JPH02252784A - Emulsion adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which has excellent storage stability and enables bonding between a highly crystalline resin molding and an arbitrary material, by incorporating a solution of a specified modified chlorinated polyolefin in an organic solvent into an aqueous emulsion of an adhesive synthetic resin. CONSTITUTION:The title composition is prepared by mixing an aqueous emulsion (A) of 100 pts.wt. adhesive synthetic resin (e.g. a resin composed mainly of an acrylic resin) with a solution (B) of 0.05-40 pts.wt. modified chlorinated polyolefin containing 5-60wt.% (meth)acrylic ester, made by graft polymerization of a chlorinated polyolefin having a chlorine content of 10-70wt.% [e.g. a chlorinated crystalline propylene homopolymer having an intrinsic viscosity zeta (measured in tetralin at 135 deg.C) of 0.01-2dl/g] with a (meth)acrylic ester, in an organic solvent. This composition has good storage stability, undergoes no reduction in bonding strength, and enables a solid molded article of highly crystalline resin, such as a polyolefin or nylon, to be joined to an arbitrary material without the necessity for any complicated surface treating process.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to adhesive compositions. More specifically, the present invention relates to an emulsion adhesive composition suitable for bonding a highly crystalline resin molded product such as polyolefin or nylon to any material, and a method for producing the same.

[Conventional technology]

In recent years, materials for automobile parts and parts for home appliances are increasingly being made of plastics, especially from the viewpoint of ufflization and economic efficiency. Resins are preferably used.

However, since polyolefins, nylons, etc. are highly crystalline, in the form of molded products, when conventional adhesives are used, the adhesion between polyolefins and nylons or with other adherends is extremely poor. For this reason, in the adhesion process of article phase H, which is a highly crystalline resin molded article, or the adhesion process for surface cylinders, such as flocking of the molded article, plasma of the article is easily applied. A method has been adopted in which adhesion is made possible by surface treatment such as treatment or coating with brimer.

Although these methods have made it possible to bond highly crystalline resin molded products, they require a complicated surface treatment process, which is extremely disadvantageous in terms of industrial production.

Some of the inventors of the present invention have already addressed this problem in their patent application filed in 1983.
No. 312592 and Japanese Patent Application No. 62-313634 (hereinafter, both may be referred to as the prior invention), an adhesive obtained by adding a specific chlorinated polyolefin to a conventionally known water-based emulsion adhesive is disclosed. It has been found that when used, the adhesive strength when bonding a highly crystalline resin molded product such as polyolefin or nylon to any material is significantly improved.

(Problem to be solved by the invention) By using the adhesive of the earlier invention, it has become possible to bond a highly crystalline resin molded product with any material, which was previously difficult. The adhesive of the claimed invention lacks storage stability after manufacturing, and has a problem in that adhesive strength decreases when used for several days after manufacturing. Therefore, when it is used, it is necessary to use it for adhesion as soon as possible.

The purpose of the present invention is to bond highly crystalline resin molded products such as solid polyolefin and nylon to arbitrary materials with good storage stability and no decrease in adhesive strength, and without the need for complicated surface treatments. An object of the present invention is to provide an emulsion adhesive composition that can

[Means to solve the problem]

The present inventors have conducted extensive research into means for solving the problems of the prior invention. As a result, an adhesive obtained by using a modified chlorinated polyolefin in which an acrylic ester and/or a methacrylic ester is grafted onto a chlorinated polyolefin, instead of the chlorinated polyolefin that is the adhesive component of the prior invention. It was discovered that the storage stability was good when the drug composition was used, and the present invention was completed based on this finding.

The present invention provides an emulsion adhesive composition in which the resin component is (1) Adhesive synthetic resin 100! I! Suspended portion, and ■ Acrylic ester and/or methacrylic ester content 5 to 60, obtained by graft polymerization of acrylic ester and/or methacrylic ester to a chlorinated polyolefin containing 110 to 70% by weight of chlorine! f1
% modified chlorinated polyolefin by weight from 0.05 to 40 parts by weight.

The adhesive synthetic resin is preferably a resin whose main component is an acrylic resin. In addition, chlorinated polyolefins include chlorinated polypropylene, chlorinated propylene-α-olefin copolymer, chlorinated polyethylene, and chlorinated ethylene-
At least one selected from α-olefin copolymers is used.

In particular, chlorinated polyolefin has an intrinsic viscosity [η] (135
A chlorinated crystalline propylene homopolymer and/or a chlorinated crystalline propylene-α-olefin copolymer of 0.01 to 26j/9 (measured in tetralin at a temperature of 0.01 to 26j/9) is preferred.

