JPH09278975A - Water-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in low-temperature adhe sion to base materials (esp. polyolefin base materials), water resistance, solvent resistance etc., and useful for coating materials, primers, adhesives, etc., compris ing a chlorinated polyolefin-contg. polymer and an oxazoline group-bearing water-soluble polymer. SOLUTION: This resin composition comprises (A) a chlorinated polyolefin- contg. polymer [e.g. also bearing carboxyl groups, composed of a monomer component, i.e., an ethylenic unsaturated dicarboxylic anhydride (monoester) or ethylenic dicarboxylic acid] and (B) an oxazoline group-bearing water-soluble polymer (e.g. a polymer also bearing OH groups) in the weight ratio A/B of pref. (1:0.01) to (1:1).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition suitable for various uses such as paints, primers, adhesives and printing inks.

[0002]

2. Description of the Related Art Conventionally, chlorinated polyolefin resins have excellent adhesiveness to polyolefin resins such as polypropylene and ethylene-propylene copolymer and solvent resistance, and thus protect the surface of plastics. It is widely used for the purpose. As a method of applying the chlorinated polyolefin resin to the surface of a plastic or the like, a method of dissolving the chlorinated polyolefin resin in an organic solvent and using it as a coating solution is mainly used.

However, since the above method uses a large amount of organic solvent, there are problems in terms of environmental impact, working environment, safety and the like. So, in order to solve these problems,
In recent years, for example, JP-A 1-245041 and JP-A 1-272670 have proposed a method of using a chlorinated polyolefin-containing water dispersion by dispersing a chlorinated polyolefin resin in water.

[0004]

However, the above-mentioned chlorinated polyolefin-containing water dispersion is not sufficient in adhesion, water resistance, solvent resistance, etc. of the obtained coating film to the substrate, and its use is restricted. It has a problem of receiving.
Therefore, there is a demand for an aqueous resin composition that can obtain a coating film having excellent properties such as adhesion to a substrate, water resistance, and solvent resistance, and can be suitably used for various purposes.

The present invention has been made in view of the above conventional problems, and an object thereof is to form a coating film excellent in adhesion to a substrate, water resistance, solvent resistance, etc. An object of the present invention is to provide an aqueous resin composition that can be suitably used for the above purpose.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, an aqueous resin composition containing a chlorinated polyolefin-containing polymer and an oxazoline group-containing water-soluble polymer is It has been found that a coating film having excellent adhesion to materials, water resistance, solvent resistance, etc. can be formed, and thus it can be suitably used for various purposes, and the present invention has been completed.

That is, the aqueous resin composition of the invention according to claim 1 is characterized by containing a chlorinated polyolefin-containing polymer and an oxazoline group-containing water-soluble polymer in order to solve the above problems.

The aqueous resin composition according to the second aspect of the invention is
In order to solve the above problems, in the aqueous resin composition according to claim 1, the chlorinated polyolefin-containing polymer is characterized by containing a carboxyl group.

The aqueous resin composition according to the third aspect of the invention is
In order to solve the above problems, in the aqueous resin composition according to claim 1 or 2, the chlorinated polyolefin-containing polymer is an ethylenically unsaturated dicarboxylic acid anhydride or a monoethylenic unsaturated dicarboxylic acid anhydride. The water-soluble polymer containing an oxazoline group, which is composed of at least one monomer component selected from the group consisting of an ester and an ethylenic dicarboxylic acid, is a hydroxyl group-containing copolymer.

According to the above construction, the adhesion to the base material, especially the adhesion to the plastic base material such as the polyolefin base material at a low temperature is very good as compared with the conventional ones, and the water resistance and the solvent resistance are excellent. It is possible to provide an aqueous resin composition capable of forming an excellent coating film. The aqueous resin composition is, for example, a paint, a primer, an adhesive,
It can be suitably used for various purposes such as printing ink.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below in detail. The aqueous resin composition of the present invention comprises a chlorinated polyolefin-containing polymer and an oxazoline group-containing water-soluble polymer. The chlorinated polyolefin-containing polymer used in the present invention can be easily obtained by using the chlorinated polyolefin resin alone or by mixing it with a polymer other than the chlorinated polyolefin resin. The chlorinated polyolefin resin is not particularly limited, but specifically, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polybutene, ethylene-vinyl acetate. Copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, natural rubber, polyolefins such as olefin rubber and modified polyolefins obtained by introducing carboxyl groups, hydroxyl groups, acid anhydride groups, etc. into these polyolefins. Examples thereof include chlorinated polyolefin resins chlorinated by known methods.

