JP2003342516A - Aqueous resin composition for coating and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin composition for one pack type coatings which have sufficiently high storage stability, solvent resistance, water resistance and adhesiveness to polyolefin raw materials that are difficult to coat, and to provide a method for producing the aqueous resin composition, by which the aqueous resin composition can efficiently and easily be obtained. <P>SOLUTION: This aqueous resin composition is characterized by containing the particles of a chlorinated polyolefin-based resin composite material which is the composite material of a chlorinated polyolefin-based resin having a chlorine content of ≤50 wt.% with the polymer of a polymerizable monomer having an unsaturated double bond and has a glass transition temperature of 20 to 120°C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint which can be applied to untreated non-paintable polyolefin materials such as polyethylene, polypropylene, ethylene-polypropylene copolymer and ethylene-polypropylene-diene copolymer. The present invention relates to an aqueous resin composition and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, synthetic resins such as polyolefins have been widely used in various industrial fields for the purpose of cost reduction, recycling, etc., and in recent years, especially in the automobile field, polyolefin materials such as polypropylene materials have been widely used. Is often used.

In such applications, the surface of the polyolefin material is usually coated in order to impart a design property, but since the polyolefin material has poor wettability, a general coating material has poor adhesion. For this reason, paints in which chlorinated polyolefins are dissolved in aromatic organic solvents such as toluene and xylene have been used for coating polyolefin materials, but such paints contain a large amount of organic solvents, so they are safe. There was room for improvement in terms of hygiene, environmental pollution, and danger.

Therefore, in order to improve the above-mentioned characteristics, an attempt has been proposed to make a chlorinated polyolefin resin containing no organic solvent aqueous. For example, Japanese Patent Laid-Open No. 9-176554
The publication discloses a method of obtaining an aqueous paint by blending an aqueous dispersion of chlorinated polyolefin with an acrylic emulsion. Further, in JP-A-9-316134, when an aqueous dispersion of chlorinated polyolefin is used,
A method for producing polymer particles by swelling chlorinated polyolefin resin particles with an acrylic monomer is disclosed.

[0005]

However, the above-mentioned Japanese Unexamined Patent Application Publication No.
In the case of the method described in JP-A-176554, since the aqueous dispersion of chlorinated polyolefin and the acrylic emulsion have to be produced separately, the production efficiency is poor, and the compatibility between the chlorinated polyolefin and the acrylic component is poor. Since it is inferior, sufficient adhesion to the polyolefin material cannot be obtained. Further, in the method described in JP-A-9-316134, since the film-forming property is not sufficient, it is necessary to use a large amount of film-forming auxiliary (organic solvent) when producing the water-based paint.

The present invention has been made in view of the above problems of the prior art, and is a one-pack type coating having sufficiently high adhesion, water resistance, solvent resistance, and storage stability to a polyolefin material having poor coating properties. An object of the present invention is to provide a water-based resin composition for use, and a production method capable of efficiently and easily obtaining such a water-based resin composition.

[0007]

In order to solve the above-mentioned problems, the aqueous resin composition for coating composition of the present invention has a chlorine content of 50.
A chlorinated polyolefin resin having a glass transition temperature of 20 to 120 ° C., which is a composite of a chlorinated polyolefin resin of less than or equal to wt% and a polymer obtained from a polymerizable monomer having an unsaturated double bond. It is characterized by containing resin composite particles.

According to the aqueous resin composition for paint of the present invention,
By containing the specific chlorinated polyolefin-based resin composite particles, since adhesion, water resistance, solvent resistance, and storage stability are all improved in a well-balanced and sufficient manner, it is applied to a non-paintable polyolefin material. Even in such a case, it is possible to easily and surely apply the paint.

