) an aqueous resin used in Comparative Example 2 was obtained.

(4) Preparation of aqueous coating composition 63 parts by weight of polyolefin resin-containing aqueous resin composition obtained in (2), 27 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene diglycol 10 Mix with parts by weight,
This was stirred until it became uniform to obtain a water-based coating composition of Comparative Example 2.

In this comparative example, a polyolefin resin-containing aqueous resin composition obtained by emulsifying a polyolefin resin composition obtained from a polyolefin resin 70% by weight and a radical polymerizable monomer mixture 30% by weight (solid Minutes)
And a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent are obtained by emulsion polymerization using 1.0 part by weight in combination with 100 parts by weight of the radical polymerizable monomer mixture, and the glass transition temperature is obtained. This is an example of an aqueous resin composition comprising (b) 30% by weight (solid content) of an aqueous resin having a weight average molecular weight of 30,000 in terms of styrene at 105 ° C. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Comparative Example 3 (1) Synthesis of Polyolefin Resin Composition Comparative Example 3 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Comparative Example 3 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) Synthesis of Aqueous Resin Using the same apparatus as in Example 1 (3), 250.0 g of ion-exchanged water and Newcol 707SF (anionic emulsifier, manufactured by Nippon Emulsifier Co., Ltd.) were used in a flask. 0.0 g was added. Separately, 52.5 g of methyl methacrylate, 64.5 g of normal butyl methacrylate, 30.0 g of normal butyl acrylate, 3.0 g of methacrylic acid, Newcol 707SF (Nippon Emulsifier Co., Ltd., anionic emulsifier) 10.0 g, 10% aqueous solution of ammonium persulfate 1
A mixture of 5.0 g, normal dodecyl mercaptan 1.5 g, and ion-exchanged water 75.0 g was vigorously stirred using a high-speed stirrer to obtain 250 g of a pre-emulsion.
After 12.5 g of this pre-emulsion was added into the flask, the temperature in the flask was increased to 80 ° C. while stirring and maintained for 1 hour. Thereafter, the entire remaining amount of the pre-emulsion prepared above was dropped into the flask over 3 hours.
After the completion of the dropping of the pre-emulsion, the temperature in the flask was kept at 80 ° C. for 3 hours and then cooled to room temperature to obtain an aqueous resin used in Comparative Example 3.

(4) Preparation of aqueous coating composition 63 parts by weight of the (a) polyolefin resin-containing aqueous resin composition obtained in (2), 27 parts by weight of aqueous resin obtained in (3), and butyl propylene diglycol 10 Mix with parts by weight,
This was stirred until it became uniform to obtain a water-based coating composition of Comparative Example 3.

In this comparative example, 70% by weight of a polyolefin resin-containing aqueous resin composition obtained by emulsifying a polyolefin resin composition obtained from 15% by weight of a polyolefin resin and 85% by weight of a radical polymerizable monomer mixture was used. % (Solid content), and a mixture of a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent in an amount of 1.0 part by weight based on 100 parts by weight of the radical polymerizable monomer mixture, and emulsion polymerization. Has a glass transition temperature of 37 ° C.,
This is an example of an aqueous resin composition comprising 30% by weight (solid content) of an aqueous resin having a weight average molecular weight of 30,000 in terms of styrene. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Comparative Example 4 (1) Synthesis of Polyolefin Resin Composition Comparative Example 4 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Comparative Example 4 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of Aqueous Resin Using the same apparatus as in Example 1, using the formulation of Example 5, (b) an aqueous resin used in Comparative Example 4 was obtained. (4) Preparation of aqueous coating composition 27 parts by weight of (a) aqueous resin composition containing polyolefin resin obtained in (2), 63 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene The aqueous coating composition of Comparative Example 4 was obtained by mixing 10 parts by weight of glycol and stirring the mixture until it became uniform.