The method for producing the chlorinated polyolefin resin is not particularly limited, and for example, it can be easily desired by dissolving or dispersing the above polyolefins in an appropriate medium and then reacting with chlorine gas. It is possible to obtain a chlorinated polyolefin resin. It is preferable to use water as the above medium in consideration of the environment. The reaction conditions and the like for carrying out the above reaction are not particularly limited, and may be appropriately set so that the reaction is completed. Further, when carrying out the reaction, ultraviolet rays or visible rays may be appropriately irradiated or a radical polymerization initiator may be used in order to allow the reaction to proceed smoothly.

Among these chlorinated polyolefin resins, chlorinated polyolefin resins obtained by chlorinating polypropylene and / or polyethylene are preferable. Furthermore, as a preferable example of the chlorinated polyolefin resin, an acid anhydride-modified chlorinated polyolefin obtained by modifying the above-mentioned chlorinated polyolefin resin with maleic anhydride or the like can be mentioned. Further, examples of commercially available chlorinated polyolefin resins include “Super Clone” (trade name; manufactured by Nippon Paper Industries Co., Ltd.) and “Hardlen” (trade name;
Manufactured by Toyo Kasei Co., Ltd.) and the like. Only one kind of these chlorinated polyolefin resins may be used, or two or more kinds thereof may be appropriately mixed and used.

Specific examples of the polymer other than the chlorinated polyolefin resin include vinyl polymers, polyesters, polyethers, polyamides, polyamines, etc. which do not correspond to the chlorinated polyolefin resin. It is not particularly limited. However, in the present invention, the presence of a carboxyl group in the chlorinated polyolefin-containing polymer, the adhesion of the coating film, the stability of the dispersion when the chlorinated polyolefin-containing polymer is used as a dispersion Are particularly preferred. Therefore, when the chlorinated polyolefin resin does not contain a carboxyl group, the polymer other than the chlorinated polyolefin resin optionally contained in the chlorinated polyolefin-containing polymer is a polymer containing a carboxyl group. Is particularly preferred.

The method for introducing the carboxyl group into the chlorinated polyolefin-containing polymer is not particularly limited, and a method using the above-mentioned modified chlorinated polyolefin resin containing a carboxyl group or an acid anhydride group is used. , A method of dispersing a polymer containing a carboxyl group in an aqueous medium together with a chlorinated polyolefin resin,
A method in which a chlorinated polyolefin resin is dissolved in a monomer containing a carboxyl group and then dispersed in an aqueous medium for polymerization, and a carboxyl group-containing water-soluble polymer is used as a dispersant, and the carboxyl group-containing aqueous solution is used. Various methods such as a method of dispersing a chlorinated polyolefin resin in an aqueous medium in the presence of a water-soluble polymer can be used.

As the monomer or polymer which can be used for containing a carboxyl group in the chlorinated polyolefin-containing polymer, specifically, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, cinnamic acid, and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, or carboxyl group-containing units such as monoesters thereof And / or acid anhydride group-containing monomers such as itaconic anhydride, maleic anhydride and citraconic anhydride, and polymers obtained by polymerizing a monomer component containing these monomers.

The amount of the carboxyl groups contained in the chlorinated polyolefin-containing polymer is not particularly limited, but the acid value based on the solid content in the chlorinated polyolefin-containing polymer is 5 mgKOH / g to 200 mgKOH. /
It is preferable to set it within the range of g.

The amount of the chlorinated polyolefin resin used in the chlorinated polyolefin-containing polymer is not particularly limited, but is preferably in the range of 10% by weight to 100% by weight. If the amount of the chlorinated polyolefin resin used is less than 10% by weight, the adhesion of the coating film formed by curing the finally obtained aqueous resin composition to the substrate tends to be impaired, which is not preferable.

The chlorinated polyolefin-containing polymer can be used in various forms such as an aqueous solution or dispersion. The method for dispersing the chlorinated polyolefin-containing polymer in an aqueous medium is not particularly limited, and, for example, (i) a chlorinated polyolefin resin dissolved in a solvent may be added to another polymer, an emulsifier or a dispersant. A method of dispersing in an aqueous medium in the presence of, (ii) aqueous by adding a basic compound to a resin mixture obtained by polymerizing a monomer containing an acid anhydride group or a carboxyl group in the presence of a chlorinated polyolefin resin Various conventionally known methods can be adopted, such as a method of dispersing in a medium, (iii) a method of dispersing a vinyl monomer in which a chlorinated polyolefin resin is dissolved in an aqueous medium and then performing polymerization.

