JPH0489832A - Aqueous dispersion - Google Patents

Abstract

PURPOSE:To obtain an aqueous dispersion free from any organic solvent, excellent in adhesion to a resin molding and desirable as a primer by dispersing a specified amount of a specified chlorinated modified alpha-olefin copolymer in water. CONSTITUTION:A chlorinated alpha-olefin copolymer of a chlorine content of 10-50wt.%, prepared by chlorinating a modified copolymer which is prepared by grafting 0.5-15wt.% at least one member selected from among a monoolefin dicarboxylic acid, its anhydride and its monoalkyl ester onto an alpha-olefin copolymer of a degree of crystallinity of 20 % or below, is dispersed in water to obtain an aqueous dispersion comprising 5-70 pts.wt. above chlorinated alpha-olefin copolymer and 95-30 pts.wt. water. This dispersion excels in adhesion to a resin molding, for example, a molding comprising an alpha-olefin copolymer such as PP, a synthetic rubber, an unsaturated polyester, an epoxy resin or the like, can form a coating film having a sufficient peeling strength and adhesion, and is desirable as a primer.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an aqueous dispersion, and in particular can be used to undercoat various resin molded products to improve the adhesion of paint to the surface of the molded product. The present invention relates to an aqueous dispersion suitable as a brimer that can maintain a good working environment because it does not contain an organic solvent.

<Prior Art> Conventionally, the added value of polyolefin molded products such as polypropylene has been increased by painting the surface or forming other resin layers. but,
Polyolefins generally have poor polarity and have poor adhesion to common paints and other resins. Therefore, conventionally, the surface of the molded product is treated in advance with chromic acid, flame, corona discharge, plasma, solvent, etc. to increase the polarity of the surface.
Attempts have been made to improve the adhesion of paints. However, these treatments have disadvantages in that they require complicated treatments and are dangerous due to the use of corrosive chemicals. In addition, in order to obtain stable treatment effects,
The drawback is that it requires strict process control.

Therefore, as an effective means to improve the defects of Gowara, there is a method of coating the surface of molded products with a brimer.
As a primer, the applicant previously proposed a surface treatment agent made by dissolving a modified polymer obtained by graft copolymerizing marinic acid or its anhydride on a specific propylene/ethylene copolymer in an organic solvent. did. (Tokuko Showa 62-2
No. 1027) In addition, monoolefin cyclophonic acid monoalkyl ester is added to an α-olefin copolymer having a crystallinity of 20% or less as measured by X-ray diffraction.
We have proposed a surface treatment agent made by dissolving a modified polymer obtained by graft copolymerization of 15% heavy king in an organic solvent.

(Japanese Patent Publication No. 61-11250) <Problem to be solved by the invention> However, it is unclear whether the surface treatment agent proposed for forward bending has good adhesion and storage stability and is useful as a brimer. Both contain organic solvents. By the way, in recent years, in order to reduce the amount of volatile organic solvents used and maintain a good working environment in factories, there have been efforts to reduce the amount of volatile organic solvents used and to maintain a good working environment in factories. There is a strong demand for surface treatment agents. Therefore, it is difficult for the above-mentioned surface treatment agents to meet such demands.

Therefore, it is an object of the present invention to mold resin products, for example, molded products made of various resins such as polyolefins such as polypropylene, synthetic rubber, unsaturated polyesters, epoxy resins, polyurethane resins, or composite resins thereof. Because of its excellent adhesion, it is necessary to obtain a coating film with sufficient peel strength and adhesion on the surface of these molded products, and it also has good storage stability and does not contain organic solvents. The object of the present invention is to provide an aqueous dispersion suitable as a brimer, which can maintain a good working environment because it is aqueous.

<Means for Solving the Problems> In order to solve the above problems, the present invention provides crystallinity of 20
% or less of an α-olefin copolymer is graft copolymerized to contain from 05 to 15% by weight of at least one species carried from a monoolefin dicarboxylic acid and its anhydride as well as a monoalkyl ester of the monoolefin dicarboxylic acid. An aqueous dispersion obtained by dispersing in water a chlorinated modified α-olefin copolymer with a chlorine content of 10 to 50% by weight obtained by further chlorinating a modified copolymer, the chlorinated modified α-olefin copolymer having a chlorine content of 10 to 50% by weight. - An aqueous dispersion containing 95 to 30 parts by weight of water to 5 to 70 parts by weight of the olefin copolymer is provided.