In this comparative example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 30% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content), and a mixture of a radical polymerizable monomer mixture and normal dodecyl mercaptan as a chain transfer agent in an amount of 3.0 parts by weight based on 100 parts by weight of the radical polymerizable monomer mixture and emulsion polymerization. This is an example of an aqueous resin composition comprising (b) 70% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C and a weight average molecular weight in terms of styrene of 10,000. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Comparative Example 5 (1) Synthesis of Polyolefin Resin-Containing Resin Composition Comparative Example 5 was prepared using the same apparatus and synthesis method as in Example 1 (1).
To obtain a polyolefin-based resin composition to be used. (2) Formulation of (a) polyolefin-based resin-containing aqueous resin composition (a) Polyolefin-based resin-containing aqueous resin used in Comparative Example 5 having a solid content of 30% by weight according to the same formulation as in Example 1 (2) A composition was obtained.

(3) (b) Synthesis of aqueous resin Using the same apparatus as in Example 1 and using the formulation of Example 5, (b) an aqueous resin used in Comparative Example 5 was obtained. (4) Preparation of aqueous coating composition 86 parts by weight of (a) polyolefin resin-containing aqueous resin composition obtained in (2), 4 parts by weight of (b) aqueous resin obtained in (3), and butyl propylene diglycol 10 Parts by weight, and the mixture was stirred until it became uniform to obtain an aqueous coating composition of Comparative Example 5.

In this comparative example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 95% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content), a radical polymerizable monomer mixture, and 3.0 parts by weight of normal dodecyl mercaptan as a chain transfer agent, based on 100 parts by weight of the radical polymerizable monomer mixture, and emulsion polymerization. This is an example of an aqueous resin composition comprising (b) 5% by weight (solid content) of an aqueous resin having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 10,000. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Examples 8 to 19 are examples in which the aqueous coating composition of the present invention was evaluated for suitability for coloring by pigment dispersion. Example 8 100 g of a polyolefin-based resin-containing aqueous resin composition of Example 4 (2), Regal R400
(Cabot Co., Ltd., carbon black) 10.0
g, 32% ammonia water 0.5 g, SN deformer 3
18 (manufactured by San Nopco Co., Ltd., defoamer) and ion-exchanged water (50.0) together with 200 g of zircon beads for dispersing a pigment having a diameter of 3 mm are placed in a plastic container, and sufficiently dispersed using a paint shaker. went. Example 8 100 g of the black paint obtained by the pigment dispersion formulation, 27 g of the aqueous resin (b) in Example 4 (3), and 9 g of butylpropylene diglycol were mixed and stirred until uniform. A water-based paint composition colored black was obtained.

In this example, 70% by weight of a polyolefin resin-containing aqueous resin composition obtained by emulsifying a polyolefin resin composition obtained from 15% by weight of a polyolefin resin and 85% by weight of a radical polymerizable monomer mixture was used. % (Solid content) and a radical polymerizable monomer mixture, obtained by emulsion polymerization, having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 30,000. It is an example of an aqueous resin composition consisting of 100% by weight (solid content), and is an example of an aqueous coating composition obtained by dispersing carbon black in the (a) polyolefin resin-containing aqueous resin composition. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 9 100 g of the aqueous resin composition containing the polyolefin resin of Example 4 (2), 10.0 g of Chromofine Red 6821 (organic red pigment manufactured by Dainichi Seika Co., Ltd.), SN 0.3 g of deformer 318 (manufactured by San Nopco Co., Ltd., antifoaming agent), 50.
0 is a zircon bead 200 for dispersing a pigment having a diameter of 3 mm.
g and placed in a plastic container, and sufficiently dispersed using a paint shaker. 100 g of the red paint obtained by the pigment dispersion formulation, 27 g of the aqueous resin (b) of Example 4 (3), and 9 g of butyl propylene diglycol were mixed, and the mixture was stirred until it became uniform. A water-based coating composition colored red was obtained.