The above aqueous medium is not particularly limited as long as it is water or an organic solvent miscible with water.
As the aqueous medium, specifically, for example, water, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, ethylene glycol,
Examples thereof include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, propylene glycol monomethyl ether, acetone and methyl ethyl ketone. Among these aqueous media, it is preferable to use water or a mixed solvent of water and an organic solvent miscible with water.

The oxazoline group-containing water-soluble polymer used in the present invention is a polymer having a plurality of oxazoline groups in its side chain, and the addition-polymerizable oxazoline compound may be used alone or in addition polymerization. It can be easily obtained by copolymerizing with another addition-polymerizable compound which can be copolymerized with the oxazoline compound (hereinafter, simply referred to as other addition-polymerizable compound).

The above-mentioned addition-polymerizable oxazoline compound is
The following general formula (1)

[0023]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group or a substituted phenyl group, and R
₅ represents an acyclic organic residue having an addition polymerizable unsaturated bond). Specific examples of the addition-polymerizable oxazoline compound include 2-vinyl-
2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl
— 2-Oxazoline and the like.

These addition-polymerizable oxazoline compounds are
Only one type may be used, or two or more types may be appropriately mixed and used. Among these addition-polymerizable oxazoline compounds, 2-isopropenyl-2-oxazoline is preferable because it is industrially easily available and has good reactivity.

The other addition-polymerizable compound is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline compound. Specific examples of the above-mentioned other addition-polymerizable compounds include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
(Meth) acrylic acid esters such as methoxypolyethylene glycol acrylate; (meth) acrylic acid salts such as sodium (meth) acrylate and ammonium (meth) acrylate; hydroxyl group-containing such as hydroxyethyl (meth) acrylate ( (Meth) acrylic acid esters;
Unsaturated nitriles such as (meth) acrylonitrile; Unsaturated amides such as (meth) acrylamide and N-methylol (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Kinds; ethylene,
Olefins such as propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride; α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene Can be mentioned. Only one kind of these other addition-polymerizable compounds may be used, or two or more kinds thereof may be appropriately mixed and used. Among these other addition-polymerizable compounds, hydrophilic monomers are preferred, and hydroxyl group-containing monomers are more preferred.

The amount of the addition-polymerizable oxazoline compound used, that is, the content of the addition-polymerizable oxazoline compound in the monomer component forming the oxazoline group-containing water-soluble polymer is in the range of 5% by weight to 100% by weight. It is preferably within the range of 5% by weight or more and less than 90% by weight. When the amount of the addition-polymerizable oxazoline compound used is less than 5% by weight, the adhesion of the coating film formed by curing the finally obtained aqueous resin composition to plastic becomes insufficient, which is not preferable. Further, since the degree of adhesion does not change even if the addition-polymerizable oxazoline compound is used in an amount of 90% by weight or more, the amount of the addition-polymerizable oxazoline compound used is set in the range of 5% by weight or more and less than 90% by weight. It is preferable from the viewpoint of cost.

In order to impart water solubility to the oxazoline group-containing water-soluble polymer, the proportion of the hydrophilic monomer in the above-mentioned monomer component is within the range of 50% by weight to 100% by weight. It is preferably in the range of 60% by weight to 90% by weight, and more preferably in the range of 60% by weight to 90% by weight. Examples of the hydrophilic monomer include the addition-polymerizable oxazoline compound and other addition-polymerizable compounds (meth) acrylate 2-hydroxyethyl acrylate,
Methoxy polyethylene glycol (meth) acrylate,
Sodium (meth) acrylate, ammonium (meth) acrylate, 2-aminoethyl (meth) acrylate and its salts, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, sodium styrenesulfonate, etc. Is mentioned. Among the oxazoline group-containing water-soluble polymers thus obtained, a hydroxyl group-containing copolymer is particularly preferable.

The method for producing the oxazoline group-containing water-soluble polymer is not particularly limited, and various conventionally known polymerization methods can be adopted. For example,
You may adopt the method of performing solution polymerization in an aqueous medium,
A method of dissolving an oxazoline group-containing water-soluble polymer prepared in advance by a known polymerization method in an aqueous medium may be adopted. The aqueous medium is not particularly limited as long as it is water or an organic solvent miscible with water. As the aqueous medium, the same compounds as those exemplified above can be used. Further, the polymerization conditions and the like when carrying out the polymerization reaction are not particularly limited, but the number average molecular weight (Mn) of the oxazoline group-containing water-soluble polymer is 1,00
It is preferable to set it to be 0 or more.