Further, it is preferable that the α-olefin copolymer is at least one selected from a propylene/ethylene copolymer and a propylene/butene/ethylene copolymer.

Hereinafter, the aqueous dispersion of the present invention will be explained in detail.

The chlorinated modified α-olefin copolymer, which is a product of the aqueous dispersion of the present invention, includes an α-olefin copolymer and at least one selected from monoolefin dicarboxylic acids and their anhydrides, and monoalkyl esters of monoolefin dicarboxylic acids. It is obtained by further chlorinating a modified copolymer obtained by graft copolymerizing one type of copolymer.

The α-olefin copolymer, which is the main component of this chlorinated modified α-olefin copolymer, consists of propylene and/or
Alternatively, the main component is ethylene, such as a propylene/ethylene copolymer or a copolymer of propylene and/or ethylene with another α-olefin. In this α-olefin copolymer, the propylene content is usually about 30 to 90 mol%, and the ethylene content is usually 30 to 90 mol%.
That's about it. Moreover, this α-olefin copolymer is
When both propylene and ethylene are contained, the propylene/ethylene content ratio is usually 9515 to 5 in terms of molar ratio.
/95. Examples of other α-olefins include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In the present invention, one or more of these other α-olefins may be contained in the α-olefin copolymer. When the α-olefin copolymer or other α-olefin is contained, its content is usually 40 mol% or less, preferably 30 mol% or less.

This α-olefin copolymer can be dissolved in organic solvents, making it easy to perform graft copolymerization in a solution state.Also, it is easy to prepare a filtrate dispersion using the solvent replacement method described later, and its crystallinity is 20% or less, preferably 2-20%
, particularly preferably 5 to 18%. This crystallinity is a value measured by X-ray diffraction.

Also, the molecule of this α-olefin copolymer! is 135
℃ The intrinsic viscosity [η] measured in decalin is usually 0.
About 3 to 20 i/g, particularly preferably 0.5 to 12 dI
It is about 1/g.

Among these α-olefin copolymers, ethylene
Propylene copolymers and propylene-butene-ethylene copolymers are preferred. In the present invention, in order to obtain a modified copolymer, a monoolefin dicarboxylic acid and its non-woody substance and a monoalkyl ester of a monoolefin dicarboxylic acid are graft-copolymerized to the α-olefin copolymer as described above. At least one type selected from (
(hereinafter referred to as "graft copolymerization unit") or graft copolymerization. Examples of monoolefin dicarboxylic acids include maleic acid, citraconic acid, itaconic acid,
Glutaconic acid, 3-methyl-2-pentene diacid, 2-
Examples include methyl-2-pentene diacid and 2-hexene diacid.

Also included are anhydrides of these monoolefin dicarboxylic acids and those obtained by esterifying one of their carboxyl groups with an alkyl alcohol, that is, monoalkyl esters of monoolefin dicarboxylic acids.

For monoalkyl esters of monoolefin dicarboxylic acids, the esterification rate (complete diesterification rate is 200
%) is preferably 4, since the aqueous dispersion has sufficient storage stability and a coating film with good water resistance can be obtained.
It is desirable that the content is 5 to 100%, more preferably 80 to 100%. Further, the alkyl group of the monoalkyl ester is represented by the general formula CnH2n (jl), and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, and the like.

Among the modified copolymers used in the present invention, a modified copolymer having a monoalkyl ester of a monoolefin dicarboxylic acid as a graft copolymer unit is, for example, a monoalkyl ester of a monoolefin dicarboxylic acid copolymerized with an α-olefin. It can be obtained by graft copolymerizing a monoolefin dicarboxylic acid or its anhydride onto an α-olefin copolymer, and then esterifying one of the carboxyl groups with an alkyl alcohol. can.

