JPH07173347A - Water dispersion type polyolefinic resin emulsion composition - Google Patents

Abstract

PURPOSE:To obtain a pollution-free water dispersion type polyolefinic resin emulsion composition having performance of sticking fast to the surface of a mold article or a film of a polyolefin without requiring cleaning of the surface with vapor of a harmful chlorine-based organic solvent such as trichloroethane in use. CONSTITUTION:(1) this water dispersion type polyolefinic resin emulsion composition is obtained by adding an alpha,beta-unsaturated carboxylic acid (IIa) and a (meth) acrylic acid ester monomer or its derivative ester monomer (III) to a polyolefin (I) and copolymerizing the polyolefin with the monomers and optionally adding a reactive oligomer (IV). Another production method is to add an alpha,beta-unsaturated carboxylic acid anhydride (IIb) and the monomer (III) to the polyolefin (I) and copolymerizing the polyolefin with the monomers and optionally adding the reacting monomer (IV). Further, an alternative method is to add the alpha,beta-unsaturated carboxylic acid (IIa), the alpha,beta-unsaturated carboxylic acid anhydride (IIb) and the monomer (III) to the polyolefin (I) and copolymerizing the polyolefin with the monomers and optionally adding the reactive oligomer (IV).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is applied to a molded product of polyolefin resin, a film or the like as a primer or a one-coat finish to coat the surface of a polyolefin molded product or film for coating, ink or adhesion. Mainly used for polyolefin resin moldings, etc., which gives a good coating with sufficient adhesion, weather resistance, coating appearance, solvent resistance, etc. without pretreatment such as washing or degreasing with an organic solvent such as trichloroethane. The present invention relates to a water dispersion type polyolefin resin emulsion for coating.

[0002]

2. Description of the Related Art A conventional method for producing a water-dispersed emulsion using polyolefin as a base is a molten polyolefin composition comprising 50 to 99 parts by weight of polyolefin and 1 to 50 parts by weight of a polyolefin containing a carboxyl group or an acid anhydride group. And a water dispersion medium containing 0.2 chemical equivalents or more of a basic substance and water with respect to the carboxyl group or acid anhydride group in the composition and heated to a high temperature of 120 to 350 ° C. under pressure. There is a method for producing an aqueous dispersion of a polyolefin composition by adding an aliphatic polycarboxylic acid ester, an aromatic carboxylic acid ester or an inorganic acid ester to the aqueous dispersion when producing the aqueous polyolefin dispersion. 122125). However, according to the method described in JP-A-3-122125, the particle size of the emulsion is not sufficiently small depending on the acid value and molecular weight of the acid-modified polyolefin used, and the stability of the emulsion itself is sufficient. Hard to become. Moreover, since it emulsifies in a high pressure state in the presence of an aqueous alkaline solution, it is dangerous if there are no necessary protective gears during the production.

Further, in an aqueous resin dispersion in which an olefin polymer having an unsaturated carboxylic acid bonded thereto is dispersed in water, a water-soluble (meth) acrylic resin containing an amino group is used as a dispersant, and Zn, Mg , Ca, and the like, and an aqueous resin dispersion containing an acetate and / or a formate of a metal belonging to Group II of the periodic table and a method for producing the same (JP-A-4-142).
355). However, the above-mentioned Japanese Unexamined Patent Publication
The resin aqueous dispersion described in No. 55 blends an amino group-containing water-soluble acrylic resin and an acid-modified polyolefin, so that these polymers cause phase separation due to the difference in mutual polarity and are applied to a polyolefin molded product. In this case, it is difficult to obtain a good coating film.

[0004]

As described above, there are various problems to be solved in each case of JP-A-3-122125 and JP-A-4-142355. The present invention solves the above problems, and further does not use a chlorine-based organic solvent that is a causative substance that destroys the ozone layer of the earth, and trichloroethane when the water-dispersible polyolefin resin emulsion of the present invention is used. Providing a non-polluting water-dispersible polyolefin resin emulsion composition that has the ability to adhere well to the surface of polyolefin molded products or films or inks without the need to wash with harmful chlorine-based organic solvent vapors. The purpose is to do.