The aqueous resin composition of the present invention can be easily obtained by mixing the chlorinated polyolefin-containing polymer and the oxazoline group-containing water-soluble polymer.
The mixing ratio of the chlorinated polyolefin-containing polymer and the oxazoline group-containing water-soluble polymer is not particularly limited, but may be in the range of 1: 0.01 to 1: 1 in terms of solid content weight ratio. preferable. If the blending ratio is out of the above range, the adhesion of the coating film formed by curing the aqueous resin composition to the substrate tends to decrease, which is not preferable.

By the way, the acid anhydride monoester, dicarboxylic acid, or dicarboxylic acid produced as a result of hydrolysis of the acid anhydride in the above-mentioned chlorinated polyolefin-containing polymer undergoes ring closure again at the curing temperature and once becomes an acid anhydride. Return. At this time, when the oxazoline group-containing water-soluble polymer contains a hydroxyl group, the acid anhydride and the hydroxyl group in the oxazoline group-containing water-soluble polymer react and crosslink, and the remaining carboxyl group is an oxazoline group. Reacts with, and the crosslinking proceeds rapidly. For this reason,
The obtained cured product has a stronger structure.

From this, as the above-mentioned chlorinated polyolefin-containing polymer and oxazoline group-containing water-soluble polymer, the chlorinated polyolefin-containing polymer is an ethylenically unsaturated dicarboxylic acid anhydride or an ethylenically unsaturated dicarboxylic acid anhydride. It is particularly preferable that the oxazoline group-containing water-soluble polymer is a copolymer containing at least one monomer component selected from the group consisting of a monoester of a product and an ethylenic dicarboxylic acid, and the oxazoline group-containing water-soluble polymer. preferable. The coating film obtained by curing the water-based resin composition has a stronger structure and is particularly excellent in solvent resistance, water resistance and adhesion.

The aqueous resin composition of the present invention may further contain other compounds having two or more functional groups that react with oxazoline groups (hereinafter referred to as other compounds), if necessary.
Aqueous resins other than the chlorinated polyolefin-containing polymer and the oxazoline group-containing water-soluble polymer (hereinafter referred to as other aqueous resins), water-based crosslinking agents, and other additives (the above other compounds, other aqueous resins) And additives other than the water-based crosslinking agent) and the like.

Specific examples of the above-mentioned other compounds include aliphatic polymercapto compounds such as 1,6-dimercaptohexane, dimercaptodiethyl ether, and 2,2-dimercaptodiethylsulfide; 3,4- Dimercaptotoluene, bis (4-mercaptophenyl) sulfide,
Aromatic polymercapto compounds such as 4-t-butyl-1,2-benzenedithiol, 1,5-dimercaptonaphthalene, 2,7-dimercaptonaphthalene, 2,5-dimercapto-1,3,4-thiadiazole; 2,4-dimercapto-6-dibutylamino-1,
General formula (2) such as 3,5-triazine, 2,4,6-trimercapto-1,3,5-triazine and 2,4-dimercapto-6-phenylamino-1,3,5-triazine

[0035]

Embedded image

(In the formula, Y is NHR ₆ , NR ₇ R ₈ , OR
₉ or SR ₁₀ , R ₆ , R ₇ , R ₈ , R ₉ , SR
₁₀ represents a hydrogen atom or a hydrocarbon group); an aliphatic polycarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, adipic acid and sebacic acid; a maleic acid, fumaric acid, etc. Saturated polycarboxylic acid compounds; aromatic polycarboxylic acid compounds such as phthalic acid, terephthalic acid, diphenylmethanedicarboxylic acid, naphthalenedicarboxylic acid, and the like.