This modified copolymer has sufficient adhesion to the coating film obtained by applying the aqueous dispersion of the present invention to the surface of the 81 resin molded product, and has sufficient volatilization resistance. In terms of oiliness, the graft amount of the graft copolymer units in the modified copolymer, that is, the content of the graft copolymer units, 05
-15% by weight, preferably 1-10% by weight.

Further, the crystallinity of this modified copolymer is almost the same or slightly smaller than the crystallinity of the α-olefin copolymer before graft copolymerization.

Various known methods can be used to produce a modified copolymer by graft copolymerizing a graft copolymer unit onto the α-olefin copolymer. For example, α
- A method of performing a graft copolymerization reaction by dissolving an olefin copolymer in an organic solvent, adding the graft copolymerization unit and a radical polymerization initiator, and heating and stirring;
A method in which a graft copolymerization reaction is carried out by heating and melting an α-olefin copolymer, adding a graft copolymerization unit and a radical polymerization initiator to the resulting melt, and stirring: Alternatively, each component is fed to an extruder. In this method, a powder of α-olefin copolymer is impregnated with a solution obtained by dissolving the graft copolymer unit and a radical polymerization initiator in an organic solvent, and then the powder is mixed with heat and then subjected to a graft copolymerization reaction. Examples include a method of heating to a temperature at which it does not melt and causing a graft copolymerization reaction. Among these methods, as a more preferred specific example, the α-olefin copolymer is mixed at 0.01 to 0.0° C. with respect to 1° C. of the organic solvent.
1 to 10 of the graft copolymer units are added to a copolymer solution prepared by dissolving 5 kg of 0.01 to 0.04 g of the graft copolymer units.
0m m o fl / min / K g-
Copolymer, preferably 2-20 mmol/m
in/Kg-copolymer dropwise. At this time, at the same time, the radical polymerization initiator also
~50 mmolmin/K g-copolymer, particularly preferably IXl 0-2-5 mmofl/
An example of a method is to carry out a graft copolymerization reaction by sequentially dropping the copolymer at an addition rate of min/Kg.

The ratio of radical polymerization initiator/graft copolymerization unit used in the graft copolymerization reaction is usually 1/1 in terms of molar ratio.
It is in the range of 00 to 60/100, preferably 1/20 to 1/2.

The reaction temperature is preferably higher than the melting point of the α-olefin copolymer, particularly preferably in the range of 120 to 160°C, and the reaction time is 2 to 1
It takes about 0 hours.

Examples of the radical polymerization initiator used in the graft copolymerization include benzoyl peroxide, dichlorohensyl peroxide, dicumyl peroxide, sheet t
-butylperoxide, 2,5-dimethyl-2,5-cy(beroxyhenzoate)hexyne-3,1,4-his(t-butylperoxyisopropyl)benzene, lauroylperoxide, 2,5-dimethyl-2, Organic peroxides such as 5-di(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, t-butylberacetate, t
- Organic bers such as butylberhenzoate, t-butylberphenylacetate, t-butylberisobutyrate, t-butylber-5ee-octoate, t-butylberpivalate, cumylberbivalate, t-butylberdiethyl acetate, etc. Examples include esters, azo compounds such as azohisisobutyronitrile, and dimethylazoisobutyronitrile. Among these, organic peroxides and organic peresters are preferred, especially dicumyl peroxide, t-butyl peroxide, 2.5
-dimethyl-2,5-di(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,4-his(t-butylperoxyisopropyl)benzene Dialkyl peroxides such as are preferred.

When using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; trichlorethylene, perchlorethylene,
Examples include halogenated hydrocarbons such as dichloroethylene and chlorobenzene. Among these, aromatic hydrocarbons are preferred, and alkyl group-substituted aromatic hydrocarbons are particularly preferred.

The aqueous dispersion of the present invention has as its main component a chlorinated modified α-olefin copolymer obtained by further chlorinating the modified copolymer obtained as described above. This chlorinated modified α-olefin copolymer is easily soluble in a solvent,
It is easy to produce an aqueous dispersion by the solvent substitution method described later,
In addition, the water dispersion that can be applied to molded products to obtain a coating film with high paint adhesion is obtained because the chlorine content is 10%.
-50% by weight, preferably 12-30% by weight. In addition, the intrinsic viscosity [η] of this chlorinated modified α-olefin copolymer is usually 0.00, since it is easily dispersed in water and has good adhesive properties. It is about 1 to 206 fl/g, preferably about 0.2 to 10 du/g.