[0005]

The first object of the present invention is to add α, β-unsaturated carboxylic acid (IIa) and (meth) acrylic acid ester monomer or its derivative monomer (III) to polyolefin (I). Further, a water-dispersible polyolefin resin emulsion characterized in that the main component is a resin composition obtained by copolymerization with or without addition of a reactive oligomer (IV) to these compositions. The second is a composition, which is obtained by adding the α, β-unsaturated carboxylic acid anhydrides (IIb) and (III) to the above (I), and further adding (IV) or without adding (IV). A water-dispersible polyolefin resin emulsion composition comprising a copolymerized resin composition as a main component, the third of which is (I).
(IIa) and (IIb) and (III) are added, and (IV) is further added to these compositions or copolymerized without adding them. A water-dispersible polyolefin resin emulsion. Composition, the fourth of which is for (I)
A water-dispersible polyolefin resin emulsion composition according to the above-mentioned first invention, characterized in that 0.1 to 50% by weight of (IIa) is added and graft-copolymerized, the fifth of which is
A water-dispersible polyolefin resin emulsion composition according to the second invention, wherein 0.1 to 50% by weight of α, β-unsaturated carboxylic acid anhydride (IIb) is added to (I) and graft-copolymerized. , The sixth is (IIa) + (II
b) is added in an amount of 0.1 to 50% by weight and graft-copolymerized to obtain the water-dispersible polyolefin resin emulsion composition according to the second invention, the seventh of which is 0.1 to (I).
The water-dispersible polyolefin resin emulsion composition according to the first, second, third, fourth, fifth or sixth invention, wherein the graft copolymerization is carried out by adding (III) of about 1000% by weight. And eighthly, the water according to the first, second, third, fourth, fifth, sixth or seventh invention, wherein the copolymerization is carried out in the presence of a chain transfer modifier. Dispersion type polyolefin resin emulsion composition is provided.

The above water-dispersible polyolefin resin emulsion composition of the present invention produced by the present inventors provides a good water-dispersible emulsion and at the same time, the surface of the polyolefin molding or film is treated with trichloroethane or the like. It should be applied on the surface of a polyolefin molding or film without steam cleaning or degreasing with an organic solvent to give a good coating with sufficient adhesion, weather resistance, coating appearance, solvent resistance, etc. Was found. Generally, the polarity of the polyolefin (I) solid is significantly lower than the polarity of the acrylic ester polymer composed of the acrylic ester monomer such as ethyl (meth) acrylate, and the polyolefin (I) is ) Acrylic ester monomer or (meth) acrylic ester derivative monomer is dissolved in an emulsion medium and then emulsion polymerization or suspension polymerization in an aqueous medium is attempted, so that both polymer components repel each other, and thus stable or stable It is difficult to obtain a uniform water dispersion emulsion. However, by suspension polymerization or emulsion polymerization while compatibilizing the two components that repel each other, it was possible to smoothly react the fine particles with each other from the initiation of the polymerization reaction to the completion of the reaction.

As a method for compatibilizing the above-mentioned two components, a conventional method (a) is a method in which graft copolymerization is performed to stabilize the incompatible components. (B) There is a method of stabilizing the system by adding a compatibilizer, but in the present invention, the compatibilization was achieved by adopting the method of simultaneously realizing the methods of (a) and (b) above. . That is, acrylic acid ester monomers that are easily compatible with both the acrylic acid ester polymer and the low chlorinated polyolefin are selected, and those and the polyolefin (I) are selected.
An α, β-unsaturated carboxylic acid (IIa) and / or its acid anhydride (IIb), and a monomer (III) such as a (meth) acrylic acid ester monomer or a (meth) acrylic acid ester derivative monomer. When the copolymer is copolymerized, a graft copolymer is produced, and the graft copolymer portion easily makes the polymer compatible with the polyolefin. The addition amount of the α, β-unsaturated carboxylic acid (IIa) and / or its acid anhydride (IIb) to the polyolefin (I) is less than 0.1% by weight or more than 1000% by weight. A suitable graft copolymer for the purpose of (1) cannot be obtained.