Further, the method for producing an aqueous resin composition for coating material of the present invention comprises chlorinated polyolefin resin particles (A) having a chlorine content of 50% by weight or less dispersed in water and having an unsaturated double bond. After swelling with the polymerizable monomer (B), the polymerizable monomer (B) is polymerized to have a glass transition temperature of -60 to
Chlorinated polyolefin resin composite particles (C) at 20 ° C
And a swelling of the chlorinated polyolefin resin composite (C) dispersed in water with a polymerizable monomer (D) having an unsaturated double bond, followed by polymerization. Glass transition temperature of 20 to 120 by polymerizing the polymerizable monomer (D)
The second compounding step of obtaining chlorinated polyolefin resin composite particles (E) at 0 ° C.

According to the above-mentioned production method of the present invention, the chlorinated polyolefin resin composite particles (E) having a glass transition temperature of 20 to 120 ° C. can be easily and surely formed, which is excellent as described above. It is possible to efficiently and easily obtain the aqueous resin composition for coating of the present invention having characteristics.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The chlorinated polyolefin resin composite contained in the aqueous resin composition for coating of the present invention comprises a chlorinated polyolefin resin having a chlorine content of 50% by weight or less,
It is a complex with a polymer obtained from a polymerizable monomer having an unsaturated double bond, and has a glass transition temperature of 20 to 120.
℃.

Examples of the chlorinated polyolefin resin used in the present invention include chlorinated polyethylene resin, chlorinated polypropylene resin, maleic anhydride modified chlorinated polypropylene resin, urethane modified chlorinated polypropylene resin, and chlorinated ethylene-propylene resin. Among polymers and chlorinated ethylene-vinyl acetate copolymers, those having a chlorine content of 50% by weight or less can be mentioned, and these can be used alone or in combination of two or more.

The chlorine content of the chlorinated polyolefin resin is 50% by weight or less as described above. Chlorine content is 5
If it exceeds 0% by weight, the adhesion to the polyolefin material and the water resistance will deteriorate. Further, the chlorine content of the chlorinated polyolefin resin is appropriately determined within the above range in consideration of various intended coating performances, and the coating performance of the resulting aqueous resin composition is significantly reduced. The lower limit is not limited unless otherwise specified, but the chlorine content is preferably 10 to 40% by weight, and preferably 15 to 3 from the viewpoint of adhesion and water resistance of the resin composition to the polyolefin-based material.
It is more preferably 0% by weight. In the present invention, the chlorine content means the value measured by the combustion method.

The chlorinated polyolefin resin has a weight average molecular weight (standard polystyrene conversion value by gel permeation chromatography) of 10,000 to
It is preferably 300,000 and preferably 40,000-
More preferably, it is 250,000. If the weight average molecular weight is less than 10,000, the solvent resistance and water resistance of the resulting coating aqueous resin composition when used to form a coating film tend to decrease, while 300,0
If it exceeds 00, the adhesiveness of the resulting aqueous resin composition for coating tends to decrease.

The chlorinated polyolefin resin used in the present invention is preferably in the form of particles. The average particle size of such particles is preferably 200 nm or less, and more preferably 50 to 150 nm. If the average particle size exceeds 200 nm, the storage stability of the resulting aqueous resin composition for coating tends to decrease.

The polymerizable monomer used in the present invention has an unsaturated double bond as described above. Specific examples of the polymerizable monomer include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and other alkyl groups having 1 to 20 carbon atoms. Acrylic acid alkyl ester; cycloalkyl group such as cyclohexyl acrylate having 3 to 20 carbon atoms; Cycloalkyl ester of acrylate; tricyclodecyl acrylate, tricyclodecyloxyethyl acrylate, tricyclodecyloxypropyl acrylate, etc. Tricycloalkyl group having 5 to 20 carbon atoms in tricycloalkyl group: Methyl methacrylate, ethyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-methacrylic acid
An alkyl methacrylate such as ethylhexyl or lauryl methacrylate having 1 to 20 carbon atoms in the alkyl group;
A cycloalkyl group such as cyclohexyl methacrylate having a carbon number of 3 to 20; a cycloalkyl group such as tricyclodecyl methacrylate, tricyclodecyloxyethyl methacrylate, tricyclodecyloxypropyl methacrylate Carbon number 5
Methacrylic acid tricycloalkyl ester having 20 to 20 carbon atoms; methacrylic acid aminoalkyl ester having 1 to 20 carbon atoms in the alkyl group such as aminomethyl methacrylate and N, N-dimethylaminoethyl methacrylate; styrene, vinyltoluene, α-methyl Styrene-based monomers such as styrene and t-butyl styrene; vinyl derivatives such as vinyl chloride, vinylidene chloride, vinyl acetate, isopropenyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylamide and methacrylamide; dimethyl maleate and malein. Dialkyl ester of unsaturated dibasic acid such as acid diethyl ester, acrylic acid ester or methacrylic acid ester having a hindered amino group, acrylic acid ester having a benzotriazole group or methacrylic acid ester , Acrylonitrile, methacrylonitrile, and the like. These polymerizable monomers have 1
They may be used alone or in combination of two or more.