In this example, 70% by weight of a polyolefin resin-containing aqueous resin composition obtained by emulsifying a polyolefin resin composition obtained from 15% by weight of a polyolefin resin and 85% by weight of a radical polymerizable monomer mixture was used. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition consisting of an organic red pigment dispersed in the above-mentioned (a) polyolefin resin-containing aqueous resin composition. . The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 10 100 g of the polyolefin resin-containing aqueous resin composition of Example 4 (2), 10.0 g of cyanine blue 314 (organic blue pigment, Sanyo Dye Co., Ltd.), SN deformer 318 (manufactured by San Nopco Co., Ltd., antifoaming agent) 0.3 g, ion-exchanged water 50.0
With 200 g of 3 mm diameter zircon beads for pigment dispersion
Together with a plastic container, and sufficiently dispersed using a paint shaker. 100 g of the blue paint obtained by the pigment dispersion formulation, 27 g of the aqueous resin (b) of Example 4 (3), and 9 g of butylpropylene diglycol were mixed, and the mixture was stirred until it became uniform. A water-based coating composition colored blue was obtained.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture, obtained by emulsion polymerization, having a glass transition temperature of 105 ° C. and a weight average molecular weight in terms of styrene of 30,000. It is an example of an aqueous resin composition consisting of a weight% (solid content), and is an example of an aqueous coating composition obtained by dispersing an organic blue pigment in the (a) polyolefin resin-containing aqueous resin composition. . The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

[Example 11] 58.0 g of the (a) polyolefin resin-containing aqueous resin composition of Example 4 (2), 25.0 g of (b) the aqueous resin of Example 4 (3), butyl propylene diglycol 9.0 g, Aqua Fine Black E-2B (Dainichi Seika Co., Ltd., black pigment dispersion paste)
8.0 g were mixed, and the mixture was stirred until it became uniform to obtain a black-colored aqueous coating composition of Example 11.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of the aqueous resin composition which consists of weight% (solid content), and is an example of the aqueous paint composition obtained by coloring black using a processed pigment paste for aqueous paint. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 12 55.5 g of (a) a polyolefin resin-containing aqueous resin composition of Example 4 (2), 24.0 g of (b) aqueous resin of Example 4 (3), butyl propylene diglycol 9.0g, Aqua Fine Red E
-17 (Red pigment dispersion paste manufactured by Dainichi Seika Co., Ltd.) 1
Then, 2.0 g of the mixture was mixed and stirred until the mixture became uniform, thereby obtaining a red-colored aqueous coating composition of Example 12.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of the aqueous resin composition which consists of weight% (solid content), and is an example of the aqueous paint composition obtained by coloring red using a processed pigment paste for aqueous paint. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 13 55.5 g of the polyolefin resin-containing aqueous resin composition of Example 4 (2), 24.0 g of the aqueous resin (b) of Example 4 (3), butyl propylene diglycol 9.0g, Aqua Fine Blue E
-2B (blue pigment dispersion paste, manufactured by Dainichi Seika Co., Ltd.) 1
2.0 g, and the mixture was stirred until it became uniform to obtain a blue-colored aqueous coating composition of Example 13.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of the aqueous resin composition which consists of weight% (solid content), and is an example of the aqueous paint composition obtained by coloring in blue using a processed pigment paste for aqueous paint. The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

[Example 14] New call 707SF
(Nippon Emulsifier Co., Ltd., anionic emulsifier) 50.0
g, Regar R400 (carbon black, manufactured by Cabot Corporation) 30.0 g, 32% ammonia water 1.0 g,
69.0 g of ion-exchanged water and 200 g of zircon beads for dispersing a pigment having a diameter of 3 mm were placed in a plastic container, and sufficiently dispersed using a paint shaker to obtain a black pigment paste. Example 4 (2)
(A) Polyolefin resin-containing aqueous resin composition 5
8.0 g, (b) aqueous resin of Example 4 (3) 25.0
g, butyl propylene diglycol 9.0 g, and the black pigment paste 8.0 g obtained by the above-mentioned pigment dispersion formulation were mixed, and the mixture was stirred until it became uniform. I got

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition consisting of a weight% (solid content), and is an example of an aqueous paint composition obtained by coloring black using a pigment paste for an aqueous paint obtained by the above formulation. . The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