The polyolefin (I) used in the present invention is a component having a function of imparting adhesiveness as a physical property of a coating film, and it comprises (a) ethylene, propylene, 1-butene and 4-methyl-1-pentene. Resins and rubber-like materials made of a copolymer or homopolymer of α-olefin-based unsaturated hydrocarbons such as For example, propylene-α-butene copolymer, ethylene-propylene-diene copolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, poly- 1-butene, poly-4-methyl-
One penten or the like.

Further (b), a propylene-α-olefin copolymer, a copolymer of two or more α-olefins and a conjugated or non-conjugated diene, for example, ethylene-propylene-
Butadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-
1.5-hexadiene copolymer, (c), a copolymer of α-olefin and a conjugated or non-conjugated diene, for example, propylene-butadiene copolymer, propylene-ethylidene norbornene copolymers, etc. d), a copolymer of a monomer such as vinyl monomer and α-olefin and a partially saponified product thereof, and (e) a composition comprising two or more kinds of the above copolymer or the above copolymer, etc. are used. To be done. Further, a modified polyolefin resin in which a carboxyl group, a hydroxyl group, an acid anhydride group or the like is introduced into these can also be used. The modification of the polyolefin with the α, β-unsaturated carboxylic acid (IIa) or its acid anhydride (IIb) can be easily carried out by an ordinary reaction method. For example, a propylene-ethylene-1-butene copolymer is dissolved in toluene, and maleic anhydride and a peroxide are added dropwise to the flask while the reaction temperature is kept at 111 ° C to carry out the reaction. The obtained reaction liquid may be put into a non-solvent such as methanol to be resinified and dried. When the present invention is carried out using this maleic anhydride-modified polyolefin, the adhesion and solvent resistance are further improved.

As the α, β-unsaturated carboxylic acid (IIa) or its acid anhydride (IIb) used in the present invention, in a monocarboxylic acid system, carbon atoms such as acrylic acid, methacrylic acid and crotonic acid are contained. There are 6 or less aliphatic carboxylic acids, and in the dicarboxylic acid system, there are aliphatic carboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid, and other unsaturated carboxylic acids having an alicyclic or aromatic ring. Acids and the like are also used. Unsaturated acids of this system are, for example,
An acid anhydride such as maleic anhydride or fumaric anhydride can also be used. It is also possible to use the above (IIa) and (IIb) at the same time.

The (meth) acrylic acid ester monomer or its derivative ester monomer used in the present invention is also used.
(III) is preferentially selected such that it easily dissolves polyolefin (I) and acrylic oligomer. For example, ethyl (meth) acrylate, isobutyl (meth) acrylate
, Normal butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobonyl (meth) acrylate −
Monofunctional (meth) acrylates such as styrene, dimethylaminoethyl (meth) acrylate, monofunctional methacrylates having functional groups such as acrylamide, styrenes such as styrene, chloromethylstyrene and α-methylstyrene. One kind or two or more kinds of monomers selected from the above may be mixed and used. In particular, examples of the monomer which easily dissolves the polyolefins (I) include (meth) acrylates such as cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate. , (Butyl) (meth) acrylate, isobonyl (meth) acrylate and other (meth) acrylates,
Examples thereof include vinyl esters such as vinyl ester of versatic acid and styrenes such as paramethylstyrene. If the content of (meth) acrylic monomers or their conductors to be graft-copolymerized with polyolefin (I) is less than 0.1% by weight, the polyolefin (I) and acrylic oligomer will be difficult to dissolve, and more than 1000% by weight will be added. Then, the polyolefin solution becomes too thin, and it is difficult to obtain a graft copolymer resin suitable for the present invention. Conversely, polyolefins (I)
Examples of monomers which are difficult to dissolve include methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and polar monomers containing (meth) acrylates of glycidyl (meth) arylate. .

Further, the reactive oligomer used in the present invention
As (IV), as a typical feature, it has a certain repeating unit in the molecule and has at least one or two or more double bonds in the molecule. Further, of course, those which should be called macromers or macromonomers are included, but usually macromers or macromonomers (hereinafter referred to as macromonomers etc.) refer to those having a double bond at the end of the molecule. Also, those having a functional group such as a hydroxyl group or a carboxyl group at both ends of the molecule are included. The molecular weights of these macromonomers and the like are in the range of several hundreds to 10,000, and the physical properties of the coating film of the copolymer obtained and the stability of emulsion differ depending on the type of macromonomers and the molecular weights used.