As the other water-based resin, various conventionally known water-based resins can be used. Specific examples of the above-mentioned other aqueous resins include water-dispersible or water-soluble materials such as "Acryset" (trade name; manufactured by Nippon Shokubai Co., Ltd.) and "Alloron" (trade name; manufactured by Nippon Shokubai Co., Ltd.). Acrylic resin; "Hydran" (trade name;
Made by Dainippon Ink and Chemicals, Inc., "Bondick"
(Product name: Dainippon Ink and Chemicals, Inc.), "Poise" (Product name: Kao Corporation), "Superflex" (Product name: Dai-ichi Kogyo Seiyaku Co., Ltd.), "Neolets" (Product name) Water-based polyurethanes such as Zeneca Co., Ltd .; Water-based polyesters such as "Bylonal" (trade name; manufactured by Toyobo Co., Ltd.), Finetex (trade name; manufactured by Dainippon Ink and Chemicals, Inc.); "Horus"
(Product name; manufactured by Kansai Paint Co., Ltd.), water-dispersible, water-diluted or water-soluble alkyd resin; "Isoban" (trade name; manufactured by Kuraray Isoprene Chemical Co.), product name "Primacol" (manufactured by Dow Chemical Co., Ltd.) ), "High Tech" (trade name; manufactured by Toho Chemical Industry Co., Ltd.), water-dispersed, water-diluted or water-soluble polyolefin resin; "Epiclon"
(Trade name; manufactured by Dainippon Ink and Chemicals, Inc.) and the like, water-dispersed epoxy resins; vinyl chloride emulsion and the like, but are not particularly limited.

Specific examples of the water-based crosslinking agent include water-soluble, water-dispersible or water-dilutable melamine compounds, isocyanate compounds, blocked isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, and hydrazide compounds. Can be mentioned.

Further, as the above-mentioned other additives, specifically, for example, plasticizers such as phthalic acid ester and benzyl alcohol; fillers such as calcium carbonate, talc, clay and mica; titanium white, zinc white, Examples include pigments such as red iron oxide, phthalocyanine; dyes; thickeners such as polyvinyl alcohol, hydroxyethyl cellulose and starch; dispersants; wetting agents; antifoaming agents such as silicones.

Only one kind of each of these various additives (the above-mentioned other compounds, the other aqueous resin, the water-based crosslinking agent and the other additives, etc.) contained in the above-mentioned aqueous resin composition as necessary is used. Alternatively, two or more kinds may be appropriately mixed and used. The addition amount of these various additives is
There is no particular limitation as long as it does not impair the desired physical properties of the aqueous resin composition.

In the present invention, the method for preparing the above aqueous resin composition is not particularly limited, and various conventionally known methods can be applied. For example, an aqueous dispersion of a chlorinated polyolefin-containing polymer, an oxazoline group-containing water-soluble polymer, and optionally the above-mentioned various additives are added and mixed to easily adjust the desired aqueous resin composition. be able to. The mixing method and the order of addition in this case are not particularly limited. Further, the aqueous resin composition according to the present invention can be used by further adding an aqueous medium and dissolving or dispersing the above aqueous resin composition in the aqueous medium depending on the application. The amount of the aqueous medium used may be appropriately set according to the application and is not particularly limited.

When the aqueous resin composition of the present invention is used as, for example, a paint, a primer, an adhesive, a printing ink, etc., for example, a roll coater, spray, dipping,
It can be applied to the substrate using a conventional method such as brush coating. The base material is not particularly limited, and specifically, for example, plastic, wood, paper, non-woven fabric, glass fiber, polyester fiber, metal, inorganic material and the like can be used. Thus, by applying and curing the aqueous resin composition of the present invention on the substrate, it is possible to obtain a coating film (film) having good adhesion to the substrate and excellent water resistance and solvent resistance. it can. The curing conditions for curing the above aqueous resin composition are not particularly limited. By using the above aqueous resin composition, it is possible to cure at a high temperature (for example, about 120 ° C) as well as at a lower temperature (about 60 ° C to 80 ° C) in a shorter time than conventional aqueous resin compositions. Therefore, it is possible to obtain a coating film having particularly excellent adhesion at low temperature to a substrate, particularly a plastic substrate such as a polyolefin substrate.

As described above, the aqueous resin composition according to the present invention is configured to contain the chlorinated polyolefin-containing polymer and the oxazoline group-containing water-soluble polymer. Further, the aqueous resin composition according to the present invention is configured such that the chlorinated polyolefin-containing polymer contains a carboxyl group. Furthermore, the aqueous resin composition according to the present invention, the chlorinated polyolefin-containing polymer is an ethylenically unsaturated dicarboxylic acid anhydride, a monoester of ethylenically unsaturated dicarboxylic acid anhydride and a group consisting of ethylenic dicarboxylic acid. The oxazoline group-containing water-soluble polymer is composed of at least one selected monomer component and is a hydroxyl group-containing copolymer.