The type and blending amount of the chlorinated polyolefin resin particles and the polymerizable monomer, the compounding conditions, etc., are particularly so long as the glass transition temperature of the obtained chlorinated polyolefin resin composite particles is 20 to 120 ° C. Although not limited, the desired chlorinated polyolefin-based resin composite particles can be efficiently and easily obtained by the production method of the present invention described below.

In the production method of the present invention, first, the chlorinated polyolefin-based resin particles (A) having a chlorine content of 50% by weight or less (hereinafter, sometimes referred to as component (A)) dispersed in water are unsaturated. After swelling with the polymerizable monomer (B) having a double bond (hereinafter sometimes referred to as component (B)), the swelled and absorbed polymerizable monomer (A) in the chlorinated polyolefin resin particles (A) ( B) is polymerized to obtain chlorinated polyolefin resin composite particles (C) having a glass transition temperature of −60 to 20 ° C. (hereinafter sometimes referred to as component (C)) (first composite step).

When preparing an aqueous dispersion in which the chlorinated polyolefin resin particles (A) are dispersed, a method of directly pulverizing the chlorinated polyolefin resin particles (A) by pulverization and directly dispersing in water, A method of melting the chlorinated polyolefin resin particles (A) by raising the temperature in water and dispersing them under high speed stirring, dissolving the chlorinated polyolefin resin particles (A) in an organic solvent such as toluene, and homogenizing this. It is possible to apply a method in which the mixture is stirred and mixed by a method such as the above to obtain an emulsion and then the organic solvent is distilled off under reduced pressure.

When a modified chlorinated polyolefin resin obtained by introducing a carboxylic acid or an acid anhydride into a chlorinated polyolefin resin is used as the chlorinated polyolefin resin particles (A), stable water is obtained by neutralizing the amine. A dispersion can be prepared.

In the present invention, HARDREN EH202 (trade name, Toyo Kasei Co., Ltd.) is used as an aqueous dispersion containing chlorinated polyolefin resin particles (A).
You may use a commercial item, such as.

From the viewpoint of polymerization stability and adhesion to the polyolefin material, the blending amount of the component (A) is the chlorinated polyolefin resin composite particles (E) finally obtained (hereinafter sometimes referred to as the component (E)). The total amount of 100% by weight
To 1 to 35% by weight, preferably 5 to 2
More preferably, it is 5% by weight. If the blending amount is less than 1% by weight, the amount of the chlorinated polyolefin resin particles (A) is too small to make it difficult to obtain the aqueous resin composition for coating material of the present invention, and if it exceeds 35% by weight, it is obtained. The solvent resistance of the aqueous resin composition for coating tends to decrease.

The amount of water used in the aqueous dispersion is not particularly limited, but it is preferably 50 to 300 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin resin fine particles (A).

The polymerizable monomer (B) used in the first compounding step (hereinafter sometimes referred to as the component (B))
Is not particularly limited as long as it has an unsaturated double bond, and one of the polymerizable monomers exemplified in the above description of the polymerizable monomer may be used alone or in combination of two or more. You can Among them, from the viewpoint of film-forming property and adhesion of the coating film, acrylic acid alkyl ester, acrylic acid cycloalkyl ester, acrylic acid tricycloalkyl ester, methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester and methacrylic acid tricycloalkyl ester. It is preferable to use at least one type of polymerizable monomer selected from the above as the component (B).