The chlorinated modified α-olefin copolymer can be produced by dissolving or dispersing the modified copolymer in a suitable organic solvent and then reacting it with chlorine scum. This reaction is generally carried out at about 50 to 120°C for about 0.5 to 5 hours. Furthermore, in order to make the reaction proceed efficiently, ultraviolet rays or visible light may be irradiated, or a radical generator may be used.

Examples of organic solvents used include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and tetradodecane, and alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclododecane. ; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cyisoflovirhenzene; chlorobenzene, bromohensen, 0-cyclohexane, carbon tetrachloride, carbon tetrabromide, chloroform,
Examples include halogenated hydrocarbons such as bromoform, trichloroethane, trichloroethylene, tetrachloroethane, and tetrachloroethylene. These may be used alone or in combination of two or more.

The aqueous dispersion of the present invention is obtained by dispersing the chlorinated modified α-olefin copolymer obtained as described above in wood. As a method for producing the aqueous dispersion of the present invention by dispersing a chlorinated modified α-olefin copolymer in water, for example, the chlorinated modified α-olefin copolymer, water, and a surfactant are mixed together. Drum emulsification method in which a chlorinated modified α-olefin copolymer that has been ground in advance is poured into water together with a surfactant and dispersed:
A solvent substitution method in which a chlorinated modified α-olefin copolymer dissolved in an organic solvent is mixed with a surfactant and water, and then the organic solvent is removed; a homomixer method in which dispersion is performed using a homomixer; a phase inversion method etc., and is appropriately selected depending on the physical properties of the chlorinated modified α-olefin copolymer used.

As the surfactants used, mention may be made of nonionic and anionic surfactants. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylfuryl ether, polyoxyethylene sorbitan ester, and polyoxyethylene alkylamine ether.

Examples of anionic surfactants include fatty acid salts,
Examples include higher alcohol sulfuric esters, sodium alkylhensensulfonate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, and sodium alkylhensensulfonate is particularly preferred.

The amount of surfactant to be used is usually determined so that the dispersion state of the chlorinated modified α-olefin copolymer is good and the resulting aqueous dispersion has good adhesion to the molded product.
- It is preferably about 0.05 to 10% by weight, particularly preferably 0.1 to 7% by weight, based on the olefin copolymer.

The blending ratio of the chlorinated modified α-olefin copolymer and water in the aqueous dispersion of the present invention is 95 to 30 parts by weight of water to 5 to 70 parts by weight of the chlorinated modified α-olefin copolymer. be selected as appropriate within the range. In particular, when spray-coating the aqueous dispersion of the present invention, uneven coating is less likely to occur on the coated surface, and variations in the adhesion of the coating film are less likely to occur.
In addition, since the layer of the coating film formed does not become thick, for example, when used as a brimer, the smoothness of the coating film after painting is improved, so it is preferable to use 3 to 45% by weight.

In addition, the aqueous dispersion of the present invention may contain a thickener,
Basic substances, antifoaming agents, etc. can also be added. Furthermore, in order to improve the wettability with the material to be coated, a small amount of organic solvent may be added as necessary.

Examples of thickeners include mineral thickeners such as ammonium alginate, sodium alginate, and bentonite clay; acrylic acid thickeners such as sodium polyacrylate, ammonium polyacrylate, and crosslinked acrylic emulsion copolymers. ; Examples include 1&fiber conductors such as carboxyl methyl cellulose, methyl ° cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose;
Particularly preferred is carboxymethylcellulose.

