JPH11263802A - Aqueous resin composition, its production method and its coated product - Google Patents

Abstract

(57) [Object] The object of the present invention is not only to show excellent adhesion to a polyolefin substrate, but also to other organic substrates,
An aqueous resin composition having excellent adhesion, inorganic (base) water resistance, oil resistance and the like even to inorganic base materials. The present invention provides (A) a chlorinated polyolefin having a chlorination degree of 5 to 50% by weight, (B) an organic solvent, (C) a vinyl monomer, (D) a surfactant, A) An aqueous resin composition characterized by emulsion polymerization of a composition comprising water and (F) a polymerization initiator, or solvent removal after emulsion polymerization, and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin composition,
The present invention relates to a production method and a coated product, and can be mainly used as a paint, a primer, an ink, an adhesive, and a sealing agent. Above all, it is possible to form a coating and an adhesive layer with excellent adhesion, (hot) water resistance and oil resistance to a polyolefin substrate having a nonpolar surface, etc. Useful as paints, primers, inks, sealants, and adhesive resins.

[0002]

2. Description of the Related Art In order to improve the disadvantages of chlorinated polyolefins conventionally used in the fields of paints, adhesives, inks, etc. Studies have been made on denaturation with vinyl monomers and aqueousization using composites. For example, JP-A-58-5271, JP-A-1-4378
In JP-A-5 (1999), an aqueous resin composition is obtained by dissolving a chlorinated polyolefin having a high chlorination degree in a vinyl monomer and subjecting it to suspension polymerization in the presence of a polymerization initiator and a dispersion stabilizer such as poval or hydroxyethyl cellulose. ing. JP-A-7-30
In Japanese Patent No. 0570, an aqueous resin composition is obtained by emulsifying an organic solvent solution of a chlorinated polyolefin having a high chlorination degree in water with a surfactant, and then polymerizing a vinyl monomer in the emulsion. . In JP-A-1-256556, an aqueous resin composition is obtained by grafting a chlorinated polyolefin with an unsaturated carboxylic acid and a (meth) acrylic monomer and self-emulsifying a chlorinated carboxylated polyolefin.

[0003]

However, the above-mentioned aqueous resin composition has the following problems. That is, JP-A-58-5271 and JP-A-1-4378.
The aqueous resin composition of JP-A No. 5 uses a polyolefin having a high chlorination degree and has poor adhesion to a substrate and is manufactured by suspension polymerization, so that a high molecular weight hydrophilic dispersion is stable. The use of a large amount of the agent had disadvantages such as poor (warm) water resistance of the film.

In Japanese Patent Application Laid-Open No. Hei 7-300570,
The resulting aqueous resin composition had disadvantages such as poor dispersion stability, and low adhesion to a polyolefin substrate due to the use of a polychlorinated polyolefin. In JP-A-1-256556, there is a limit to the amount of grafting of unsaturated carboxylic acid and (meth) acrylic monomer in the polymerization method, and the low coating film hardness, which is a drawback of chlorinated polyolefin, is improved. could not. In addition, it is necessary to increase the weight ratio in the grafting of the unsaturated carboxylic acid in the aqueous resin composition for self-emulsification,
As a result, there was a drawback that the resulting aqueous resin composition had poor (warm) water resistance.

[0005]

Means for Solving the Problems To achieve the above object, the present inventors have found that there is no problem of lowering the dispersion stability of the resin, the safety is excellent, and the adhesion and adhesion to the base material, especially the polyolefin base material, are improved. As a result of intensive studies on a resin composition capable of forming a coating film and an adhesive layer having excellent hot water resistance and oil resistance without deteriorating properties, a specific aqueous resin composition was found, and the present invention was completed.