The amount of the polymerizable monomer (B) blended is 100% by weight of the total amount of the chlorinated polyolefin resin composite particles (E) from the viewpoint of the balance between the film-forming property and the solvent resistance of the polyolefin material. 1 to 35% by weight, and more preferably 5 to 30% by weight.
If the blending amount is less than 5% by weight, the film-forming property and the adhesiveness of the resulting aqueous resin composition for coating tend to be lowered,
If it exceeds 35% by weight, the solvent resistance of the resulting aqueous resin composition for coating tends to decrease.

As a method of swelling the chlorinated polyolefin resin particles (A) with the above-mentioned polymerizable monomer (B), for example, the polymerizable monomer (B) is stirred while stirring the aqueous dispersion.
The method of dropping is mentioned. At this time, the temperature of the aqueous dispersion is preferably not less than the glass transition temperature of the chlorinated polyolefin resin particles (A) and less than the softening point, and is 40 to
More preferably, it is in the range of 100 ° C. When the temperature of the aqueous dispersion is lower than the glass transition temperature, the chlorinated polyolefin resin particles (A) are easily aggregated,
Swelling efficiency tends to decrease. When the temperature of the aqueous dispersion is equal to or higher than the softening point, the chlorinated polyolefin resin particles (A) are thermally melted to form droplets, and the chlorinated polyolefin resin particles and the polymerizable monomer are contained in the droplets. It becomes easy to separate from (B).

As a method for polymerizing the swelled polymerizable monomer in the chlorinated polyolefin resin particles (A), a usual emulsion polymerization method can be used.

Examples of the polymerization initiator used in the emulsion polymerization include water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate and hydrogen peroxide. These polymerization initiators may be used alone or in combination of two or more. further,
In the present invention, a redox polymerization initiator can be used. For example, a combination of the above-mentioned water-soluble polymerization initiator and a reducing agent (for example, a sulfite salt, a bisulfite salt, a salt having a low ionic value such as cobalt, iron and copper) can be mentioned.

The amount of the polymerization initiator used is determined depending on the intended polymerization stability in the chlorinated polyolefin resin composite particles (E), but it is usually 0.1% with respect to the total amount of the component (B). It is preferably from 0 to 1% by weight. Moreover, you may adjust a molecular weight using a chain transfer agent as needed. Examples of the chain transfer agent include n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane and the like.

A surfactant can be used in the emulsion polymerization. Examples of the surfactant include non-polymerizable surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, and sorbtan. Examples thereof include nonionic surfactants such as alkyl esters and polyglycerin esters, and anionic surfactants such as alkyl sulfate ester salts, alkylphenol sulfonates and sulfosuccinic acid ester salts. In addition, for example, as the polymerizable surfactant, commercially available ANTOX MS60 (manufactured by Nippon Emulsifier Co., Ltd.), Eleminol JS-2 (Sanyo Kasei Co., Ltd.), Adekaria Soap SE series (manufactured by Asahi Denka Co., Ltd.), Adecaria soap NE series (made by Asahi Denka Co., Ltd.), Aqualon HS series (made by Daiichi Kogyo Seiyaku Co., Ltd.), Aqualon RN series (made by Daiichi Kogyo Seiyaku Co., Ltd.), etc. are mentioned. These surfactants may be used alone or in combination of two or more.

The amount of the surfactant used is determined according to the intended polymerization stability and water resistance in the chlorinated polyolefin resin composite (E), but usually (E)
It is preferably 0.1 to 5% by weight, and more preferably 0.5 to 4% by weight, based on 100% by weight of the total amount of the components.

The reaction temperature during emulsion polymerization is 50 to 100.
C. is preferable, and 60 to 95.degree. C. is more preferable. Also,
The reaction time is preferably 1 to 10 hours, more preferably 2 to 8 hours. The reaction pressure is not particularly limited, but usually
It is performed under normal pressure.