Examples of the above-mentioned reactive oligomer (IV) include caprolactone-modified (meth) acrylate oligomers, terminal hydroxyl group-containing (meth) acrylate oligomers, oligoesters (meth) in addition to macromonomers and the like. Examples thereof include acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate. Among these, those having a hydroxyl group, a carboxyl group, an acid anhydride group or an amino group are also included.

Polyolefin (I), α, β according to the invention
-Unsaturated carboxylic acid (IIa) and / or its acid anhydride (I
The copolymerization of Ib), the monomer (III) such as (meth) acrylic acid or its derivative monomer and the reactive oligomer (VI) is carried out by suspension polymerization or emulsion polymerization. Examples of the dispersant used at that time include gelatin, tragacanth, starch, methyl fibrin, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and the like natural polymers or derivatives thereof and polyvinyl alcohol, partial. Water-soluble polymers such as saponified polyvinyl alcohol, vinyl alcohol copolymers, polyacrylic acid salts and the like, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate,
A poorly water-soluble finely powdered inorganic compound such as magnesium carbonate and calcium phosphate or a mixture thereof and an inorganic polymer substance such as talc, bentonite, silicic acid, diatomaceous earth and clay, and a metal and metal oxide powder are used. These dispersants have a large dispersing effect when used in combination of one or more of these.

[0015]

In the dispersant used in the present invention, when the droplets of the monomer solution collide with each other, the droplets collide with the above-mentioned dispersant dispersed in water, and other It has the effect of preventing collision with droplets and preventing coalescence of droplets. Further, before entering the suspension polymerization or emulsion polymerization, it is necessary to make the liquid droplets uniform and fine particles using the above dispersant. At this time, if an emulsifier is used in combination and a homogenizer is used. It becomes easier to achieve the purpose of copolymerization. The reason for using an emulsifier in combination is that the dispersant has the effect of preventing adhesion of droplets, whereas the emulsifier has a large ability to reduce surface tension and has a strong penetrating power, so that oil droplets (droplets) can be made smaller. It has a function to make it. Examples of emulsifiers (surfactants) used include aromatic compounds such as polyoxyethylene alkylphenyl ether, higher alcohol compounds such as polyoxyethylene alkyl ether, and fatty acid derivative compounds such as polyoxyethylene fatty acid ester. A nonionic surfactant represented by the formula: polyoxyethylene alkyl (or alkylphenyl) ether sulfate ester salt,
Examples thereof include anionic surfactants such as sodium salt of dialkylsulfosuccinate and higher alcohol alcohol sulfate ester soda, and one or more of these may be used in combination. Rather generally, H. L. It is often the case that two or more kinds of surfactants having different Bs or both anionic and nonionic surfactants are used in combination to give a good effect.

The polymerization initiator used during the polymerization is
Peroxide systems such as benzoylperoxide and azobis systems such as azobisisobutyronitrile can be used. Further, in order to control the degree of polymerization, if a chain transfer regulator is used, the degree of polymerization can be greatly reduced and the chain length can be made uniform. As a chain transfer regulator,
Mercaptan and disulfides are used. Examples of mercaptans include n-dodecyl mercaptan, n-tetradecyl methylcaptan, n-decyl mercaptan, and t.
-Decyl mercaptan, t-tetradecyl mercaptan, t-hexadecyl mercaptan, 3-ethoxypropanediol, etc. are mentioned, and as the disulfides,
Bis-2-aminodiphenyl disulfide, bis-2-
Examples thereof include dibenzothiazoyl disulphide and diisopropyl xanthogen disulphide. The polymerization method is a homogenized emulsion containing a solution of a chlorinated polyolefin in which a polymerization initiator is dissolved, a monomer such as an acrylic acid ester monomer and a reactive oligomer, and an aqueous solution in which a dispersant and an emulsifier are dissolved. (Hereinafter, referred to as pre-emulsion) is added dropwise to a reaction vessel previously charged with deionized water, and is agitated and polymerized in a nitrogen atmosphere.