That is, the present invention relates to (A) a chlorinated polyolefin having a chlorination degree of 5 to 50% by weight, (B) an organic solvent, (C)
Aqueous resin characterized by emulsion polymerization of a composition comprising a vinyl monomer, (D) surfactant, (E) water, and (F) a polymerization initiator, or solvent removal after emulsion polymerization. Composition, 5-5
Chlorinated polyolefin (A) 1 with chlorination degree up to 0% by weight
100 parts by weight of the organic solvent (B) and 100 to 1900 parts by weight of the vinyl monomer (C) with respect to 00 parts by weight. And the surfactant (D) is a chlorinated polyolefin (A) 100
2 to 100 parts by weight, 5 to 50 parts by weight
A chlorinated polyolefin (A) having a chlorination degree of up to% by weight dissolved in an organic solvent (B), a vinyl monomer (C),
Surfactant (D), a composition comprising water (E) is mechanically emulsified and dispersed, then a polymerization initiator is added, and the monomer (C)
A method for producing an aqueous resin composition, which is characterized by emulsion polymerization of (A) chlorinated polyolefin, which was mechanically emulsified and dispersed, (B) an organic solvent, (C) a vinyl monomer, and (D) an interface. The average particle diameter of the activator and (E) water dispersion is 1 μm or less, further, the emulsion polymer is desolvated by distillation under reduced pressure, and the aqueous resin composition obtained in any of the above is placed on a substrate. It is intended to provide a coated article characterized by being coated on a surface.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The chlorination degree of the present invention is 5 to 50% by weight.
The chlorinated polyolefin (A) is, for example, polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber,
A polyolefin obtained by chlorinating an ethylene-vinyl acetate copolymer or the like in a range of 5 to 50% by weight, preferably a polyolefin obtained by chlorination in a range of chlorination degree of 10 to 30% by weight is used. Is done. Chlorination degree is 50% by weight
If it is too high, the adhesion to the polyolefin substrate will decrease, and if the chlorination degree is too low, the solubility in organic solvents will decrease.

As the organic solvent (B) in the organic agent solution of the chlorinated polyolefin (A) of the present invention, an aromatic organic solvent such as toluene and xylene and an aliphatic organic solvent such as hexane and cyclohexane are mainly used. used. Also, this organic solvent
(B) can be used as it is as a film-forming auxiliary.
The organic solvent (B) used in the present invention can be distilled off after the polymerization to remove the solvent. The amount of the organic solvent (B) used in the present invention is preferably 100 to 900 parts by weight based on 100 parts by weight of the chlorinated polyolefin. When the amount of the organic solvent (B) is 900 parts by weight or more, it is not preferable in terms of odor and safety, and when the amount of the organic solvent is less than 100 parts by weight, it is difficult to dissolve the chlorinated polyolefin (A) or the chlorinated polyolefin. This is not preferable because the fluidity of the organic solvent solution significantly decreases.

The vinyl monomer used in the present invention
(C) is one or more kinds capable of emulsion polymerization, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
Monofunctional (meth) acrylates such as isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; monofunctional monomers containing a carboxyl group or anhydride such as acrylic acid, methacrylic acid, itaconic acid and maleic anhydride; Monofunctional (meth) acrylates having a functional group such as diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and acrylamide; ethylene glycol di (meth) acrylate; 1,6-hexanediol Polyfunctional (meth) acrylates such as di (meth) acrylate and trimethylolpropane tri (meth) acrylate; styrenes such as styrene, chloromethylstyrene and α-methylstyrene; and γ-methacryloxypropyltrimethoxysilane and the like. Various unsaturated bond-containing silane compounds, diallyl phthalate, divinylbenzene, allyl acrylate, etc., monomers having two or more unsaturated bonds in one molecule, vinyl acetate, vinyl propionate or "Veoba" (Shell, Netherlands) One or more selected from various vinyl esters such as vinyl esters of branched aliphatic carboxylic acids) and various cyano group-containing monomers such as acrylonitrile. Is used alone or as a mixture.

The amount of the vinyl monomer (C) used in the present invention is 100 parts by weight per 100 parts by weight of the chlorinated polyolefin.
~ 1900 parts by weight are preferred. When the amount of the vinyl monomer is
If the amount is too small, the properties of the product are controlled by the chlorinated polyolefin itself, so that the oil resistance of the film is reduced and the dispersion stability of the resin is also reduced. If the amount of the vinyl monomer is too large, the adhesion of the product film, particularly the adhesion to a polyolefin substrate, is reduced. The proportion of the carboxyl group-containing monomer in the vinyl monomer used in the present invention is preferably from 0 to 10% by weight. If the amount of the carboxyl group-containing monomer is large, the water resistance of the product film decreases.

When a carboxyl group-containing monomer is used in combination with the vinyl monomer (C), an aqueous resin composition having better dispersion stability is formed by neutralizing the carboxyl group with an amine. The amount of the amine to be added is preferably the pH value (or hydrogen ion concentration) of the aqueous resin composition, preferably 7.5 to 7.5.
The ratio is 9.0.

The amine used for neutralization is ammonia,
Or at least one selected from primary, secondary and tertiary amines.