The manufacturing method involves adding an acrylic ester and/or a methacrylic ester to an aqueous emulsion containing 100 parts by weight of an adhesive synthetic resin; /or 0.05 m5 to 601 m% modified chlorinated polyolefin containing methacrylic acid ester
An emulsion adhesive composition is produced by adding and mixing a solution consisting of ~40 parts by weight and (1) an organic solvent.

The aqueous emulsion of adhesive synthetic resin used in the present invention may be any aqueous emulsion of adhesive synthetic resin obtained by a known method. For example, in an aqueous medium, one or more polymerizable vinyl monomers are polymerized using a polymerization initiator in the presence of an emulsifier, and if necessary, a molecular weight regulator, a water-soluble polymer compound, or an inorganic compound is added. In the presence of the agent, the polymerization temperature is generally 3
It is obtained by emulsion polymerization for 1 hour to 20 hours under conditions of 0° C. to 90° C. and a polymerization pressure of atmospheric pressure to 50 Ky/ciG.

A polymerizable vinyl monomer is a compound having at least one unsaturated bond in the molecule that can be radically polymerized or copolymerized, such as acrylic acid, methyl acrylate, edyl acrylate, and methyl acrylate. , hexyl acrylate, hebutyl acrylate, acrylic acid 2
- Acrylic acids and esters such as ethylhexyl and octyl acrylate, methacrylic acid and methyl methacrylate, edyl methacrylate, butyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate,
Methacrylic acid esters such as 2-hydroxyethyl methacrylate, aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, hydroxystyrene, 1.3-
Dienes such as butadiene, isoprene, chlorobrene, 1,5-hexadiene, maleic acid and diethyl maleate, maleic acid esters such as di-n-butyl maleate, fumaric acid and diethyl fumarate, di-n fumarate - Fumaric acid esters such as butyl, acrylonitrile, methacrylonitrile, acrylamide, N-methylolacrylamide, methacrylamide, vinyl chloride,
Examples include vinylidene chloride, vinyl acetate, and copolymerizable ethylene. These monomers may be used singly or in combination
More than one species is used.

Examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide and t-butylhydride peroxide, hydrogen peroxide, 2,2-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, etc. A radical initiator consisting of persulfate and a combination thereof with a reducing agent such as sodium thiosulfate or ferrous chloride is used.

Examples of emulsifiers include anionic surfactants such as fatty acid salts and higher alcohol sulfuric esters, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, and sorbitan alkyl esters. A surfactant such as a surfactant is used.

The aqueous emulsion after polymerization obtained as described above can be used as it is as an aqueous emulsion for adhesive synthetic resin, but after adjusting the viscosity with aqueous ammonia etc., if necessary, it can be used as an aqueous emulsion for adhesive synthetic resin. , fillers, crosslinking agents, preservatives, ultraviolet absorbers, etc. may be added.

Although the aqueous emulsion of the adhesive synthetic resin obtained as described above is used in the present invention, it is also possible to use a commercially available aqueous emulsion type adhesive as it is. At that time, the vinyl used)
There are many types depending on the body type, but you can choose the best one depending on the material you want to bond. For example, acrylic water-based emulsion adhesives containing acrylic acid esters as the main vinyl monomer, vinyl acetate water-based emulsion adhesives containing vinyl acetate as the main vinyl monomer, and styrene adhesives containing styrene as the main vinyl monomer. Water-based emulsion adhesives are preferably used, and acrylic water-based emulsion adhesives are particularly preferred from the viewpoint of weather resistance.

A modified chlorinated polyolefin (hereinafter sometimes referred to as modified chlorinated polyolefin) obtained by graft polymerization of an acrylic ester and/or a methacrylic ester, which is the second resin component of the emulsion adhesive composition of the present invention.

) can be prepared by dissolving a polyolefin prepared by a known method in a solvent such as tetrachloroethane, in an aqueous suspension, or in a gas phase at a reaction temperature of 30°C to 120°C and a pressure of atmospheric pressure to 10°C. The chlorination reaction is usually carried out for 1 to 10 hours by adding chlorine gas under the conditions of 9/aiG and, if necessary, using means to increase reaction efficiency such as using a radical initiator or irradiating ultraviolet light. After that, the chlorinated polyolefin obtained by removing the solvent and water is dissolved in, for example, an organic solvent, and acrylic ester and/or methacrylic ester is dissolved in the presence of a radical initiator and, if necessary, a chain transfer agent. 1 using a known method such as adding acid nisdel and graft polymerizing at a temperature of 50°C to 200°C.
be qed.

