JP2001163984A - Aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have excellent adhesion, coating appearance, solvent resistance and excellent flexibility as a primer for paints, inks or adhesives to a polyolefin resin molding or film. To provide an aqueous dispersion which gives a good coating. The carboxylic acid-modified chlorinated polyolefin having a chlorine content of 15 to 35% by weight and a mixture of a carboxylic acid-modified ethylene-vinyl acetate copolymer in a ratio of 90/10 to 10/90 are used. An aqueous dispersion neutralized with a substance and dispersed in water using a nonionic surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of a resin composition for a paint or an adhesive obtained for the purpose of protection or cosmetics of a polyolefin resin, for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer and the like. It is about.

[0002]

2. Description of the Related Art Conventionally, olefin resins such as polypropylene have been used in automobile parts because of their high chemical stability, low cost, excellent balance of physical properties, and recyclability. , And the number of products for household appliances and household goods is increasing year by year. However, since the olefin-based resin does not contain a polar group in the molecular chain, it has a drawback that it is difficult to be applied and that adhesion and the like are difficult. For this reason, in the case of polypropylene-based coating or bonding, it is common to use a resin containing chlorinated polypropylene as a main component as a primer or one coat. However, chlorinated polypropylene generally uses an aromatic organic solvent such as toluene or xylene, and has a problem in terms of safety and health and environmental pollution.

[0003] Attempts have been made to produce aqueous dispersions of chlorinated polypropylene. Aqueous dispersion of carboxyl group-containing chlorinated polyolefin (JP-B8-600
9), a method for producing a resin composition emulsion (Patent 272703)
2) Use of a reactive surfactant (Patent No. 2603173) has been proposed.

[0004] In recent years, due to these environmental problems, especially for automotive interior applications, the use of water has been actively studied. In this case, the required performance requires not only adhesion but also flexibility. However, in order to satisfy the recent demand for improving the flexibility of the coating film in automotive interior paints, a flexibility-imparting component is required. However, the aqueous resin dispersion of chlorinated polypropylene alone has good adhesion to polypropylene, but cannot improve flexibility. Further, the aqueous resin dispersion of the chlorinated polypropylene alone has poor adhesion to materials other than polypropylene, particularly ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) used for shoes.

On the other hand, EVA copolymer emulsions include inventions such as water-based adhesives for paper, OPP film and wood (Japanese Patent Application Laid-Open Nos. 62-135583 and 6-65550), but they are not used for olefins. Further, as an aqueous adhesive for a polyolefin substrate, an aqueous adhesive obtained by mixing a chlorinated resin with an acrylate copolymer (Patent No. 2561495) has been proposed, but an aromatic solvent such as toluene and xylene is used in chlorine. It is hard to say that it is a complete aqueous system because it is added 2 to 20 times by weight to the modified resin. Also, since the chlorinated resin used is not acid-modified, it can be used only for adhesives. When used as a primer, it has poor adhesion to the top coat and has a practical problem.

[0006] Further, for a system in which an aqueous dispersion of a chlorinated polyolefin and an aqueous dispersion of an EVA copolymer are mixed, a water-soluble polyethylene primer composition (JP-A-4-35
1681) and a water-based adhesive composition for polyolefin and a primer (JP-A-6-25628). But,
The former is to provide a solvent-type polyethylene primer which is made water-soluble by using a large amount of an aromatic solvent in order to increase the solubility of a raw material resin during the production of an aqueous dispersion, and is hardly an aqueous dispersion.

On the other hand, for the latter, 2 to 50 parts by weight of a surfactant solution (component 1) having a chlorinated polyolefin concentration of 5 to 25% is prepared, and 50 to 98 parts by weight of an EVA copolymer emulsion (component 2) are prepared. Mixed. Therefore, when the amount of the component 1 is small, the adhesion to the polyolefin is inferior. On the other hand, when the amount of the component 1 is large, the amount of the surfactant is relatively large. It can be easily analogized that it is inferior. In addition, when used as a primer, a preliminary washing treatment is required with a chlorinated solvent such as 1,1,1-trichloroethylene, which is complicated in the process.