[Example 15] New call 707SF
(Nippon Emulsifier Co., Ltd., anionic emulsifier) 75.0
g, Chromo Fine Red 6821 (Dainichi Seika Co., Ltd.)
45.0 g, ion-exchanged water.
0 g of zircon beads 2 for pigment dispersion having a diameter of 3 mm.
The resulting mixture was placed in a plastic container together with 00g, and sufficiently dispersed using a paint shaker to obtain a red pigment paste. Example 4 (2) (a) 55.5 g of a polyolefin resin-containing aqueous resin composition, Example 4
(3) 24.0 g of the aqueous resin (b), 9.0 g of butylpropylene diglycol, and 12.0 g of the red pigment paste obtained by the above-mentioned pigment dispersion formulation were mixed, and the mixture was stirred until it became uniform. 15 water-based paint compositions colored red were obtained.

In this example, 70% by weight of a polyolefin resin-containing aqueous resin composition obtained by emulsifying a polyolefin resin composition obtained from 15% by weight of a polyolefin resin and 85% by weight of a radical polymerizable monomer mixture was used. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition consisting of 100% by weight (solid content), and is an example of an aqueous coating composition obtained by coloring red using a pigment paste for an aqueous coating obtained by the above-mentioned formulation. . The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

[Example 16] New call 707SF
(Nippon Emulsifier Co., Ltd., anionic emulsifier) 75.0
g, 45.0 g of cyanine blue 314 (manufactured by Sanyo Dyeing Co., Ltd., organic blue pigment) and 30.0 g of ion-exchanged water.
A blue pigment paste was obtained by putting it in a plastic container together with 200 g of pigment dispersing zircon beads having a diameter of 3 mm and sufficiently dispersing it using a paint shaker. Example 4 (2) (a) 55.5 g of a polyolefin resin-containing aqueous resin composition, Example 4 (3) (b) 24.0 g of an aqueous resin, 9.0 g of butyl propylene diglycol, the pigment dispersion formulation Was mixed, and the mixture was stirred until it became uniform to obtain a blue-colored aqueous coating composition of Example 15.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition consisting of a weight% (solid content), and is an example of an aqueous paint composition obtained by coloring blue using a pigment paste for an aqueous paint obtained by the above-mentioned formulation. . The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 17 100 g of aqueous resin (b) of Example 4 (3), Regar R400 (Cabot Corporation)
23.0 g, 32% ammonia water 1.0 g, SN Deformer 318 (manufactured by San Nopco Co., Ltd., defoamer) 0.3 g, ion-exchanged water 80.0 g
With 200 g of 3 mm diameter zircon beads for pigment dispersion
Together with a plastic container, and sufficiently dispersed using a paint shaker. 63. (a) Polyolefin resin-containing aqueous resin composition of Example 4 (2)
0 g of the black paint obtained by the pigment dispersion formulation 55.
0 g and 9 g of butyl propylene diglycol were mixed, and the mixture was stirred until it became uniform to obtain a water-based coating composition of Example 17 colored black.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition comprising 100% by weight (solid content), and an example of a black aqueous coating composition obtained by dispersing carbon black in the aqueous resin (b). The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 18 100 g of aqueous resin (b) of Example 4 (3), Chromofine Red 6821 (organic red pigment, manufactured by Dainichi Seika Co., Ltd.), SN Deformer 3
18 (manufactured by San Nopco Co., Ltd., defoamer) and 80.0 g of ion-exchanged water together with 200 g of zircon beads for dispersing a pigment having a diameter of 3 mm in a plastic container,
The dispersion was sufficiently performed using a paint shaker. Example 4 (2) (a) 63.0 g of a polyolefin-based resin-containing aqueous resin composition, 55.0 g of a red paint obtained by the pigment dispersion formulation, and 9 g of butyl propylene diglycol
And the mixture was stirred until it became uniform to obtain a red-colored aqueous coating composition of Example 18.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of a water-based resin composition consisting of a weight percent (solid content), and is an example of a red water-based coating composition obtained by dispersing an organic red pigment in the water-based resin (b). Also,
The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