The surfactant (D) used in the present invention includes a non-reactive surfactant having no ethylenically unsaturated group and a reactive surfactant having an ethylenically unsaturated group. They may be used alone or in combination.

Examples of the non-reactive surfactant include non-reactive surfactants represented by polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene-polyoxypropylene block copolymer and the like. Examples thereof include anionic surfactants, anionic surfactants represented by sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium dialkyl sulfosuccinate, sodium salt or ammonium salt of alkylphenyl polyoxyethylene sulfate, and the like. Further, two or more of these surfactants may be combined.

As the reactive surfactant, sodium vinyl sulfonate, sodium styrene sulfonate, polyoxyethylene ammonium (meth) acrylate sulfate,
Sodium (meth) acrylate polyoxyethylene sulfonate, ammonium polyoxyethylene alkenyl phenyl sulfonate, sodium polyoxyethylene alkenyl phenyl sulfate, sodium allyl alkyl sulfosuccinate, sodium polyoxypropylene (meth) acrylate sulfonate, 2- Anionic reactive emulsifiers such as hydroxyethyl (meth) acryloyl phosphate: nonionic reactive emulsifiers such as polyoxyethylene alkenyl phenyl ether and polyoxyethylene (meth) acryloyl ether, which are generally used in emulsion polymerization reactions. Can be used without any problem.

The use amount of these surfactants is preferably 2 to 100 parts by weight based on 100 parts by weight of the chlorinated polyolefin (A). If it exceeds 100 parts by weight, the (warm) water resistance of the film is lowered, which is not preferable. If it is less than 2 parts by weight, the polymerization stability is lowered.

According to the production method of the present invention, the chlorine content is 5 to 5
Emulsion dispersion of 0% by weight of chlorinated polyolefin (A) dissolved in organic solvent (B) and vinyl monomer (C) in the presence of surfactant (D) dissolved in pure water (E) And a step of emulsion-polymerizing the monomers in the emulsion with the polymerization initiator (F).

In the present invention, the above chlorinated polyolefin
(A), an organic solvent (B), a vinyl monomer (C) as a surfactant (D)
And mechanically emulsified and dispersed in the presence of water (E). In this emulsification / dispersion step, emulsification / dispersion is performed using a mechanical emulsification / dispersion device such as a homomixer. Further, such an emulsified dispersion is preferably uniform and fine particles, and the particle size is 1.0 μm.
m or less. In the case of fine particles having a particle diameter of more than 1.0 μm, when the emulsion polymerization reaction is performed, the particle diameter of the polymer becomes non-uniform, generation of aggregated particles, sedimentation of the particles, and the like occur, causing problems in production and storage stability. There are cases.

The polymerization initiator (F) used in the present invention
Known and commonly used ones can be used, for example, persulfates such as sodium persulfate, ammonium persulfate, and potassium persulfate; 2,2′-azobis (2-aminodipropane) dibasic acid; Azo compounds such as' -azobis (4-cyanovaleric acid) and organic peroxides such as tertiary butyl (tert-butyl) hydroperoxide and cumene hydroperoxide are used, and these are used in combination with a reducing agent and redox. Polymerization can also be performed. or,
At the time of redox polymerization, a compound that generates a so-called polyvalent metal salt ion typified by an iron ion or a copper ion can be used in combination as a promoter.

As a reducing agent that can be used in combination with the above polymerization initiator during redox polymerization, sodium sulfoxylate formaldehyde, sodium pyrosulfite, L-ascorbic acid and the like can be used. At the time of redox polymerization, a compound that generates a so-called polyvalent metal salt ion typified by an iron ion or a copper ion can be used in combination as a promoter.

The amount of the polymerization initiator and the reducing agent to be used is preferably in the range of 0.1 to 10% by weight based on the weight of the vinyl monomer.

In the present invention, a chain transfer agent can be used to control the degree of polymerization. Examples of the chain transfer agent include alkyl mercaptans such as n-butyl mercaptan, n-octyl mercaptan and n-lauryl mercaptan; thioglycolic acid esters such as butyl thioglycolate and octyl thioglycolate; thiomalic acid; and 3-mercapto. Examples include water-soluble mercaptans such as propionic acid and thioglycolic acid, and alcohols such as isopropyl alcohol.

In the present invention, the vinyl monomer in the emulsified dispersion obtained as described above is subjected to emulsion polymerization with stirring in a nitrogen atmosphere in the presence of a polymerization initiator. The reaction temperature is preferably in the range of 40 to 100 ° C. Further, the emulsified dispersion and the polymerization initiator may be added in advance to the reaction vessel in their entirety, or may be added sequentially as the polymerization reaction proceeds.