The content of acrylic ester and/or methacrylic ester in the modified chlorinated polyolefin is 5 to 6.
0% by weight is desirable. If it is less than 5% by weight, the storage stability of the obtained adhesive composition will be insufficient, and if it is less than 60% by weight.
If it exceeds this, the adhesive strength will be insufficient.

The chlorinated polyolefin used in the production of the above-mentioned modified chlorinated polyolefin includes polyolefins obtained by known methods regardless of stereoregularity, such as polypropylene, propylene-α-olefin copolymer, polyethylene, and ethylene. - Chlorinated polypropylene, chlorinated propylene-α-olefin copolymer, which is obtained by chlorinating polyolefin such as α-olefin copolymer, t3i! Examples include z-polyethylene, chlorinated ethylene-α-olefin copolymer, etc., and the chlorine content of the chlorinated polyolefin is preferably 10 to 70% by weight. If the chlorine content deviates from this range, the adhesive strength of the resulting adhesive composition will be insufficient. In addition to ethylene and propylene, examples of α-olefins used for copolymerization with J3, propylene, and ethylene include butene-1, hexene-1,
Examples include straight chain olefins such as octene-1, branched chain olefins such as 4-methylpentene-1, and dienes such as butadiene and isoprene.

Among the above chlorinated polyolefins, from the viewpoint of adhesiveness and heat resistance, the intrinsic viscosity [η] (measured in tetralin at 135°C, the same applies hereinafter) is 0.01 to 2 (1/9 of the chlorinated crystalline polypropylene). and chlorinated crystalline propylene-α-olefin copolymers are preferably used.

In addition, acrylic esters and/or methacrylic esters used in the production of modified chlorinated polyolefins include methyl acrylate, ethyl acrylate, in-butyl acrylate, 1li-ethyl acrylate, hexyl acrylate, octyl acrylate, Acrylic acid esters such as acrylic 1m2-ethylhexyl, methacrylic esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, hexyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate. can give.

These monomers may be used alone or in combination.

In addition to these 1lffi forms, monomers copolymerizable with the above monomers, such as styrene, acrylonitrile, vinyl acetate, etc., in an amount that does not impede various performances of the adhesive composition of the present invention. It is also possible to use them together.

Furthermore, as the radical initiator used in the production of the modified chlorinated polyolefin, the same radical initiators as those used for the adhesive synthetic resin emulsion mentioned above can be mentioned, but in particular, organic peroxide initiators can be used. Preferably. Specifically, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, 2゜5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2, 5-dimethyl-2,5 di(t
-butylperoxy)hexane, etc.

The emulsion adhesive composition of the present invention essentially contains the above two components as synthetic resin components, and the composition ratio of each component is 0.00 parts by weight of the modified chlorinated polyolefin per 100 parts by weight of the adhesive synthetic resin component. Must be between 05 and 40 Confucian language.

If the modified chlorinated polyolefin is outside the above range, the adhesive strength of the resulting adhesive composition will decrease.

The emulsion adhesive composition of the present invention is an aqueous emulsion that essentially contains a synthetic resin component having the above composition, and the following method is shown as a manufacturing method.

That is, it can be obtained by adding a solution consisting of (B) (1) modified chlorinated polyolefin and (2) an organic solvent to the previously described (A) synthetic resin aqueous emulsion. If no organic solvent is used, the resulting adhesive composition will have insufficient adhesive strength. The organic solvent 1 to be used is not particularly limited as long as it can dissolve the modified chlorinated polyolefin, but -
Inside the shell is about 2 to 30 times the modified chlorinated polyolefin.

Any solvent can be used as long as it dissolves the above-mentioned modified polyolefin, but examples include aromatic hydrocarbons such as toluene and xylene, trichloroethylene, trichloroethane, and trichloroethane. Chlorinated hydrocarbons, furthermore, ketones, esters, etc. are included, and one or more of these may be used.

In addition, a resin such as rosin ester or petroleum resin may be added to this solution in an amount that does not impede various performances of the adhesive composition of the present invention, or an aqueous solution of a surfactant may be further added. It is also possible to add it to the adhesive synthetic resin aqueous emulsion after mixing.

In addition, when using a commercially available water-based emulsion type adhesive as the water-based emulsion of the adhesive synthetic resin, the resulting adhesive may become pasty when the above solution is added. By adding water to a commercially available water-based emulsion type adhesive in advance, it is possible to maintain a stable emulsion state even after adding the solution.