Examples of antifoaming agents include vegetable oils such as castor oil, soybean oil, and linseed oil; mineral oils such as spindle oil and liquid paraffin; fatty acids such as stearic acid and oleic acid, nioleyl alcohol, polyoxyalkylene glycol, and octyl alcohol. Alcohols such as ethylene glycol cystearate, polyoxyethylene solhitane monolaurate, etc. Fatty acid esters such as tributyl phosphate, sodium octyl phosphate, etc. Amides such as polyoxyalkylene amide; Aluminum stearate, olein Examples include metal soaps such as potassium acid and calcium stearate; silicones such as dimethyl silicone and polyether-modified silicone; and amines such as cyamylamine and polyoxyfuropylene alkylamine.

Furthermore, in addition to the above, the aqueous dispersion of the present invention may optionally contain various stabilizers such as antioxidants, weather-resistant stabilizers, and heat-resistant inhibitors, titanium oxide, coloring agents such as organic pigments: carbon black, ferrite, etc. The conductivity imparting agent may be contained.

The aqueous dispersion of the present invention can be applied to the surface of a molded article made of an α-olefin copolymer or other polymer, and used as a brimer or the like to improve the adhesion of paint to the surface. In particular, the aqueous dispersion of the present invention can be used, for example, in high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1
-α-olefin copolymers such as butene and polystyrene;
It can be suitably used for molded articles made of olefin copolymers such as ethylene/propylene copolymer, ethylene/butene copolymer, and propylene/butene copolymer.

Furthermore, in addition to the above-mentioned α-olefin copolymer and its copolymer, the aqueous dispersion of the present invention also includes molded articles made of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, It can also be used for surface treatment of molded products made of polycarbonate resin or the like, such as molded products such as automobile bumpers, and furthermore, steel plates and steel plates for electrodeposition treatment. In addition, undercoat the surface coated with paints, primers, adhesives, etc. whose main components are polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc. to improve the adhesion of the paint, etc. to the surface. It is also used to improve the image quality and form coating films with excellent image clarity and low-temperature impact resistance.

In addition, the molded products to which the aqueous dispersion of the present invention can be used include the above-mentioned various polymers or resins formed by any of the known molding methods such as injection molding, compression molding, blow molding, extrusion molding, and rotary molding. It may be molded.

The aqueous dispersion of the present invention can be applied to molded products that contain inorganic fillers such as talc, zinc white, glass fiber, titanium white, magnesium sulfate, pigments, etc. It is possible to form a brimer coating film with good adhesion.

Moreover, the molded article coated with the aqueous dispersion of the present invention may contain various stabilizers, ultraviolet absorbers, hydrochloric acid absorbers, etc. in addition to the above.

Preferably used stabilizers include, for example, 2.6-
Di-t-butyl-4-methylphenol, tetrakis [
Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, metaoctadecyl-3-
(4'-Hydoxy-3,5-sheet-t-butylphenyl)
Propionate, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 4.4'-butylidenebis(3-methyl-6-7-butylphenol), 1
4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2-thiobis(4-methyl-6-t-
butylphenol) 1,3,5-trimethyl-2
, 4,6-1-lis(3,5-t-butyl-4-hydroxyhensyl)benzene, 1°3,5-tris(2
- Phenol stabilizers such as methyl-4-hydroxy-5-t-butylphenol) butane, sulfur stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate, tridecyl phosphite, trinonylphenyl phosphite, etc. Examples include phosphorus stabilizers such as Phite.

Further, as the ultraviolet absorber used, for example, 2-
Examples include hydroxy-4-octoxyhensophenone, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and paraoctylphenyl salicylate.

Examples of the hydrochloric acid absorbent include calcium stearate.

As a method for applying the aqueous dispersion of the present invention to the surface of a molded article, spray coating is suitable; for example, it is sprayed onto the surface of the molded article using a spray gun. The coating on the molded article can be carried out at room temperature, and after coating, it can be dried by an appropriate method such as natural drying or forced drying under heat to form a coating film.

As described above, after the aqueous dispersion of the present invention is applied to the surface of a molded article and dried, the surface of the molded article is coated with paint by electrostatic coating, spray painting, brush coating, etc. can be applied.

The paint may be applied by applying an undercoat and then a topcoat. After applying the paint, use nichrome wire, infrared rays,
A molded article having a desired coating film on its surface can be obtained by curing the coating film according to a conventional heating method using high frequency waves or the like. The method of curing the coating film depends on the material of the molded product,
Appropriate selection is made depending on the shape, properties of the paint used, etc.