[0017]

Example 1 2-Ethylhexyl methacrylate 400
g and cyclohexyl methacrylate 100 g, Tahuma-XR106L (propylene-α olefin copolymer;
Mitsui Petrochemical Industry Co., Ltd.), 220 g of maleic anhydride, 5.0 g of methacrylic acid and 2.0 g of methacrylic acid were placed in a 2-necked 4-necked flask equipped with a stirrer, dissolved at 80 ° C. until uniform, and then heated to 50 ° C. Cool down to room temperature and use perbutyl PV
(Nippon Yushi-Seiyaku Co., Ltd. radical initiator) 3 g and t-dodecyl mercaptan 0.2 g were charged and uniformly dissolved to obtain a uniform solution. In addition, 1300 g of deionized water, 54 g of Kuraray Poval 217EE (polyvinyl alcohol by Kuraray Co., Ltd.), 8 g of Nisso HPC-SL (hydroxypropyl cellulose by Nippon Soda Co., Ltd.), Neocol P (Daiichi Kogyo) Pharmaceutical Co., Ltd. anionic surfactant) 1
5 g and 33 g of Neugen EA-190D (Daiichi Kogyo Seiyaku Co., Ltd. nonionic surfactant) were added to obtain a uniform and transparent aqueous solution. Put the solution and into a 5-liter polyethylene cap, and mix with a homomixer-HV-SL.
(Tokushu Kika Kogyo Co., Ltd.) After homogenizing at 2000 rpm for 30 minutes, it was filtered through a # 400 SUS wire mesh to obtain a pre-emulsion. 2 liters with a dropping funnel 4
A two-necked flask was charged with 200 g of deionized water, and the system was sufficiently replaced with nitrogen. The temperature inside the system is 50 by an oil bath.
The temperature was raised to 0 ° C., the pre-emulsion in the dropping funnel was added dropwise uniformly over 3 hours with stirring, and the mixture was reacted, and further aged at 50 ° C. for 7 hours. The obtained emulsion is # 400
The emulsion was filtered to obtain an emulsion. This emulsion has a nonvolatile content of 35.5% and an emulsion viscosity of 2.2.
It was a poise.

[0018]

Comparative Example 1 The same operation as in Example 1 was carried out to obtain a uniform solution. In addition, 1300g of deionized water, Neocol-P
(Daiichi Kogyo Seiyaku Co., Ltd. anionic surfactant) 15
g and Neugen EA-190D (Daiichi Kogyo Seiyaku Co., Ltd. nonionic surfactant) 33 g and potassium persulfate 5.
5 g was added to obtain a uniform and transparent aqueous solution. The aqueous solution was charged into a 2-liter 4-necked flask equipped with a dropping funnel, the system was sufficiently replaced with nitrogen, the temperature in the system was raised to 50 ° C. by an oil bath, and the contents of the dropping funnel were stirred. The solution was added dropwise over 3 hours to react, and after aging for 7 hours at 50 ° C., it was filtered through a # 400 wire mesh to give emulsion (11).

[0019]

Examples 2 to 10 Under exactly the same operation and conditions as in Example 1,
The emulsions (2) to (10) are changed by changing only the type and amount of the monomer (mixture) used, the type and amount of the polyolefin, or the type and amount of the added oligomer.
(Collected in Examples 2 to 10 of Table 1-1) were obtained. In addition,
The changed compositions are summarized in [Table 1-1]. The coating properties of these emulsions are summarized in [Table 2].

[0020]

[Table 1-1]

[0021]