According to the above constitution, the adhesion to the base material, particularly the adhesion to the plastic base material such as the polyolefin base material at a low temperature is extremely good as compared with the conventional one, and the water resistance and the solvent resistance are excellent. It is possible to provide an aqueous resin composition capable of forming an excellent coating film. That is, the aqueous resin composition of the present invention contains an oxazoline group-containing water-soluble polymer as the oxazoline group-containing polymer, so that the aqueous resin composition can be cured at a lower temperature as compared with the conventional one, and has good adhesion to a substrate. Is excellent. Further, the aqueous resin composition of the present invention can reduce the addition amount of the oxazoline group-containing polymer by including the oxazoline group-containing water-soluble polymer as the oxazoline group-containing polymer.
The aqueous resin composition can be suitably used for various applications such as paints, primers, adhesives and printing inks.

[0045]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, "part" means "part by weight" and "%" means "% by weight".

The performance of the coating film obtained by curing the water-soluble resin composition was evaluated by the following test method. (A) Adhesion According to the cross-cut test method described in JIS K500,
A grid was placed on the test sample. That is, the coating film was divided into 100 small pieces (mesh) by putting a grid on the 10 mm square coating film on a polypropylene plate at 1 mm intervals. Then, after crimping the cellophane tape to the small piece, the cellophane tape was vigorously peeled from the polypropylene plate,
The number of grids of the coating film that was not peeled from the polypropylene plate by this peeling operation was counted and used as an index of the adhesiveness.

(B) Water-resistant adhesion The adhesion of the test sample immersed in deionized water at 30 ° C. for 7 days was evaluated by the same method as in (a) above.

(C) Solvent Resistance The surface of the test sample was rubbed with absorbent cotton containing methyl ethyl ketone. Then, the state of the coating film on the surface of the test sample after the rubbing operation was performed 50 times was visually confirmed. In the table, (◎) indicates that there is no change in the state of the coating film on the surface of the test sample before and after the rubbing operation.
() Indicates that the coating film on the surface of the test sample was slightly scratched by the rubbing operation, and (Δ) indicates that the coating film on the test sample surface was scratched by the rubbing operation.
(X) indicates that the coating film on the surface of the test sample was dissolved or peeled off from the polypropylene plate due to the frictional action.

Example 1 A flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, a thermometer, and a dropping funnel was charged with "Supercron 892L" (trade name; maleic acid-modified chlorination manufactured by Nippon Paper Industries Co., Ltd.). 20 of polypropylene resin
% Toluene solution, chlorine content 22%) 375 parts, "Epicoat 82B" (epoxy resin manufactured by Shell Chemical Co., Ltd.) 5
And 5 parts of "NK Ester M-230G" (Methoxypolyethylene glycol methacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) were charged and heated to 80 ° C. while gently blowing nitrogen gas. On the other hand, a mixed solution obtained by mixing 4 parts of methacrylic acid, 8 parts of 2-ethylhexyl methacrylate, 7 parts of cyclohexyl methacrylate, and 1 part of benzoyl peroxide as a polymerization initiator was placed in a dropping funnel. Next, nitrogen gas was blown into the flask, and the mixed solution in the dropping device was dropped into the flask over 3 hours while maintaining the temperature in the flask at 80 ± 1 ° C.

After completion of dropping, the reaction solution was heated to 90 ° C. and stirred for 2 hours to continue the reaction, and then 25 parts of butanol as an aqueous medium was added. On the other hand, the aqueous solution obtained by mixing 300 parts of deionized water and 6 parts of 28% ammonia water was put into a dropping funnel. Next, the aqueous solution in the dropping device was dropped into the flask over 1 hour to obtain a dispersion liquid. Then, the solvent was removed by distillation under reduced pressure to obtain an aqueous dispersion of a chlorinated polyolefin-containing polymer having a nonvolatile content of 25.5% (hereinafter, referred to as an aqueous dispersion (A-1) for convenience of description). Obtained.

A flask equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, a thermometer, and a dropping funnel was charged with 370 parts of deionized water, and p was added with an appropriate amount of 28% ammonia water.
After adjusting H to 9.0, the mixture was heated to 60 ° C. while slowly blowing nitrogen gas. On the other hand, 5 parts of ethyl acrylate,
A monomer component prepared by mixing 10 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl acrylate and 75 parts of 2-isopropenyl-2-oxazoline was put in a dropping funnel. Next, while blowing nitrogen gas into the flask and maintaining the temperature in the flask at 60 ± 1 ° C., a 5% aqueous solution of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator. 50 parts was injected, and then the above-mentioned monomer components in the dropping apparatus were dropped into the flask over 3 hours.