In addition, the aqueous dispersion of the present invention can be applied to a wide range of applications in addition to the above-mentioned applications as a brimer for molded products, taking advantage of its excellent adhesion, peel strength, and water resistance. Of course, it can also be used as an additive for adhesives and paints.

<Examples> Hereinafter, the present invention will be specifically explained by giving Examples and Comparative Examples of the present invention, but the present invention is not limited in any way by these Examples.

Further, in the following, the physical properties of the coating film were evaluated according to the following method.

Base grain test A test piece with a base grain was prepared according to the method of the base grain test described in JIS K5400, and a piece of sellotape made by Chiban (trade name) was pasted on the base grain of the test piece. Thereafter, this was quickly pulled in a 90° direction to peel it off, and the number of base grains that were not peeled out of 100 base grains was counted and used as an index of adhesion.

Prepare a coating film on the base material, make a 1 cm wide cut with a cutter blade until the blade reaches the base material, peel off the edge, and then cut the edge of the peeled coating film. 1 at a speed of 50+nm/min
The peel strength was measured by pulling the coating in an 80° direction until it peeled off.

The water resistance test piece was immersed in water at 40° C. for 240 hours and then subjected to a substrate test to evaluate adhesion.

(Example 1) In a pressurized reaction vessel, a propylene/ethylene copolymer (propylene content: 60 mol%, intrinsic viscosity [η(decalin 135°C)) 193 dfl/g, crystallinity determined by X-ray diffraction 12 %) and 240 mρ of toluene were charged, and the inside of the reaction vessel was replaced with nitrogen for 1 hour.
After heating to 145°C to completely dissolve the propylene/ethylene copolymer, a solution of 6.9 g of maleic anhydride dissolved in 30 m of toluene and 2.4 g of sheet t-butyl peroxide were dissolved in 3 omU of toluene. The resulting solution was simultaneously added dropwise continuously over 4 hours. After the dropwise addition was completed, the temperature was maintained at 145° C. and the reaction was allowed to proceed for 2 hours to obtain a toluene solution containing the produced modified copolymer as a reaction mixture. After the reaction was completed, a large amount of acetone was added to the reaction mixture, and the resulting modified copolymer was precipitated and separated, washed with H7 with acetone, and then dried under reduced pressure.

The content of maleic anhydride in the obtained modified copolymer was measured and found to be 4.2% by weight.

The modified copolymer obtained above was heated to 110°C in a chlorohenzene solvent to completely melt it, and while maintaining the temperature, light was completely blocked and chlorine gas was supplied to react for about 2 hours. Ta. A large excess of methanol was added to the resulting reaction mixture to precipitate a reaction product, which was separated, washed repeatedly with methanol, and dried under reduced pressure to obtain a chlorinated modified copolymer. The chlorine content of the obtained chlorinated modified copolymer was measured and found to be 30% by weight.

Next, the obtained chlorinated modified copolymer was dissolved in toluene to prepare a solution having a polymer concentration of 125 g/JZ.
500 g of this polymer melt, 500 g of distilled water, and 1.44 g of sodium todecylhenzenesulfonate (Neoperex F-25, manufactured by Kao ■) were mixed at a rotational speed of 10
The mixture was mixed by stirring at 00 rpm for 15 minutes. Next, polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., Hihiswako-30)
4) 0.72g was added and stirred and mixed to obtain an emulsion.

Toluene in the obtained emulsion was distilled off under reduced pressure using an evaporator to obtain an aqueous dispersion with a polymer concentration of 20% by weight.

This aqueous dispersion was applied by spraying onto a square plate made of polypropylene (X440, manufactured by Mitsui Petrochemical Industries, Ltd.) which had been washed with 1,1.1-1-lichloroethane vapor in an amount of 200 g and 7 m 2 . Next, this square plate was heat-dried at 100° C. for 30 minutes in an open air environment, and then subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.

(Example 2) In the same manner as in Example 1, a water dispersion was applied to a polypropylene square plate, and after drying, a urethane paint (R-271, manufactured by Nippon B Chemical @) was applied to Zara to a dry film thickness of 60 μm. I painted it like this.