[0008]

DISCLOSURE OF THE INVENTION The present invention has excellent adhesion, coating film appearance, solvent resistance to moldings or films of polyolefin resins as primers for paints, inks or adhesives, and The present invention relates to an aqueous dispersion which gives a coating film having good flexibility.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the chlorine content is 15 to 15%.
It has been found that a 35% by weight chlorinated polyolefin and ethylene-vinyl acetate copolymer can be achieved by an aqueous dispersion having a mixing ratio of 90/10 to 10/90.

That is, the chlorinated polyolefin component is a chlorinated polyolefin having a chlorine content of 15 to 35% by weight, preferably a carboxylic acid-modified one.
The acid value is 10 to 100, and the number average molecular weight is 2,000 to 40,000. On the other hand, the ethylene-vinyl acetate copolymer component is preferably a carboxylic acid-modified component. Neutralizing a mixture of the (A) carboxylic acid-modified chlorinated polyolefin and (B) carboxylic acid-modified ethylene-vinyl acetate copolymer with a basic substance,
An aqueous dispersion dispersed in water using a nonionic surfactant can be used as a primer for paints, inks or adhesives on molded products or films of polyolefin resins to improve adhesion, flexibility and appearance of coatings. It has been found that it gives a good coating film.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The aqueous dispersion used in the present invention contains, as a main component, a mixture of (A) a carboxylic acid-modified chlorinated polyolefin and (B) a carboxylic acid-modified ethylene-vinyl acetate copolymer. This will be described in detail below.

(A) The carboxylic acid-modified chlorinated polyolefin is obtained by dissolving the polyolefin in a solvent inert to chlorine, such as chloroform, and chlorinating by blowing a chlorine gas. The olefin is unsaturated before or after chlorination. A carboxyl group can be introduced by graft copolymerizing a carboxylic acid or its anhydride.

The polyolefin is a homopolymer of ethylene or polypropylene, or a comonomer of ethylene or propylene, for example, butene-1, pentene-
1, hexene-1, butene-1, heptene-1, octene-1, etc., are random copolymers of α-olefin comonomers having 2 or more carbon atoms, preferably 2 to 6, and are more random copolymers than block copolymers. Polymers are preferred. Further, two or more comonomers may be copolymerized.

When the chlorine content of the carboxylic acid-modified chlorinated polyolefin (A) is less than 15% by weight, the melting point and the melt viscosity are too high, so that the water cannot be dispersed well. If it exceeds 35% by weight, the adhesion to the substrate will be poor. Preferably 18-28
% By weight.

The carboxylic acid-modified polyolefin is a polyolefin obtained by modifying the above polyolefin with an α, β-unsaturated carboxylic acid or its anhydride by a graft reaction.

(A) The acid value of the carboxylic acid-modified chlorinated polyolefin is preferably from 10 to 100. If the acid value is less than 10, the adhesion to polar materials is poor. If the acid value exceeds 100, the adhesion to polypropylene is poor. Become inferior.

Α, β used for modification of polyolefin
-Examples of unsaturated carboxylic acids or anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, aconitic acid, and acid anhydrides thereof. In addition, esters of these carboxylic acids are also included. Of these, acid anhydrides are preferred. The method of graft copolymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof with a polyolefin may be performed by a known method (for example, Japanese Patent No. 2019232). For example, it is preferable to carry out the method by heating and melting a polyolefin above its melting point and graft copolymerizing in the presence of a radical generator.

The number average molecular weight of the chlorinated polyolefin obtained by graft copolymerization of an α, β-unsaturated carboxylic acid or its anhydride is preferably from 2,000 to 40,000. If it exceeds 40,000, the operability at the time of dispersing in water deteriorates, which is not preferable. In order to keep the molecular weight within this range, it is possible to select the molecular weight of the raw material and the conditions for performing the graft reaction, and it is also possible to perform the graft reaction after the molecular weight of the raw material is lowered once. . The number average molecular weight can be measured by GPC (gel permeation chromatography).