In the present invention, the organic solvent in the aqueous resin composition obtained by the polymerization can be removed by distillation under reduced pressure. The conditions for vacuum distillation are as follows:
C., a pressure reduction degree of 0.0008 MPa to 0.04 MPa, and a pressure reduction time of 1 to 4 hours are preferable.

The composition of the present invention can be used mainly as a paint, a primer, an ink, an adhesive or a sealing agent. Among them, coatings and primers for polyolefin films / sheets and polyolefin moldings can be formed, especially because they can form coatings and adhesive layers having excellent adhesion, (hot) water resistance and oil resistance to polyolefin substrates having nonpolar surfaces. Used for inks, sealants, and adhesives. It can be used in a wide range of fields such as automotive parts, electric and electronic parts, civil engineering and construction materials.

The base material of the present invention is not limited to typical ones, and various metals such as iron, stainless steel or aluminum; olefin resins such as polycarbonate, polypropylene and polyethylene; Various plastics such as polymethyl methacrylate, ABS resin or polystyrene; woods, papers, fibers, FRPs, glass, slate board or concrete, silicates such as calcium silicate,
Various inorganic substances such as gypsum, asbestos or ceramics. Preferably, it is a polyolefin resin.

When the composition of the present invention is used, for example, it may be clear in a paint or the like, or may be a colored paint containing a pigment or any form. The pigments include various organic pigments and various inorganic pigments such as titanium oxide, iron oxide, aluminum flake, and titanium coated mica.

The method for forming a cured coating film is as follows: air spray method, airless spray method,
Various known coating methods such as brush coating or roll coating can be used.

The drying may be carried out at room temperature for one day (day and night) for about two weeks at room temperature, depending on the drying properties of the composition or the heat resistance of the base material, and the like. Hardening, or about 60 to about 25
A wide range of drying conditions can be set, such as drying in a temperature range of about 0 ° C. for about 30 seconds to about 3 hours.

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) To 333 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo), 245 g of methyl methacrylate, 230 g of butyl acrylate and 12 g of methacrylic acid were added. 6 g of oxide nonyl phenyl ether (Emulgen 920; manufactured by Kao), 4 g of polyoxyethylene nonyl phenyl ether sulfate (Hytenol N-08; manufactured by Dai-ichi Kogyo Chemical), water 2
After adding 00 g, the mixture was atomized using a homogenizer (TK Auto Homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.) at 9000 rpm for 30 minutes.

At this time, when the particle size of the atomized product was measured with a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics Co., Ltd.), it was 0.4 μm.

467 g of water was charged into a 2 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours while stirring under a nitrogen atmosphere. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

Example 2 The aqueous resin composition obtained in Example 1 was distilled under reduced pressure at 0.0039 MPa and 40 ° C. for 2 hours using a water flow depressurizer (A-3S, manufactured by Tokyo Rika Kikai). . The distilled water-based resin composition was adjusted to a nonvolatile content of 40% with pure water. The content of toluene in this emulsion was determined by gas chromatography (GC-7A: manufactured by Shimadzu Corporation).
Was 1% or less (based on solid content).

(Example-3) A solution prepared by dissolving 100 g of chlorinated polypropylene having a chlorination degree of 45% in 233 g of toluene, 245 g of methyl methacrylate, 230 g of butyl acrylate and 12 g of methacrylic acid were added. Further, polyethylene oxide nonylphenyl ether (Emulgen 920) was added. 6 g), polyoxyethylene nonyl phenyl ether sulfate salt (Hytenol N-08;
4 g of Daiichi Kogyo Chemical Co., Ltd. and 200 g of water were added, and the mixture was pulverized using a homogenizer (TK Auto Homo Mixer: manufactured by Tokushu Kika Kogyo) at 9000 rpm for 30 minutes.

At this time, when the particle size of the atomized product was measured by a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics), it was 0.4 μm.

467 g of water was charged into a 2 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours under a nitrogen atmosphere. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

Comparative Example 1 333 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 60% was mixed with 245 g of methyl methacrylate and 230 g of butyl acrylate.
12 g of methacrylic acid was added, and 6 g of polyethylene oxide nonyl phenyl ether (Emulgen 920; manufactured by Kao), 4 g of polyoxyethylene nonyl phenyl ether sulfate (HITENOL N-08; manufactured by Daiichi Kogyo Kagaku), and 200 g of water were added. TK Auto Homo Mixer: 9000
The particles were atomized over 30 minutes at rpm.