The glass transition temperature of the chlorinated polyolefin resin composite particles (C) thus obtained is -6.
It is necessary to be in the range of 0 ° C to 20 ° C, and -55
It is preferably in the range of 0 ° C. If the glass transition temperature is lower than -60 ° C, the solvent resistance of the resulting aqueous resin composition for coating material is significantly lowered, and if it is higher than 20 ° C, the film-forming property of the coating film is significantly lowered.

The glass transition temperature in the present invention means
Thermal analyzer DSC (eg Seiko Instrum)
ent Inc. Manufactured by M.D.).

Next, the above chlorinated polyolefin resin composite (C) is used as a polymerizable monomer (D) having an unsaturated double bond in an aqueous dispersion (hereinafter referred to as a component (D) in some cases). ), The chlorinated polyolefin resin composite (C) is polymerized with the swelled and absorbed polymerizable monomer (D) to have a glass transition temperature of 20 to 120 ° C. (E) is obtained (second compounding step).

The polymerizable monomer (D) used in the second compounding step is not particularly limited as long as it has an unsaturated double bond, but the following (d1) and (d2): (d1) ) A polymerizable monomer having a carboxyl group and an unsaturated double bond (hereinafter sometimes referred to as component (d1)); (d2) A polymerizable monomer having an unsaturated double bond and having no carboxyl group. It is preferable to use both of the monomers (hereinafter sometimes referred to as the component (d2)) in combination.

The component (d1) is a polymerizable monomer having a carboxyl group and an unsaturated double bond, and examples thereof include acrylic acid, methacrylic acid, itaconic acid and maleic acid. The carboxyl group may exist as an acid anhydride group, and maleic anhydride or the like can also be used. These components (d1) are used alone or in combination of two or more. The blending amount of the component (d1) in the component (D) is 100% by weight of the total amount of the component (D) from the viewpoint of the balance between the adhesion of the resulting aqueous resin composition for coating material to the polyolefin material and the solvent resistance. 0.1-
5 wt% is preferable, 0.5-3.0 wt%
Is more preferable. This blending amount is 0.1% by weight
If it is less than 5, the solvent resistance of the resulting aqueous resin composition for coating tends to decrease, and if it exceeds 5% by weight,
The water resistance of the resulting aqueous resin composition for coating tends to decrease.

The component (d2) is a polymerizable monomer having an unsaturated double bond and no carboxyl group. Specific examples of the component (d2) include an alkyl acrylate having 1 to 20 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. Ester; cycloalkyl group such as cyclohexyl acrylate having 3 to 20 carbon atoms; cycloalkyl ester; tricyclodecyl acrylate, tricyclodecyloxyethyl acrylate, tricycloalkyl such as tricyclodecyloxypropyl acrylate Acrylic acid tricycloalkyl ester having 5 to 20 carbon atoms: methyl methacrylate, ethyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-methacrylic acid
An alkyl methacrylate such as ethylhexyl or lauryl methacrylate having 1 to 20 carbon atoms in the alkyl group;
A cycloalkyl group such as cyclohexyl methacrylate having a carbon number of 3 to 20; a cycloalkyl group such as tricyclodecyl methacrylate, tricyclodecyloxyethyl methacrylate, tricyclodecyloxypropyl methacrylate Carbon number 5
Methacrylic acid tricycloalkyl ester having 20 to 20 carbon atoms; methacrylic acid aminoalkyl ester having 1 to 20 carbon atoms in the alkyl group such as aminomethyl methacrylate and N, N-dimethylaminoethyl methacrylate; styrene, vinyltoluene, α-methyl Styrene-based monomers such as styrene and t-butyl styrene; vinyl derivatives such as vinyl chloride, vinylidene chloride, vinyl acetate, isopropenyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylamide and methacrylamide; dimethyl maleate and malein. Dialkyl ester of unsaturated dibasic acid such as acid diethyl ester, acrylic acid ester or methacrylic acid ester having a hindered amino group, acrylic acid ester having a benzotriazole group or methacrylic acid ester , Acrylonitrile, methacrylonitrile, and the like. Among these, from the viewpoint of adhesion of the coating film and water resistance, acrylic acid alkyl ester, acrylic acid cycloalkyl ester, acrylic acid tricycloalkyl ester, methacrylic acid alkyl ester,
It is preferable to use at least one kind of polymerizable monomer selected from methacrylic acid cycloalkyl ester and methacrylic acid tricycloalkyl ester.