After completion of dropping, the reaction solution was heated to 70 ° C. and stirred for 3 hours to complete the reaction. Then, after cooling the reaction solution, the pH of the reaction solution was adjusted to 8.0 with an appropriate amount of 28% ammonia water, so that the nonvolatile content was 20.2%.
% Aqueous solution of oxazoline group-containing water-soluble polymer (hereinafter,
For convenience of description, an aqueous solution (B-1) was obtained.

Next, an aqueous resin composition was obtained by mixing 4 parts of the aqueous solution (B-1) with 100 parts of the above aqueous dispersion (A-1). The obtained aqueous resin composition was applied to a polypropylene plate whose surface was washed with isopropanol so that the dry film thickness was about 60 μm, and then forcedly dried at 80 ° C. for 30 minutes to obtain a test sample. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

Example 2 In Example 1, the mixing ratio of the aqueous dispersion (A-1) and the aqueous solution (B-1) was changed to 100 parts by weight of the aqueous dispersion (A-1). -1) An aqueous resin composition was obtained in the same manner as in Example 1 except that 8 parts was used. Example 1 was carried out using the obtained aqueous resin composition.
A test sample was obtained in the same manner as in. The performance of this test sample was evaluated by the method described above. This result
It shows in Table 1 with the above-mentioned compounding conditions.

Comparative Example 1 By the same method as in Example 1 except that the aqueous solution (B-1) was not blended and only 100 parts of the aqueous dispersion (A-1) was used. A test sample for comparison was obtained. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

Comparative Example 2 In a flask equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube, a thermometer, and a dropping funnel, 782.4 parts of deionized water and "Hitenol N-0" were placed.
8 "(trade name; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 15% aqueous solution
Charge 128 parts and adjust the pH to 9.0 with an appropriate amount of 28% ammonia water.
After adjusting it to 70, while blowing nitrogen gas gently
Heated to ° C. On the other hand, 330 parts of butyl acrylate, 246 parts of styrene, and 64 parts of 2-isopropenyl-2-oxazoline
The monomer components prepared by mixing the parts were put into a dropping funnel. Next, 64 parts of a 5% aqueous solution of potassium persulfate as a polymerization initiator was injected into the above flask while blowing nitrogen gas and maintaining the temperature in the flask at 70 ± 1 ° C., followed by a dropping device. The above-mentioned monomer component therein was dropped into the flask over 3 hours.

After completion of dropping, the reaction solution was heated to 80 ° C. and stirred for 1 hour to complete the reaction. Next, after cooling the reaction solution, the pH of the reaction solution was adjusted to 8.0 with an appropriate amount of 28% aqueous ammonia, so that the nonvolatile content was 39.8%.
% Of an oxazoline group-containing polymer aqueous dispersion (hereinafter, referred to as an aqueous dispersion (B′-1) for convenience of description) was obtained.

Then, 20 parts of the above water dispersion (B'-1) was mixed with 100 parts of the water dispersion (A-1) obtained by the same method as in Example 1 for comparison. A water-based resin composition of Then, a test sample for comparison was obtained by the same method as in Example 1 using the obtained aqueous resin composition for comparison. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

[Embodiment 3] "Super Clone 822"
(Product name: 20% toluene solution of chlorinated polypropylene resin modified with maleic acid manufactured by Nippon Paper Industries Co., Ltd., chlorine content 24.5
%) 250 parts, methyl methacrylate 10 parts and butyl acrylate 39 parts, maleic anhydride 1 part in a mixed solution, deionized water 35 parts and "Perex OTP" (trade name; Kao Corporation anionic surfactant ) 5 parts were added, and a homogenizer (manufactured by Nippon Seiki Co., Ltd., BM-4 type)
A monomer emulsion was obtained by treating at 18000 rpm for 30 minutes.

Next, 200 parts of deionized water was charged into the same flask as in Example 1 and heated to 80 ° C. while slowly blowing nitrogen gas. On the other hand, a mixed solution prepared by mixing 340 parts of the previously prepared monomer emulsion and 0.5 part of "Perbutyl O" (trade name; manufactured by NOF CORPORATION) as a polymerization initiator was placed in a dropping funnel. Next, while blowing nitrogen gas into the flask, the temperature in the flask was adjusted to 80
While maintaining the temperature at ± 1 ° C., the mixed solution in the dropping device was dropped into the flask over 3 hours.