In this way, the emulsion adhesive composition of the present invention is obtained, but from the viewpoint of workability, the concentration of the resin component in the composition is 10 to 6.
It is preferable that the viscosity is about 0.01% and the viscosity is about 100 to 30.000 cps.

In addition, if a relatively large amount of organic solvent is used during production, the desired amount of organic solvent can be removed by distilling the obtained emulsion under reduced pressure at temperatures between room temperature and 80°C. It is possible.

The emulsion adhesive composition of the present invention obtained as described above can be used for adhesion between molded products of highly crystalline resin such as polyolefin and nylon, and for surface modification such as flocking of the molded products. used for. As for the method of adhesion, a known method similar to that used for conventional aqueous emulsion adhesives is used.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.

Examples will be described separately for 1. adhesion of an injection molded piece of polypropylene and a nylon nonwoven fabric, and 2. adhesion of an injection molded piece of polypropylene and a nylon pile.

1. Adhesion test between polypropylene injection molded piece and nylon nonwoven fabric The materials and test method are as follows.

1) Test material injection molded polypropylene piece with length 10α, width 21, and thickness 3M, and nylon nonwoven fabric with length 10cm11 and width 2cm 2) Adhesive polypropylene injection molded piece, nylon nonwoven fabric, each edge 2α square After applying the adhesive to the area with a brush, both coated and non-coated surfaces were overlapped and bonded. Subsequently, it was dried at 80° C. for 30 minutes and then left at room temperature for 24 hours.

3) Measurement of adhesive strength At room temperature, each end of the unbonded test material was tested in a 180° direction using a Tensilon tensile tester.
The tensile strength (Kg f /α) was measured at a rate of wear/min.

(Example 1) Intrinsic viscosity (η) is 0.70 dj!/g, chlorine content is 3
Acrylic acid obtained by dissolving 0.0% by weight of a chlorinated crystalline propylene homopolymer in xylene and then graft polymerizing acrylic in-butyl onto the chlorinated crystalline propylene homopolymer under graft polymerization conditions. 12 g of n-butyl acrylate modified chlorinated crystalline propylene homopolymer with an n-butyl content of 35% by weight was mixed with xylene 150a
i! and dissolved to obtain a solution.

Next, adhesive synthetic 81III water-based emulsion, which was prepared by adding 80 g of water to acrylic-styrene copolymer resin water-based emulsion adhesive (manufactured by Kanebo NSC, trade name Yodozol AA57, resin component 40% by weight) 4009, was added. The solution obtained was added and mixed to obtain an emulsion adhesive composition. An adhesion test was conducted on the obtained adhesive composition, and the peel strength was found to be 2.30/If/cn. In addition, after putting the obtained adhesive composition into a glass flask and capping it, under the lighting of a 30W fluorescent lamp, 1.5
After leaving it at a 7FL location for 2 months, an adhesion test was conducted on the adhesive composition, and the peel strength was 2.1 (
It was lf/α.

(Comparative Example 1) In Example 1, instead of the acrylic@n-butyl modified chlorinated crystalline buOpyrene homopolymer, acrylic 1ln
- Unmodified chlorinated crystalline propylene homopolymer without butyl graft polymerization (intrinsic viscosity (η) is 0.70
An adhesive composition was obtained in the same manner except that 12 g of the adhesive was used (6j/g, chlorine content was 30.0M1%). An adhesion test was conducted on the obtained adhesive composition in the same manner as in Example 1.

The test results after Comparative Example 1 are shown in Table 1 together with the test results of Example 1.

(Comparative Example 2) In Example 1, a commercially available acrylic-styrene copolymer resin water-based emulsion adhesive was used as it was without adding a xylene solution of n-butyl acrylate modified chlorinated crystalline propylene homopolymer. An adhesion test was conducted in the same manner as in Example 1 except for the following.

(Comparative Example 3.4 and Example 2.3) In Example 1, the ratio of the n-butyl acrylate modified chlorinated crystalline propylene homopolymer to the adhesive synthetic resin component was changed as shown in the table. An adhesive composition was obtained in the same manner except for the above, and an adhesion test was conducted.

(Comparative Example 5) In Example 1, instead of the n-butyl acrylate modified chlorinated crystalline propylene homopolymer, the average molecular nail was 5.
．． An adhesive composition was obtained in the same manner except that 4.2 g of 80,000 acrylic 1ln-butyl homopolymer was used, and an adhesion test was conducted.