The content of the component (d2) in the component (D) is 100% by weight of the total amount of the component (D) from the viewpoint of adhesion and water resistance of the resulting aqueous resin composition for coating material to a polyolefin material. Therefore, it is preferably 95 to 99.9% by weight, and more preferably 97 to 99.5% by weight. If the content is less than 97% by weight, the water resistance of the resulting aqueous resin composition for coating tends to decrease, and if it exceeds 99.9% by weight, the solvent resistance of the obtained aqueous resin composition for coating is low. It tends to decrease.

The total amount of the component (D) is 30 to 98% by weight based on 100% by weight of the total amount of the component (A) from the viewpoint of the balance of adhesion to the polyolefin material, water resistance and solvent resistance. %, Preferably 40 to 8
More preferably, it is 5% by weight. This amount is 30
If it is less than wt%, the hardness and solvent resistance of the obtained aqueous resin composition for coating tend to be lowered, and if it exceeds 98 wt%, the polymerization stability tends to be lowered.

Chlorinated paraffin resin composite particles (C)
When polymerizing the polymerizable monomer (D) swollen and absorbed in, the usual emulsion polymerization method can be used as in the case of polymerizing the polymerizable monomer (B). Also in this case, the above-mentioned polymerization initiator can be used, and the amount thereof is preferably 0.01 to 1% by weight based on the total amount of the component (D).

The glass transition temperature of the aqueous dispersion containing the chlorinated polyolefin resin composite particles (E) of the present invention must be in the range of 20 to 120 ° C. It is preferably in the range of 100 ° C. If the glass transition temperature is lower than 20 ° C, the solvent resistance is significantly lowered, and if it is higher than 120 ° C, the film-forming property is significantly lowered.

By the production method of the present invention, the aqueous coating composition of the present invention can be efficiently and easily obtained as an aqueous dispersion containing the chlorinated polyolefin resin composite particles (E).

The aqueous resin composition for coating material of the present invention contains the above-mentioned specific chlorinated polyolefin resin composite particles, but may further contain an inorganic pigment, an organic pigment or the like, if necessary. Good. Examples of inorganic pigments include titanium white and carbon black, and examples of organic pigments include phthalocyanine pigments and azo pigments. As a method of incorporating these inorganic pigments, organic pigments, etc., for example, a usual pigment dispersion method can be used. When using these, it is preferable to set it as 0.5 to 60 weight% in the resin composition for coating materials of this invention.

Further, the aqueous resin composition for paint of the present invention comprises
If necessary, each additive, for example, aluminum paste, plasticizer, coating film reinforcing resin, pigment dispersant, pigment settling agent, coating surface adjusting agent, rheology control agent, ultraviolet absorber,
It is also possible to add an ultraviolet stabilizer, an antioxidant, etc. at the time of making a paint or after making a paint.

The aqueous resin composition for coating material according to the present invention can be used as a coating material for coating the surface of various substrates and articles. In particular, since it can be used as a paint for directly coating polyolefin materials such as polyolefin-based molded products, sheets and films, it is very useful as a primer, enamel paint, metallic paint and the like.

When coating is carried out using the aqueous resin composition for coating of the present invention, for example, an air spray coating machine, an airless spray coating machine, an electrostatic coating machine, a roll coater coating machine,
It can be applied by dipping, brushing or the like.

When the coating resin composition of the present invention is applied to a polyolefin material, the drying time can be shortened by applying such heating after the application. The heating and drying conditions are appropriately selected in consideration of the deformation temperature of the base material,
The drying temperature is preferably in the range of room temperature to 150 ° C., and the drying time is preferably in the range of 1 to 100 minutes.

[0049]

EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, "parts" and "%" indicate parts by weight and% by weight, respectively.