After completion of dropping, the reaction was completed by stirring the above reaction solution at 80 ° C. for 2 hours. After that, the solvent is removed by distilling the obtained dispersion liquid under reduced pressure, followed by cooling and adjusting the pH with an appropriate amount of 28% ammonia water.
Adjusted to 8.0. As a result, an aqueous dispersion of a chlorinated polyolefin-containing polymer having a nonvolatile content of 29.1% (hereinafter, referred to as an aqueous dispersion (A-2) for convenience of description) was obtained.

Next, with respect to 100 parts of the above aqueous dispersion (A-2), an aqueous solution (B-
1) An aqueous resin composition was obtained by mixing 4 parts. Then, a test sample was obtained in the same manner as in Example 1 by using the obtained aqueous resin composition. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

Comparative Example 3 By the same method as in Example 3, except that the aqueous solution (B-1) was not blended and only 100 parts of the aqueous dispersion (A-2) was used. A test sample for comparison was obtained. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

Example 4 To 100 parts of the aqueous dispersion (A-2), 10 parts of the aqueous solution (B-1) and "Acryset 210E" as another aqueous resin (trade name; manufactured by Nippon Shokubai Co., Ltd.) , Non-volatile content 50% acrylic emulsion: hereinafter referred to as other aqueous resin (C-1) for convenience of description) 40 parts and "Neo Let's R960" (trade name; manufactured by Zeneca Corporation, non-volatile content 33% aqueous urethane Hereinafter, for convenience of description, 10 parts of another aqueous resin (C-2) will be mixed to obtain an aqueous resin composition. A test sample was obtained in the same manner as in Example 1, using the obtained aqueous resin composition. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

Comparative Example 4 By mixing 40 parts of another aqueous resin (C-1) and 10 parts of another aqueous resin (C-2) with 100 parts of the aqueous dispersion (A-2), An aqueous resin composition for comparison was obtained. Using the obtained aqueous resin composition, a test sample for comparison was obtained in the same manner as in Example 4, that is, Example 1. The performance of this test sample was evaluated by the method described above. The results are shown in Table 1 together with the above blending conditions.

[0066]

[Table 1]

From the results shown in Table 1, the coating film obtained from the aqueous resin composition according to the present example has good curability at low temperature, and compared with the coating film obtained in Comparative Example. It can be seen that the adhesiveness with the polypropylene plate is excellent. Also,
The coating film obtained from the aqueous resin composition according to this example,
It can be seen that, as compared with the coating film obtained in the comparative example, it is also excellent in performance such as water-resistant adhesion and solvent resistance.

[0068]

As described above, the aqueous resin composition according to the first aspect of the present invention is configured to contain the chlorinated polyolefin-containing polymer and the oxazoline group-containing water-soluble polymer.

The aqueous resin composition according to claim 2 of the present invention is, as described above, configured such that the chlorinated polyolefin-containing polymer contains a carboxyl group.

Further, in the aqueous resin composition according to claim 3 of the present invention, as described above, the chlorinated polyolefin-containing polymer is an ethylenically unsaturated dicarboxylic acid anhydride or an ethylenically unsaturated dicarboxylic acid anhydride. Of the monoester and the ethylenic dicarboxylic acid of at least one monomer component, and the oxazoline group-containing water-soluble polymer is a hydroxyl group-containing copolymer.

According to the above constitution, the adhesion to the base material, particularly the adhesion to the plastic base material such as the polyolefin base material at a low temperature is very good as compared with the conventional one, and the water resistance, the solvent resistance, etc. It is possible to provide an aqueous resin composition capable of forming an excellent coating film. The aqueous resin composition is, for example, a paint, a primer, an adhesive,
It has an effect that it can be suitably used for various purposes such as printing ink.

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Claims (3)

[Claims] 1. An aqueous resin composition comprising a chlorinated polyolefin-containing polymer and an oxazoline group-containing water-soluble polymer. 2. The chlorinated polyolefin-containing polymer,
The aqueous resin composition according to claim 1, which contains a carboxyl group. 3. The chlorinated polyolefin-containing polymer,
It is composed of at least one monomer component selected from the group consisting of ethylenically unsaturated dicarboxylic acid anhydrides, monoesters of ethylenically unsaturated dicarboxylic acid anhydrides and ethylenic dicarboxylic acids, and also contains the above-mentioned oxazoline group-containing water-soluble polymer. The aqueous resin composition according to claim 1 or 2, wherein the combined product is a copolymer containing a hydroxyl group.