At this time, when the particle size of the atomized product was measured by a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics), it was 0.4 μm.

A 2-L four-necked flask equipped with a stirrer was charged with 467 g of water, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours while stirring under a nitrogen atmosphere. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

(Comparative Example 2) To 333 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo), 50 g of methyl methacrylate, 46 g of butyl acrylate, and 2 g of methacrylic acid
6 g of polyethylene oxide nonyl phenyl ether (Emulgen 920; manufactured by Kao), 4 g of polyoxyethylene nonyl phenyl ether sulfate (Hytenol N-08; manufactured by Dai-ichi Kogyo Kagaku), and 40 g of water were added, and a homogenizer (TK Auto Homogen) was added. Using a mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 9000 rpm for 30 minutes.

At this time, the particle size of the atomized product was measured by a particle size analyzer (DLS-7000: manufactured by Otsuka Electronics Co., Ltd.) and found to be 0.4 μm.

45 g of water was charged into a 1 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours under a nitrogen atmosphere. It was added at a constant rate and reacted for another 2 hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

(Comparative Example 3) Methyl methacrylate 2 was added to 70 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo).
45 g, butyl acrylate 230 g, methacrylic acid 1
2 g were added, and further 6 g of polyethylene oxide nonylphenyl ether (Emulgen 920; manufactured by Kao), 4 g of polyoxyethylene nonylphenyl ether sulfate (HITENOL N-08; manufactured by Dai-ichi Kogyo Chemical), and water 2
After adding 00 g, the mixture was atomized using a homogenizer (TK Auto Homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.) at 9000 rpm for 30 minutes.

At this time, when the particle size of the atomized product was measured with a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics), it was 0.4 μm.

530 g of water was charged into a 2 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours under a nitrogen atmosphere. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

(Comparative Example 4) 220 g of methyl methacrylate, 217 g of butyl acrylate and 50 g of methacrylic acid were added to 333 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo Co., Ltd.). 6 g of oxide nonyl phenyl ether (Emulgen 920; manufactured by Kao), 4 g of polyoxyethylene nonyl phenyl ether sulfate (Hytenol N-08; manufactured by Dai-ichi Kogyo Chemical), water 2
After adding 00 g, the mixture was atomized using a homogenizer (TK Auto Homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.) at 9000 rpm for 30 minutes. At this time, when the particle size of the atomized product was measured with a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics Co., Ltd.), it was 0.4 μm.

Into a two-liter four-necked flask equipped with a stirrer, 467 g of water was charged, and after raising the temperature of the system to 80 ° C., 3 g of sodium persulfate was charged. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

(Comparative Example 5) To 333 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo), 245 g of methyl methacrylate, 230 g of butyl acrylate, and 12 g of methacrylic acid were added. 0.5 g of oxide nonylphenyl ether (Emulgen 920; manufactured by Kao)
Polyoxyethylene nonyl phenyl ether sulfate salt (HITENOL N-08; manufactured by Daiichi Kogyo) 0.5
g, water 200 g, and 9000 rpm using a homogenizer (TK Auto Homo Mixer: manufactured by Tokushu Kika Kogyo).
m, over 30 minutes. At this time, when the particle size of the atomized product was measured with a particle size measuring device (DLS-7000: manufactured by Otsuka Electronics Co., Ltd.), it was 0.4 μm.

454 g of water was charged into a 2 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., 3 g of sodium persulfate was charged, and the above-mentioned finely divided product was stirred for 3 hours under a nitrogen atmosphere. Add at a constant rate and add 2
Allowed to react for hours. A large amount of aggregates were generated in the obtained emulsion, and no aqueous resin composition was obtained.

(Comparative Example-6) To 166 g of a 30% toluene solution of chlorinated polypropylene having a chlorination degree of 26% (Hardlen 14-ML: Toyo Kasei Kogyo), 245 g of methyl methacrylate, 230 g of butyl acrylate, and 12 g of methacrylic acid were added. 30 g of oxide nonyl phenyl ether (Emulgen 920; manufactured by Kao), 25 g of polyoxyethylene nonyl phenyl ether sulfate (HITENOL N-08; manufactured by Dai-ichi Kogyo Chemical),
200 g of water was added, and 9000 rpm, 3 rpm using a homogenizer (TK Auto Homo Mixer: manufactured by Tokushu Kika Kogyo).
Micronized over 0 minutes.