[Table 2] (1) Adhesion: Polypropylene plate (hereinafter abbreviated as PP plate).
Mitsui Noblen SB-E3 is molded by a conventional method.
The surface (100 mm x 50 mm, thickness 2 mm) is thoroughly washed with tap water and dried. Dilute the emulsion concentration to 20% by weight with ion-exchanged water and keep it at 25 ° C with air-
Type spray gun (Meiji Kikai Seisakusho Co., Ltd. F-88
Type) and the air pressure to 2.0 Kg / cm ² G, and
Spray painted from a distance of cm. Coating thickness is 5-10μ
(Resin base). Drying was performed at 80 ° C. for 30 minutes, and after returning to room temperature, 24 hours passed was tested.
The evaluation was based on JIS K5400. (2) Water resistance: PP coated by the method described in (1) and dried.
The plate is placed in warm water kept at 40 ° C., and the state of the coating film is observed and evaluated. (3) Gasoline resistance: The PP plate coated by the method described in (1) was wiped 30 times with a cotton cloth containing gasoline (Idemitsu Petroleum Reguyura Gasoline), and the surface condition was observed and evaluated. . (4) Weather resistance: The coated piece described in (6) was fixed on a weathering test plate having an elevation angle of 45 °, exposed to the sun and wind and rain on the roof facing south for one year, and then the surface was observed. (5) 1 part of emulsion with water and isopropyl alcohol
P diluted to 0 to 15% by weight and thoroughly washed with tap water
Spray paint on P board and thickness is 5-10μ (resin base
Of the same amount), dried at 80 ° C. for 30 minutes and returned to room temperature for 24 hours, and then 100 to 150 of Retan PG-80 (Kansai Paint Co., Ltd .: urethane coating).
Apply so that it becomes μ (resin base). 80 ° C
After being dried for 30 minutes at room temperature and returned to room temperature for 24 hours, it is used as a test piece. (6) Acrylic emulsion EMN-210E (manufactured by Nippon Shokubai Co., Ltd.) and the emulsion of the present invention were blended at a ratio of 1: 1 (resin base), diluted with water, and then the surface was treated by the method described in (1). A well-washed and dried PP plate was spray-coated, coated so as to have a thickness of 100 to 150 μm (resin base), dried at 80 ° C. for 30 minutes, and allowed to stand at room temperature for 24 hours. ○: Good

[0022]

[Comparative Examples 2 to 10] The emulsions (12) to (20) (Table 1
-1), which is summarized in Comparative Examples 1-10. The changed compositions are summarized in [Table 1-1].

[0023]

Example 11 (Using Polyolefin / Acrylic Monomer) Example 1 except that only maleic anhydride in the monomer (mixture) used was removed under exactly the same operations and conditions as in Example 1.
Completely the same operation as described above to obtain emulsion (11). The changed composition is summarized in (Table 1-2). The coating physical properties of this emulsion are summarized in (Table 2).

[0024]

[Table 1-2] (1) CH: Cyclohexyl methacrylate EH: 2-Ethylhexyl methacrylate IB: Isobutyl methacrylate M: Methyl methacrylate St: Styrene Maleic anhydride 5.0 g and methacrylic acid 2.
0g is charged. (2) XR106L: Mitsui Petrochemical Co., Ltd. propylene-α olefin copolymer UT2715: Ube Lexen Co. propylene-
Butene 1-copolymer (3) FM3: manufactured by Daicel Chemical Industries, Ltd. Polycaprolactone-modified 2-hydroxyethyl methacrylate
FA3: manufactured by Daicel Chemical Industries, Ltd. polycaprolactone-modified 2-hydroxyethyl acrylate AW6: manufactured by Toagosei Chemical Industry Co., Ltd. isobutyl methacrylate macromonomer (molecular weight: 1000)

[0025]

Comparative Example 11 (Similar to Example 11) Comparative Example 1 except that only maleic anhydride in the monomer (mixture) used was removed under exactly the same operations and conditions as in Comparative Example 1.
Completely the same operation as described above to obtain emulsion (11). The changed composition is summarized in (Table 1-2). The coating physical properties of this emulsion are summarized in (Table 2).

[0026]

Example 12 (Using Maleic Anhydride Modified Olefin / Acrylic Monomer) Tuffuma-XR10 under exactly the same operation and conditions as in Example 11.
The procedure of Example 11 was repeated except that 6 L was replaced with Umex 1010 [maleic anhydride-modified isotactic PP (maleic anhydride content 10% by weight, number average molecular weight = 4,000)]. ) Got. In addition,
The changed compositions are summarized in (Table 1-2). The coating film physical properties of this emulsion are summarized in (Table 2).