(B) The carboxylic acid-modified ethylene-vinyl acetate copolymer can be produced by a known method. For example, as disclosed in JP-A-3-12836, EVA is dissolved in an aromatic hydrocarbon such as toluene or xylene, a lower alcohol such as methyl alcohol or ethyl alcohol is added, and an alkali alcoholate catalyst is added in the presence of a specific amount of water. And a saponification reaction. The resulting saponified product is an unsaturated carboxylic acid or an acid anhydride thereof, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, aconitic acid and acid anhydrides of these and the like and these carboxylic acids Esters are also mentioned, and can be obtained by reacting them with a radical initiator.

(B) The carboxylic acid-modified ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 5 to 60% by weight.
If the vinyl acetate content is less than 5% by weight, it is difficult to produce because of difficulty in melting, and if it exceeds 60% by weight, adhesion to an olefin resin molded product or film is insufficient. The acid value is preferably from 1 to 60, and if it is less than 1, it is difficult to disperse in water, and if it exceeds 60, the water resistance becomes poor.

In the present invention, the aqueous dispersion is disclosed in Patent 2700
It can be obtained by a known method as described in 526. That is, (A) a carboxylic acid-modified chlorinated polyolefin or (B) a carboxylic acid-modified ethylene-vinyl acetate copolymer is mixed at a ratio of (A) / (B) = 90/10 to 10/90, and about 10
0 ° C, melted and kneaded by adding 0.4 to 1.5 chemical equivalents of a basic substance to the nonionic surfactant and carboxyl group, and in a molten state, adding water at 80 to 98 ° C,
An aqueous dispersion of the present invention is formed by forming a dispersion of the / O type and subsequently inverting this phase to an O / W type dispersion with the addition of water and, if necessary, adding an additional amount of water. Can be obtained.

(A) / (B) = 90 using a twin-screw extruder.
After mixing and melt-kneading at a ratio of / 10 to 90/10, a nonionic surfactant and a basic substance are added and melt-kneaded, and then water is added to cause phase inversion from W / O to O / W. Thus, the aqueous dispersion of the present invention can be obtained.

The components (A) and (B) are melted singly, and an aqueous dispersion is obtained by the above method.
(B) = 90/10 to 10/90 may be mixed.

Examples of the nonionic surfactant include polyoxyethylene alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, sorbitan alkyl ester, and polyoxyalkylene alkyl ether. The nonionic surfactant may be used by mixing two kinds having different HLB. Further, a small amount of an anionic surfactant may be used in combination mainly with a nonionic surfactant.

The amount of the surfactant to be used is preferably 1 to 25% by weight, more preferably 3 to 15% by weight, based on the resin components (A) carboxylic acid-modified chlorinated polyolefin and (B) carboxylic acid-modified EVA. Is desirable. If the amount of the surfactant is less than 1% by weight, the stability of the aqueous dispersion will be poor, and if it exceeds 25% by weight, the adhesion and water resistance of the coating film will be poor.

The reason why the basic substance is added is to neutralize the carboxyl group and ionize it to improve the dispersion in water. Without adding the basic substance, a stable dispersion cannot be obtained. . As the basic substance, sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine,
Examples include octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, triethylamine, and morpholine.

The amount of the basic substance used is 0.4 to 1.5 chemical equivalents based on the carboxyl groups of the resin components (A) the carboxylic acid-modified chlorinated polyolefin and (B) the carboxylic acid-modified EVA. Preferably it is. 0.
If less than 4 chemical equivalents or more than 1.5 chemical equivalents are used, the resulting aqueous dispersion will have poor stability.