At this time, the particle size of the atomized product was measured by a particle size analyzer (DLS-7000: manufactured by Otsuka Electronics Co., Ltd.) and found to be 0.4 μm.

824 g of water was charged into a 2 L four-necked flask equipped with a stirrer, the temperature of the system was raised to 80 ° C., and then 3 g of sodium persulfate was charged. Add at a constant rate and add 2
Allowed to react for hours. The obtained emulsion was filtered through a 200 mesh nylon gauze to obtain an aqueous resin composition having a solid content of 40%.

<Aqueous resin composition evaluation method> (Dispersion stability test) A water resin composition sample (solid content: 40%) was placed in a glass container having a capacity of 100 ml, and the degree of separation of the aqueous phase from the emulsion phase at 50 ° C. The change with time of the degree of formation of resin aggregates was compared.

◎: No change for one month ○: No change for one week △: Change within one week ×: Change within 24H

<< Coating Evaluation Method >> (Method of preparing a co-specimen) The aqueous resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were adjusted to a film thickness of 10 to 15 μm on a black colored polypropylene plate by spraying. Then, drying was performed at 70 ° C. for 30 minutes using a hot air drying group. After the obtained test plate was dried at room temperature for one week, the coating was tested.

<< Coating Test Method >> (Adhesion Test) A cut is made on the coating surface to reach the substrate with a cutter, and 100 grids are made at 1 mm intervals. 5 times, and the number of remaining grids was counted.

◎: 100 ○: 85 to 99
△: 65 to 85 ×: 35 to 65 ××: 35 or less

(Warm Water Resistance Test) The coated plate was immersed in warm water at 40 ° C. for 48 hours, and the whitening of the coated film was examined.

：: no change Δ: whitened but black underground can be confirmed ×: whitening was severe and black underground could not be confirmed

(Oil resistance test) 15 g of grease was applied to the surface of the coating film.
m, and then applied at 80 ° C using a hot air dryer.
After heating for 1 hour, the deterioration (whitening) state of the coating film was determined. ：: No change Δ: Whitened but black underlayer can be confirmed
×: The whitening was so severe that black underground could not be confirmed.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

EFFECT OF THE INVENTION The resin of the present invention has no problem of lowering dispersion stability, is excellent in safety, and is excellent in hot water resistance and oil resistance without impairing the adhesion and adhesion of a substrate, especially a polyolefin substrate. Since it can form an adhesive layer, it is useful as a paint, primer, ink, adhesive or sealant for polyolefin substrates.

Claims (8)

[Claims] 1. A chlorinated polyolefin having a chlorination degree of 5 to 50% by weight, (B) an organic solvent, (C) a vinyl monomer, (D) a surfactant, (E) water, (F) An aqueous resin composition obtained by subjecting a composition comprising a polymerization initiator to emulsion polymerization, or removing the solvent after emulsion polymerization. 2. An organic solvent (B) based on 100 parts by weight of a chlorinated polyolefin (A) having a chlorination degree of 5 to 50% by weight.
100 to 900 parts by weight and vinyl monomer (C) 100 to
2. The aqueous resin composition according to claim 1, comprising 1900 parts by weight. 3. The aqueous resin composition according to claim 1, wherein the vinyl monomer (C) contains a carboxyl group-containing vinyl monomer in an amount of 0 to 10% by weight. 4. The surfactant (D) is a chlorinated polyolefin.
The aqueous resin composition according to any one of claims 1 to 3, wherein the amount is 2 to 100 parts by weight based on 100 parts by weight of (A). 5. A chlorinated polyolefin (A) having a chlorination degree of 5 to 50% by weight dissolved in an organic solvent (B), a vinyl monomer (C), and a surfactant (D). A method for producing an aqueous resin composition, comprising mechanically emulsifying and dispersing a composition comprising water (E), and then adding a polymerization initiator to emulsion-polymerize the monomer (C). 6. A mechanically emulsified and dispersed (A) chlorinated polyolefin, (B) an organic solvent, (C) a vinyl monomer, and (D)
The method for producing an aqueous resin composition according to claim 5, wherein the average particle diameter of the dispersion of the surfactant and (E) water is 1 µm or less. 7. The method for producing an aqueous resin composition according to claim 5, wherein the solvent is removed from the emulsion polymer by distillation under reduced pressure. 8. A coated article characterized by coating the aqueous resin composition obtained in any one of claims 1 to 4 on a substrate.