[0027]

COMPARATIVE EXAMPLE 12 (Similar to Example 12) Tuffuma-XR10 under exactly the same operation and conditions as in Comparative Example 11.
6 L was replaced with Yumex 1010 [maleic anhydride-modified isotactic PP (maleic anhydride content 10% by weight, number average molecular weight = 4,000); manufactured by Sanyo Kasei Co., Ltd.], except that maleic anhydride was further removed. The same operation as in Comparative Example 11 was carried out to obtain an emulsion (12). In addition,
The changed compositions are summarized in (Table 1-2). The coating film physical properties of this emulsion are summarized in (Table 2).

[0028]

The effects of the present invention are summarized as follows. The polyolefin-based aqueous emulsion according to the present invention has a storage stability of 3 months or more at room temperature, and by coating or coating on a polyolefin-based molding or film, and drying in a temperature range from room temperature to 160 ° C., A one-coat finish coating film or primer coating film that is pollution-free can be obtained. The obtained coating film had various excellent physical properties such as excellent adhesion, solvent resistance and weather resistance. The above-mentioned product of the present invention, when coating or coating the product of the present invention onto a polyolefin molded product, does not require steam cleaning or degreasing of the material of the polyolefin molded product with a chlorine-based organic solvent such as trichloroethane. Excellent adhesion, weather resistance,
Gives a good coating appearance and solvent resistance. Therefore, the present invention largely contributes to prevention of environmental destruction on a global scale without using the above-mentioned organic solvent which is a causative agent of ozone layer depletion.

Front page continuation (72) Inventor Ryozo Oda 2900 Sone Town, Takasago City, Hyogo Prefecture Toyo Kasei Kogyo Co., Ltd.

Claims (8)

[Claims] 1. An α, β-unsaturated carboxylic acid (IIa) and a (meth) acrylic acid ester monomer or its derivative monomer (III) are added to the polyolefin (I), and the composition is further reactive with these compositions. A water-dispersible polyolefin-based resin emulsion composition comprising a resin composition obtained by copolymerization with or without addition of an oligomer (IV) as a main component. 2. Polyolefin (I) is added with an anhydride (IIb) of an α, β-unsaturated carboxylic acid and a (meth) acrylic acid ester monomer or its derivative monomer (III) to obtain a composition thereof. A water-dispersible polyolefin-based resin emulsion composition, which comprises a resin composition obtained by copolymerizing with or without addition of a reactive oligomer (IV) as a main component. 3. Polyolefin (I) containing α, β-unsaturated carboxylic acid (IIa) and α, β-unsaturated carboxylic anhydride (I
Ib) and (meth) acrylic acid ester monomer or its derivative monomer (III) are added, and further, reactive oligomer (IV) is added to these compositions or copolymerization is performed without addition. A water dispersion type polyolefin resin emulsion composition characterized by the following: Here, the (meth) acrylic acid ester monomer or a derivative monomer thereof means an acrylic acid ester monomer, a methacrylic acid ester monomer, an acrylic acid ester monomer derivative, or a methacrylic acid ester monomer derivative. 4. The water-dispersion type composition according to claim 1, wherein 0.1 to 50% by weight of α, β-unsaturated carboxylic acid (IIa) is added to the polyolefin (I) for graft copolymerization. Polyolefin resin emulsion composition. 5. A graft copolymerization of 0.1 to 50% by weight of α, β-unsaturated carboxylic acid anhydride (IIb) based on polyolefin (I).
The water dispersion type polyolefin resin emulsion composition described. 6. A total of 0.1 based on polyolefin (I).
4. Graft copolymerization by adding .about.50% by weight of .alpha.,. Beta. Unsaturated carboxylic acid (IIa) and its acid anhydride (IIb).
The water dispersion type polyolefin resin emulsion composition described. 7. 0.1 to 1000 relative to polyolefin (I)
The water-dispersible polyolefin resin according to claim 1, 2, 3, 4, 5 or 6, which is obtained by adding (wt)% of (meth) acrylic acid ester monomer or its derivative monomer (IV) to graft copolymerization. Emulsion composition. 8. The copolymerization is carried out in the presence of a chain transfer regulator, 1, 2, 3, 4, 5, 5.
The water-dispersible polyolefin resin emulsion composition of 6 or 7.