When the content of (A) the carboxylic acid-modified chlorinated polyolefin exceeds 90%, the effect of (B) the carboxylic acid-modified EVA is not sufficient, the flexibility is insufficient, and especially the adhesion to the EVA substrate is poor. bad. On the other hand, if the amount of the carboxylic acid-modified chlorinated polyolefin (A) is less than 10%, the adhesion to a polypropylene-based substrate is particularly reduced.

The aqueous dispersion thus obtained has excellent adhesion to polyolefin-based resins, especially polypropylene and EVA base materials, and has excellent flexibility of the coating film, small particle size and good stability. is there. The aqueous dispersion of the present invention may be used as it is, or may be mixed with a pigment, or may be blended with another aqueous resin.

The aqueous dispersion of the present invention may be used as a component of a top coat, a coating agent for a polyolefin film, an ink resin component or a resin molding, particularly as a primer for a polyolefin resin molded article which is an interior / exterior material for automobiles. Can be. It can also be used as an adhesive primer for shoes made of EVA.

[0031]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

[Production Example 1] 500 g of isotactic polypropylene having a number average molecular weight of 30,000 was placed in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser for refluxing monomers, and kept constant at 180 ° C. Dissolved completely in the oil bath. After replacing the nitrogen in the flask for about 10 minutes, 20 g of maleic anhydride was added thereto over about 5 minutes while stirring, and then 2 g of di-t-butyl peroxide was added.
It was dissolved in 10 ml of heptane and charged by a dropping funnel over about 30 minutes. At this time, the inside of the system was kept at 180 ° C., and the reaction was further continued for 1 hour. Then, while reducing the pressure in the flask with an aspirator, unreacted maleic anhydride was removed over about 30 minutes. Next, about 300 g of this product was put into a reaction vessel, and 5 liters of chloroform was added. After sufficiently dissolving under a pressure of ² kg / cm ² , while irradiating ultraviolet rays, the chlorine content was reduced to 24% by weight. Gaseous chlorine was blown from the bottom of the reaction vessel so as to make it possible. After completion of the reaction, chloroform as a solvent was distilled off under reduced pressure using a twin-screw extruder to obtain a solid pellet of carboxyl group-containing chlorinated polypropylene. Its acid value was 26, melting point was 90 ° C., and number average molecular weight was 28,000.

[Production Example 2] 500 g of an ethylene-propylene copolymer having a number average molecular weight of 30,000 and an ethylene content of 6.1 mol% was mixed with a stirrer, a dropping funnel, and a cooling pipe for refluxing the monomer. Place in flask, 180
Dissolved completely in an oil bath kept constant at ° C. After purging with nitrogen in the flask for about 10 minutes, 33 g of maleic anhydride was graft-copolymerized in the same manner as in Production Example 1 while stirring. Next, about 300 g of this product was charged into the reactor, and gaseous chlorine was blown from the bottom of the reactor so as to have a chlorine content of 18% by weight in the same manner as in Production Example 1. After completion of the reaction, chloroform as a solvent was distilled off under reduced pressure using a twin-screw extruder to obtain a solid pellet of carboxyl group-containing chlorinated polypropylene. Its acid value is 62 and melting point is 72
° C, the number average molecular weight was 22,000.

[Production Example 3] E having a vinyl acetate content of 28% by weight
VA was saponified to obtain saponified EVA having a saponification degree of 20. One part by weight of maleic anhydride and 0.2 part by weight of benzoyl peroxide are mixed well with 100 parts by weight of this saponified EVA, and the mixture is kneaded and extruded with an extruder set at 150 ° C. to give a melt flow rate of 7.0 g / 10. In a minute, a carboxyl-modified EVA having an acid value of 5 to which maleic anhydride was grafted was obtained.

Production Example 4 E having a vinyl acetate content of 28% by weight
VA was saponified to obtain saponified EVA having a saponification degree of 20. To 100 parts by weight of the saponified EVA, 2 parts by weight of maleic anhydride and 0.2 parts by weight of benzoyl peroxide were thoroughly mixed and kneaded and extruded with an extruder set at 150 ° C. to give a melt flow rate of 5.0 g / 10. In a minute, a carboxyl-modified EVA having an acid value of 10 to which maleic anhydride was grafted was obtained.