[Examples 1 to 4] A 1-liter separable flask equipped with a condenser, a thermometer, a dropping funnel, a nitrogen gas blowing tube and a stirrer contains chlorinated polypropylene resin particles as the component (A). Water dispersion (trade name, HARDREN EH202, manufactured by Toyo Kasei Co., Ltd., chlorine content of chlorinated polypropylene resin particles: 16%, resin solid content: 20% by weight), ion-exchanged water and surfactant (trade name) , Monogen Y100, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
The mixture was mixed in the mixing ratio shown in and heated to 70 ° C. The blending ratio of the component (A) in Table 1 means the net blending ratio of the resin (the same applies hereinafter). Thereafter, the component (B) was added dropwise at the blending ratio shown in Table 1 over 1 hour, and the temperature was kept at the same temperature for 1 hour to swell the chlorinated polypropylene resin particles. Then, the aqueous dispersion was heated to 90 ° C., an aqueous solution prepared by dissolving 0.1 part of ammonium persulfate in 5 parts of ion-exchanged water was added, and the mixture was kept at the same temperature for 2 hours,
Chlorinated polypropylene resin composite particles (C) as the component (C) were obtained. Table 1 shows the glass transition temperature T _g of the chlorinated polypropylene resin composite particles (C) obtained in each example.

Next, the aqueous dispersion was cooled to 70 ° C., and the component (D) was added dropwise at the compounding ratio shown in Table 1 over 2 hours.
Further, the chlorinated polypropylene polymer particles were swollen by keeping the temperature at the same temperature for 1 hour. Thereafter, the mixture was heated to 90 ° C., an aqueous solution in which 0.1 part of ammonium persulfate was dissolved in 5 parts of ion-exchanged water was added, and the mixture was kept at the same temperature for 2 hours. Then, the flask was cooled to room temperature, ion-exchanged water was added so that the nonvolatile content became 25% by weight, and the aqueous resin composition for coating (R-1) containing chlorinated polypropylene polymer particles (E).
~ (R-4) were obtained. Glass transition temperature T _{g of} chlorinated polypropylene-based resin composite particles (E) obtained in each example
Are shown in Table 1.

[0052]

[Table 1] [Comparative Examples 1 to 3] For coating materials in the same manner as in Examples 1 to 3 except that the amounts of components (A) to (D), ion-exchanged water, and surfactant were set as shown in Table 2, respectively. Aqueous resin compositions (R-5) to (R-7) were obtained. Chlorinated polypropylene-based resin composite particles (C) obtained in each comparative example,
Table 2 shows the glass transition temperature T _g of (E). In the case of the chlorinated polypropylene resin composite particles (C) in Comparative Example 1, no glass transition temperature was observed.

[0053]

[Table 2] (Preparation of 1-coat lacquer water-based paint) Water-based resin composition for paint (R-1) to (R-4) obtained in Examples 1 to 4 and water-based resin composition for paint obtained in Comparative Examples 1 to 4 Thing (R-
5) to (R-7) in the blending ratios shown in Table 3, talc and carbon black (carbon black MA10).
0, manufactured by Mitsubishi Chemical Corporation, thickener (Adecan UH7)
52, manufactured by Asahi Denka Co., Ltd., antifoaming agent (BYK028, manufactured by Big Chemie Japan Co., Ltd.), wetting agent (BKY34)
8, mixed with Big Chemie Japan KK and a film-forming auxiliary (3-methyl-methoxybutylacetate) to prepare an aqueous paint. Each of the obtained water-based paints was diluted with ion-exchanged water in a Ford cup # 4 at 25 to 30 seconds / 25 ° C to prepare a 1-coat lacquer water-based paint.