Next, baking was performed in an air oven at 100° C. for 30 minutes to obtain a coating film sample.

The obtained coating film sample was subjected to a base grain test, measurement of ff1lJ m strength, and evaluation of water resistance. The results are shown in Table 1.

(Example 3) Toluene solution of the modified copolymer produced in Example 1 300
ml of methanol. Add smR and heat to 145°C
The reaction mixture was heated and stirred for 2 hours to obtain a toluene solution of a maleic acid monomethyl ester graft-modified copolymer.

When the infrared absorption spectrum of the obtained maleic acid monomethyl ester graft modified copolymer was measured and its esterification rate was determined, it was confirmed that maleic acid monomethyl ester with an esterification rate of 10% IE was graft copolymerized. . Next, this maleic acid monomethyl ester graft-modified copolymer was chlorinated in the same manner as in Example 1 to prepare an aqueous dispersion. Using the obtained aqueous dispersion, a coating film sample was prepared in the same manner as in Example 2, and the sample was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.

(Example 4) The molar ratio of propylene/butene/ethylene is 65/25/
10, 3 kg of α-olefin copolymer, 120 g of maleic anhydride, and 29.5 dimethyl-2,5-di(t
-Butylperoxy) Hexane (12 g) was mixed in advance with a Henschel mixer, then supplied to a twin-screw extruder (manufactured by Ikegai Iron Works, PCM-45) and extruded while kneading at a heating temperature of 230°C and a rotation speed of 260 rpm. A modified copolymer was obtained.

The maleic anhydride content (grafting amount) of the obtained modified copolymer was measured and found to be 2.9% by weight.
After chlorinating this modified copolymer in the same manner as in Example 1, an aqueous dispersion was prepared, and a coating film sample was prepared in the same manner as in Example 2 to conduct a substrate surface test, peel strength measurement, and water resistance test. It was submitted for evaluation. The results are shown in Table 1.

(Example 5) An aqueous dispersion was prepared in the same manner as in Example 1, except that the α-olefin copolymer used in Example 4 was used instead of the propylene-ethylene copolymer. The maleic anhydride content (grafting amount) of the modified copolymer produced during the preparation of the aqueous dispersion was 4.0% by weight.

A coating film sample was prepared in the same manner as in Example 2 using the obtained aqueous dispersion, and subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.

(Comparative Example 1) An aqueous dispersion was prepared in the same manner as in Example 1 except that the modified copolymer was not chlorinated, and using this, Example 2
A coating film sample was prepared in the same manner as above, and was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.

(Comparative Example 2) A coating film sample was prepared in the same manner as in Example 2, except that the water dispersion was not applied, and this sample was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.

Table 1 <Effects of the Invention> The aqueous dispersion of the present invention can be applied to resin molded products, such as α-olefin copolymers such as polypropylene, synthetic rubbers, unsaturated polyesters, epoxy resins, polyurethane resins, etc., or composite resins thereof. Because it has excellent adhesion to molded products made of various resins such as, it can be applied to the surface of these molded products to obtain a coating film with sufficient peel strength and adhesion, and it does not contain organic solvents. Since it is water-based, it is suitable as a primer because it can maintain a good working environment.

Peel strength: g/10mm

Claims (2)

[Claims] (1) 0.5 to 15% by weight of at least one selected from monoolefin dicarboxylic acids, their anhydrides, and monoalkyl esters of monoolefin dicarboxylic acids to an α-olefin copolymer with a crystallinity of 20% or less. An aqueous dispersion obtained by dispersing in water a chlorinated modified α-olefin copolymer with a chlorine content of 10 to 50% by weight obtained by further chlorinating a modified copolymer obtained by graft copolymerization so as to contain An aqueous dispersion containing 95 to 30 parts by weight of water to 5 to 70 parts by weight of the chlorinated modified α-olefin copolymer. (2) The aqueous dispersion according to claim 1, wherein the α-olefin copolymer is at least one selected from propylene/ethylene copolymers and propylene/butene/ethylene copolymers.