Production Example 5 E having a vinyl acetate content of 42% by weight
VA was saponified to obtain saponified EVA having a saponification degree of 40. To 100 parts by weight of this saponified EVA, 3 parts by weight of maleic anhydride and 0.2 parts by weight of benzoyl peroxide were mixed well, and kneaded and extruded with an extruder set at 150 ° C., so that the melt flow rate was 10.0 g / 10 After that, a carboxyl-modified EVA having an acid value of 15 to which maleic anhydride was grafted was obtained.

Example 1 85 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and 15 g of the carboxylic acid-modified EVA obtained in Production Example 3 were placed in a flask equipped with a stirrer, and heated and melted at 100 ° C. Was. Thereafter, 10 g of a nonionic surfactant was added, and the mixture was stirred well, and 1.5 g (0.7 chemical equivalent) of morpholine was added. While maintaining the temperature at 100 ° C., water at 90 ° C. was added little by little with vigorous stirring. Although the viscosity increased,
Continued addition of water reduced the viscosity. When 150 g of water was added, the contents were taken out to obtain a milky white emulsion.

Example 2 The same procedure as in Example 1 was carried out except that 70 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and 30 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 were used. The operation was performed to obtain a milky white emulsion.

Example 3 The same procedure as in Example 1 was performed except that 50 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and 50 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 were used. The operation was performed to obtain a milky white emulsion.

Example 4 The same procedure as in Example 1 was carried out except that 30 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and 70 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 were used. The operation was performed to obtain a milky white emulsion.

Example 5 The same procedure as in Example 1 was carried out, except that 85 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 2 and 15 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 were used. The operation was performed to obtain a milky white emulsion.

Example 6 The same procedure as in Example 1 was carried out except that 15 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 2 and 85 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 were used. The operation was performed to obtain a milky white emulsion.

Example 7 The same procedure as in Example 1 was carried out except that 70 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 2 and 30 g of the carboxylic acid-modified EVA (B) obtained in Production Example 4 were used. The operation was performed to obtain a milky white emulsion.

Example 8 The same procedure as in Example 1 was carried out except that 70 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 2 and 30 g of the carboxylic acid-modified EVA (B) obtained in Production Example 5 were used. The operation was performed to obtain a milky white emulsion.

Comparative Example 1 The same operation as in Example 1 was carried out on 100 g of the carboxylic acid-containing chlorinated polyolefin (A) obtained in Production Example 1 to obtain a milky white aqueous dispersion.

Comparative Example 2 The same operation as in Example 1 was carried out on 100 g of the carboxylic acid-modified EVA (B) obtained in Production Example 3 to obtain a milky white aqueous dispersion.

Example 9 The aqueous dispersions obtained in Comparative Examples 1 and 2 were mixed at (A) / (B) = 70/30 to obtain a milky white aqueous dispersion.

Example 10 The same operation as in Example 1 was carried out except that the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and the carboxylic acid-modified EVA (B) obtained in Production Example 5 were used. This gave a milky white emulsion.

Comparative Example 3 70 g of the carboxylic acid-modified chlorinated polyolefin (A) obtained in Production Example 1 and commercially available unmodified E
The same operation as in Example 1 was performed using 30 g of VA (V5772ET, acid value 0, Mitsui DuPont Chemical Co., Ltd.).

Test Example 1 Table 1 shows the results of storage stability of each aqueous dispersion at 50 ° C. for one month. Only in Comparative Example 3, the aqueous dispersion was separated into two layers. Measurement method / Appearance: Determined visually.・ PH: Measured with a pH meter after immersion in a thermostat at 25 ° C for about 1 hour.・ Average particle diameter: Zetasizer (measurement range 1 μm or less, M
ARVARON).