[0054]

[Table 3] (Evaluation of Storage Stability) Aqueous resin compositions for coating (R-1) to (R-4) obtained in Examples 1 to 4 and Comparative Examples 1 to 3
Each of the coating resin compositions (R-5) to (R-7) obtained in step 1) was placed in a glass container having a volume of 50 ml, and the mixture was stirred at 5 ° C for 1
After storing for one month or one month at 50 ° C., the state of the aqueous resin composition was visually observed. The obtained results are shown in Tables 4 and 5. (Evaluation of Initial Adhesion) Each of the 1-coat lacquer water-based paints obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was dried on a polyolefin molded plate (polypropylene molded plate) which had not been surface-treated to obtain a dry film thickness. Was 10 to 15 μm. Then, the coated molded plate was left at room temperature for 5 minutes and further dried at 70 ° C. for 20 minutes to obtain a coated film plate.

With respect to the coated plate thus obtained,
The initial adhesiveness was evaluated according to the gourd eye test method of JIS K-5400. That is, a knife was used to draw 10 lines in each length and width at 2 mm intervals, and a cellophane tape was adhered so as to cover the 100 goggles formed. Then, when the tape was peeled off, the number of goggles left on the coating film was measured, and the following criteria were used: A: All 100 gobangs remained B: 51 to 99 gobangs C: Remaining C: The initial adhesiveness was evaluated according to the presence of 50 or less gourd eyes. The results obtained are shown in Table 4,
5 shows. (Water resistance: Evaluation of coating film appearance and adhesion after hot water treatment) A coating film plate prepared in the same manner as in the case of evaluation of initial adhesion,
It was immersed in warm water at 40 ° C. for 1 week. The appearance of the coating film thus treated with the hot water was observed and the water resistance was evaluated according to the following criteria: A: No change B: Slight blisters C: Blister D: Whitening and blisters . Further, with respect to the coated film plate after the hot water treatment, the tape was adhered and peeled off in the same manner as in the case of the evaluation of the initial adhesion, and the following criteria: A: All 100 scoring cells remained B: Adhesion was evaluated according to the fact that 51 to 99 goggles remained C: 50 or less goggles remained. The results obtained are shown in Table 4,
5 shows. (Evaluation of solvent resistance) Regular gasoline (manufactured by Mitsubishi Nisseki Co., Ltd.) was dropped on the coating film of the coating plate obtained in the same manner as in the case of the evaluation of initial adhesion, and the droplet was immediately gauze. After wiping with, the appearance of the coating film is observed and the following criteria are used: A: No trace B: Slight trace C: Swelling or whitening of the coating D: Solvent resistance according to dissolution or cracking of the coating Was evaluated. The obtained results are shown in Tables 4 and 5.
Shown in.

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

As described above, the aqueous resin composition for paints of the present invention is excellent in storage stability, adhesiveness, water resistance and solvent resistance, and is a paint-resistant polyolefin that does not require an organic solvent. It is very useful as a water-based paint that can be applied to materials.

Further, according to the method for producing the aqueous resin composition for coating material of the present invention, the aqueous resin composition for coating material of the present invention having excellent properties as described above can be obtained efficiently and easily.

Continued front page    (72) Inventor Kenichi Shintani             Hitachi, Hasaki-machi, Kashima-gun, Ibaraki             Kasei Industry Co., Ltd. Yamazaki Office F-term (reference) 4J038 CB171 CP061 CR072 MA08                       PC08

Claims (2)

[Claims] 1. A composite of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less and a polymer obtained from a polymerizable monomer having an unsaturated double bond, having a glass transition temperature of 20. A water-based resin composition for coatings, which contains chlorinated polyolefin-based resin composite particles having a temperature of up to 120 ° C. 2. The content of chlorine dispersed in water is 50% by weight.
The following chlorinated polyolefin resin particles (A) are swollen with a polymerizable monomer (B) having an unsaturated double bond, and then the polymerizable monomer (B) is polymerized to obtain a glass transition temperature. An unsaturated double bond is formed between the first compounding step of obtaining chlorinated polyolefin resin composite particles (C) at −60 to 20 ° C. and the chlorinated polyolefin resin composite (C) dispersed in water. After swelling with the polymerizable monomer (D) having the above, the polymerizable monomer (D) is polymerized to obtain chlorinated polyolefin resin composite particles (E) having a glass transition temperature of 20 to 120 ° C. A method for producing a water-based resin composition for paint, comprising a second composite step.