Example 19 100 g of the aqueous resin (b) of Example 4 (3), cyanine blue 314 (organic blue pigment manufactured by Sanyo Dyeing Co., Ltd.), SN deformer 318
0.3 g of defoamer (manufactured by San Nopco Co., Ltd.) and 80.0 g of ion-exchanged water are put into a plastic container together with 200 g of zircon beads for dispersing a pigment having a diameter of 3 mm, and sufficiently dispersed using a paint shaker. Was. Example 4
(2) (a) 63.0 g of a polyolefin-based resin-containing aqueous resin composition, 55.0 g of a blue paint obtained by the pigment dispersion formulation, and 9 g of butylpropylene diglycol were mixed, and the mixture was stirred until uniform. Thus, an aqueous coating composition colored in blue in Example 19 was obtained.

In this example, the polyolefin resin composition obtained from 15% by weight of the polyolefin resin and 85% by weight of the radical polymerizable monomer mixture was emulsified (a) 70% by weight of the polyolefin resin-containing aqueous resin composition. % (Solid content) and a radical polymerizable monomer mixture obtained by emulsion polymerization, the glass transition temperature is 105 ° C., and the weight average molecular weight in terms of styrene is 30,000. It is an example of an aqueous resin composition consisting of a weight% (solid content) and an example of a blue aqueous coating composition obtained by dispersing an organic blue pigment in the aqueous resin (b). Also,
The glass transition temperature of a copolymer obtained by copolymerizing only the radical polymerizable monomer mixture used in the polyolefin resin composition is 105 ° C.

[Coating Film Evaluation Method] (a) Coating Treatment and Coating Drying The aqueous coating compositions obtained in the above Examples and Comparative Examples were applied to a polypropylene-based plastic molding material for automobile interior by air spray coating to obtain a dry film thickness. The coating was performed uniformly so as to have a thickness of 15 μm. After the spraying is completed, heating and drying are performed for 30 minutes using a drying oven set at 80 ° C., and then the drying process is completed by leaving the room temperature at room temperature for 2 days.
Various tests were performed. The results are shown in Tables 1 to 4.

(B) Coating film test items and evaluation method Adhesion test: 1 mm × 1 mm × 100 square cuts, evaluated from the number of remaining squares after the cellophane tape peeling test. Moisture resistance adhesion test: 10 at 50 ° C and 95 RH%
Adhesion after standing for days. 1 mm x 1 mm x 100 cross cuts, evaluated from the number of crosses remaining after the cellophane tape peeling test. Water resistance test: Evaluated from color change such as whitening and adhesion after immersion in hot water at 40 ° C for 240 hours. Oil resistance test: 2 g of tallow (reagent) per 100 square centimeters is coated on a coating film, a cloth piece is placed on the coating, and after being left in an environment of 80 ° C. for 1 week, changes in adhesion, appearance, etc. Evaluation. Cosmetic resistance test: 1 g of Brabus (manufactured by Shiseido, alcoholic hair styling agent) per 100 square centimeters is applied on the coating film, and a cloth piece is placed thereon, followed by leaving it in an environment of 80 ° C. for one week and then adhesion. Evaluation based on properties, changes in appearance, etc. Finish appearance: The finish state such as glossiness and flatness of the coating film formed after coating is relatively visually evaluated. Coloring finish: The finished appearance such as coloration, glossiness, and flatness of a coating film formed after coating the colored coating composition is relatively visually evaluated.