Test Example 2 A solution obtained by filtering the aqueous dispersions of Examples 1 to 10 and the aqueous dispersion of Comparative Example 1.2 was spray-coated on a polypropylene resin plate and dried at 80 ° C. for 30 minutes.
Next, a two-component urethane top coat was applied, left at room temperature for 10 minutes, and dried at 80 ° C. for 30 minutes using a hot air drier. After leaving the obtained coated plate at room temperature for one day, the coating film was tested. Table 2 shows the results.

The test method is as follows.・ Adhesiveness Cut 2m into the surface of the coating film to reach the substrate with a cutter
100 cross-cuts were made at intervals, and a cellophane adhesive tape was stuck thereon and peeled off in the direction of 180 degrees, and the number of remaining cross-cuts was counted. If the number of grids that did not come off was 100, the result was evaluated as ○, and 99 or less was evaluated as ×. -Gasoline resistance A cut was made on the surface of the coating film to reach the substrate with a cutter, and then the state of the cut in the coating film after immersion in regular gasoline for 2 hours was visually observed. When no change was observed on the surface of the coating film, it was evaluated as ○, and when there was a change in appearance such as blistering and peeling, it was evaluated as ×.・ Flexibility After leaving the painted polypropylene plate in a freezer at -20 ° C for 1 hour, quickly set it on a DuPont impact tester, and set the height to 50c based on the painted polypropylene plate.
500 g of hard spheres were dropped from the position of m, and those having no cracks in the coating film were rated as 、, and those having cracks in the coating film were rated as x.

Test Example 3 The aqueous dispersions of Examples 1 to 10 and the aqueous dispersions of Comparative Examples 1 and 2 were filtered and spray-coated on an EVA substrate, and dried at 80 ° C. for 30 minutes. Next, apply a two-component urethane-based topcoat and leave at room temperature for 10 minutes.
It dried at 80 degreeC for 30 minutes using the hot air dryer. After leaving the obtained coated plate at room temperature for one day, the coating film was tested. The coating test results are shown in Table 2.

The test method is as follows.・ Adhesiveness Cut 2m into the surface of the coating film to reach the substrate with a cutter
100 cross-cuts were made at intervals, and a cellophane adhesive tape was stuck thereon and peeled off in the direction of 180 degrees, and the number of remaining cross-cuts was counted. If the number of grids that did not come off was 100, the result was evaluated as ○, and 99 or less was evaluated as ×.

[Test Example 4] The aqueous dispersions of Examples 1 to 10 and the aqueous dispersions of Comparative Examples 1 and 2 were applied to an EVA foam of a shoe base material so as to have a dry film thickness of 10 μm, and the temperature was 60 ° C. For 10 minutes. For comparison, a commonly used solvent primer (epoxy resin) was applied. afterwards,
A mixture of 100 parts of an aqueous urethane-based adhesive and 5 parts of a curing agent (aliphatic polyisocyanate) is used as an EVA base material.
g / m ² . On the other hand, an aqueous adhesive and a curing agent were applied to the PVC leather to be adhered to the EVA base material to 100 g / m ² in the same manner as the EVA base material. Then 6 each
After drying at 0 ° C. for 10 minutes, both coated surfaces (EVA base material / PVC leather) were bonded together.

Thereafter, the test piece was cut so as to have a width of 1 cm, and EVA was performed under the conditions of 5 kg weight and 100 mm / min using Tensilon.
The substrate and the PVC leather were peeled off, and the peel strength was measured. The test was performed three times, and the average value was used as the result. Table 3 shows the results.

[0057]

[Table 1] Table 1 Storage stability results

Measurement method / Appearance: Determined visually. No change in appearance: ○-pH: Measured with a pH meter after immersion in a thermostat at 25 ° C for about 1 hour.・ Average particle diameter: Zetasizer (measurement range 1 μm or less, M
ARVARON).