(C) Test evaluation criteria ：: extremely good ○: good △: slightly poor but usable range ×: defective

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

As described above, the aqueous coating composition of the present invention comprises (a) a polyolefin obtained by heating a mixture containing a polyolefin resin, a radical polymerizable monomer and a radical polymerization initiator. -Based resin composition, a polyolefin-based resin-containing aqueous resin composition emulsified in water,
(B) an aqueous resin obtained by emulsion polymerization of a radical polymerizable monomer and having a glass transition temperature of 60 ° C. or higher,
The ratio of the solid content of the (a) polyolefin-based resin-containing aqueous resin composition is 50% with respect to the total amount of (a) the solid content of the polyolefin-based resin-containing aqueous resin composition and (b) the solid content of the aqueous resin. % To 90% by weight, wherein (b)
The ratio of the solid content of the aqueous resin is 10% by weight to 50% by weight based on the total amount of (a) the solid content of the polyolefin-based resin-containing aqueous resin composition and (b) the solid content of the aqueous resin,
Since the content of the polyolefin-based resin is 5% by weight to 50% by weight based on the polyolefin-based resin composition, the stability of the paint is excellent, and the obtained coating film is made of polyethylene, polypropylene, or the like. It shows good adhesion to a polyolefin material and a plastic material containing polyolefin and the like, and is excellent in water resistance, chemical resistance, and color development, and can perform excellent gloss finish.

Further, (a) the radical polymerizable monomer used in the polyolefin resin-containing aqueous resin composition has a glass transition temperature of 60 ° C. or higher of the (co) polymer of the radical polymerizable monomer. If it is a film, the durability of the coating film such as chemical resistance is further excellent. Further, (b) the aqueous resin is used in an amount of from 0.3 parts by weight to 100 parts by weight of the radical polymerizable monomer.
In the presence of 20.0 parts by weight of a compound having a chain transfer effect, a radical polymerizable monomer is obtained by emulsion polymerization and has a weight-average molecular weight in terms of styrene of 100,000 or less. Good appearance such as excellent glossiness can be obtained in the appearance of the article after applying the aqueous coating composition of the present invention to the article.

The aqueous paint composition of the present invention further contains a color pigment, and if the color pigment is previously dispersed in (b) an aqueous resin, the color paint has extremely high uniformity and is flat and color-formed. It is possible to form a coating film having good properties. Further, since the coated product of the present invention has a coating film composed of the aqueous coating composition of the present invention, the coating film is a polyolefin material such as polyethylene and polypropylene, and a plastic material containing polyolefin and the like. It shows good adhesion, is excellent in water resistance, chemical resistance, and coloring, and has good appearance such as excellent glossiness.

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Claims (5)

[Claims] 1. A polyolefin resin-containing aqueous solution obtained by emulsifying a polyolefin resin composition obtained by heating a mixture containing (a) a polyolefin resin, a radical polymerizable monomer, and a radical polymerization initiator in water. A resin composition comprising: (b) an aqueous resin obtained by emulsion polymerization of a radical polymerizable monomer and having a glass transition temperature of 60 ° C. or higher; Is from 50% by weight to 90% by weight based on the total amount of (a) the solid content of the polyolefin-based resin-containing aqueous resin composition and (b) the solid content of the aqueous resin. The ratio of the solid content of the aqueous resin is 10% by weight to 50% by weight based on the total amount of the solid content of the aqueous resin composition containing the polyolefin resin and the solid content of the aqueous resin (b); The polyolefin The content of emissions based resin, relative to the polyolefin resin composition, the aqueous coating composition, which is a 5 wt% to 50 wt%. 2. The method according to claim 1, wherein (a) the radical polymerizable monomer used in the polyolefin resin-containing aqueous resin composition has a glass transition temperature of 6 (co) polymer of the radical polymerizable monomer.
The aqueous coating composition according to claim 1, wherein the temperature is 0 ° C or higher. (B) a method in which the aqueous resin is radically polymerizable in the presence of 0.3 to 20.0 parts by weight of a compound having a chain transfer action per 100 parts by weight of the radically polymerizable monomer; 3. The aqueous coating composition according to claim 1, which is obtained by emulsion polymerization of a monomer and has a weight average molecular weight in terms of styrene of 100,000 or less. 4. The aqueous coating composition according to claim 1, further comprising a color pigment, wherein the color pigment is previously dispersed in (b) an aqueous resin. object. 5. A coated article having a coating film comprising the water-based coating composition according to any one of claims 1 to 4.