[0059]

[Table 2] Table 2 Results of paint test

[0060]

[Table 3] Table 3 Results of tensile test

From Table 2, it can be seen that the carboxylic acid-modified chlorinated polyolefin alone (A) cannot provide flexibility and has no adhesion to the EVA substrate. Further, (B) carboxylic acid-modified E
VA alone has no adhesion to the polypropylene substrate. On the other hand, it can be seen that the aqueous dispersion using (A) the carboxylic acid-modified chlorinated polyolefin and (B) the carboxylic acid-modified EVA in combination is useful for both.
Furthermore, from the results in Table 3, the aqueous dispersion of the present invention has a tensile strength equivalent to that of the solvent-based primer.

[0062]

Industrial Applicability According to the present invention, it has excellent adhesion, coating appearance, solvent resistance, and good flexibility as a primer for paints, inks, or adhesives for molding or film of a polyolefin resin. The present invention relates to an aqueous dispersion which gives a good coating. That is, it is possible to obtain an aqueous dispersion which gives not only the adhesion of the coating film but also the flexibility to the polypropylene resin, and also has an excellent adhesive force to the EVA resin used for shoes and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 D 5/02 5/02 7/12 7/12 Z 123/26 123 / 26 123/28 123/28 (72) Inventor Kinichiro Koyama 2-8-1 Iidacho, Iwakuni City, Yamaguchi Prefecture Nippon Paper Industries Co., Ltd. 8-1 F-term in Nippon Paper Industries Co., Ltd. Chemical Development Laboratory (reference) 4F070 AA12 AA13 AA15 AA16 AB03 AB04 AB09 AC13 AC46 AC84 AE14 CA02 CB02 4J002 BB21W BB21X BB24W CH023 DE056 EH047 EN026 EN106 EU236 FD206 FD313J38 171 GA06 HA176 HA316 JB03 JB09 KA02 KA09 MA08 MA10 NA01 NA04 NA11 NA12 NA27 PB02 PB07 PC08 4J100 AA02P AA03P AA03Q AA04P AA07P AA15P AA16P AA19P AD02Q AG04Q BA16H BA17H BA18H BB0104 BC55H 1 HA08 HA11 HA21 HA57 HB39 HB43 HC29 HC30 HC34 HC43 JA01 JA03

Claims (10)

[Claims] 1. An aqueous dispersion of a resin, wherein the resin components are (A) a carboxylic acid-modified chlorinated polyolefin having a chlorine content of 15 to 35% by weight and (B) a carboxylic acid-modified ethylene-
An aqueous dispersion comprising a mixture of a vinyl acetate copolymer and dispersed in water using a basic substance and a nonionic surfactant. 2. The mixing ratio (A) / (B) of the resin component is 90/1.
The aqueous dispersion according to claim 1, wherein the aqueous dispersion is 0 to 10/90. 3. The aqueous dispersion according to claim 1, wherein (A) the carboxylic acid-modified chlorinated polyolefin has an acid value of 10 to 100. 4. The aqueous dispersion according to claim 1, wherein (A) the carboxylic acid-modified chlorinated polyolefin has a number average molecular weight of 2,000 to 40,000. 5. The aqueous dispersion according to claim 1, wherein (B) the carboxylic acid-modified ethylene-vinyl acetate copolymer has an acid value of 1 to 60. 6. The carboxylic acid-modified ethylene-vinyl acetate copolymer (B), wherein vinyl acetate is 5 to 6 of the copolymer.
The aqueous dispersion according to any one of claims 1 to 5, which is 0% by weight. 7. A coating primer for a polyolefin substrate, comprising the aqueous dispersion according to claim 1. 8. A primer for an adhesive for a polyolefin substrate, comprising the aqueous dispersion according to claim 1. Description: 9. The primer according to claim 7, wherein the polyolefin substrate is an ethylene-vinyl acetate copolymer. 10. The method according to claim 1, wherein the polyolefin substrate is ethylene-
9. The primer for an adhesive according to claim 8, which is a vinyl acetate copolymer.