(Comparative Example 6) In Example 1, instead of the acrylic l1n-butyl modified chlorinated crystalline propylene homopolymer, acrylic In
- Unmodified chlorinated crystalline propylene homopolymer without butyl graft polymerization (intrinsic viscosity [η] is 0.70
6J/g, chlorine content is 30.0iij amount%) 7.8g
An adhesive composition was obtained in the same manner except that 4.2 g of n-butyl acrylate polymer having an average molecular weight of 58,000 was used, and an adhesion test was conducted.

(Comparative Example 7) In Example 1, acrylic 'FIi
An adhesion test was conducted in the same manner except that only a xylene solution of n-butyl-modified chlorinated crystalline propylene homopolymer was used as the adhesive composition.

(Comparative Example 8) In Example 1, the n-butyl acrylate modified chlorinated crystalline propylene homopolymer was not dissolved in xylene,
Acrylic crushed using a crusher at a temperature of -20℃ 1! Adhesion was carried out in the same manner except that 12 g of n-butyl-modified chlorinated crystalline propylene homopolymer powder was added and mixed into an adhesive synthetic resin emulsion prepared by adding water to an acrylic-styrene copolymer resin water-based emulsion type adhesive. An adhesion test was conducted using the agent composition (7).

(Comparative Example 9.10 and Example 4.5) An adhesive was prepared in the same manner as in Example 1 except that the n-butyl acrylate modified chlorinated crystalline propylene homopolymer shown in the table was used. A composition was obtained and an adhesion test was conducted.

(Example 6) Intrinsic viscosity [η] of a chlorinated crystalline propylene-butene-1 copolymer with a butene-1 content of 2.5mf11%
is 0.47djl/g, 33! Elementary content is 22.5i
Acrylic In obtained by graft copolymerizing 1% of chlorinated crystalline propylene-butene-1 copolymer with n-ethyl acrylate and 2-ethylhexyl acrylate.
n-butyl content m is 20%, and acrylic 112
- Acrylic acid ester modified chlorinated crystalline propylene-butene-1 copolymer 89 having an ethylhexyl content of 5.01% was dissolved in 150 g of toluene. Next, we developed an acrylic/styrene copolymer resin water-based emulsion adhesive (
Manufactured by Saiden Chemical Co., Ltd., product name Cypino-/L, F
-4, resin component 351f11%) 45091. :Water 50
The previously obtained solution was added to and mixed with the adhesive synthetic resin aqueous emulsion to which g was added to obtain an emulsion adhesive composition. An adhesion test was conducted on the obtained adhesive composition in the same manner as in Example 1.

(Comparative Example 11) In Example 6, in place of the acrylic ester-modified chlorinated crystalline propylene-butene-1 copolymer, unmodified chlorinated crystalline propylene-butene-1 without graft polymerization of the acrylic ester was used. 1 copolymer (intrinsic viscosity [
η] is 0,476j/IJ, chlorine content is 22.5o
An adhesive composition was obtained in the same manner except that %>89 was used.

A species name test was conducted on the obtained adhesive composition in the same manner as in Example 6.

(Comparative Example 12) In Example 6, a commercially available acrylic-styrene copolymer resin-based aqueous emulsion adhesive was used without adding a toluene solution of an acrylic acid ester-modified chlorinated crystalline propylene-butene-1 copolymer. The adhesive test was conducted in the same manner as in Example 6 except for using the product as it was.

(Example 7) Chlorinated ethylene-propylene rubber with an ethylene content of 60% by weight, with an intrinsic viscosity [η] of 0.366j/g
, obtained by graft copolymerizing ethyl acrylate and vinyl acetate to a chlorinated ethylene-propylene rubber with a chlorine content of 40.5% by weight, the ethyl acrylate content is 40tiit%, and the vinyl acetate content m is 5%. .0i
fi% modified chlorinated ethylene-propylene rubber 12g
was dissolved in 150 d of xylene. Next, an ethylene/vinyl acetate copolymer resin water-based emulsion type adhesive (manufactured by Hoechst Gosei Co., Ltd., trade name t-vinyl 085E1 resin content 5
The previously obtained xylene solution of modified chlorinated ethylene-propylene rubber was added and mixed to an adhesive synthetic resin aqueous emulsion prepared by adding 100 g of water to 5% by weight) 4009 to obtain an emulsion adhesive composition. An adhesion test was conducted on the obtained adhesive composition in the same manner as in Example 1.

(Comparative Example 13) In Example 7, instead of the modified chlorinated ethylene-propylene rubber, unmodified chlorinated ethylene-propylene rubber (intrinsic viscosity [η]) in which ethyl acrylate and vinyl acetate were not graft polymerized was used. is 0,366j/a,
An adhesive composition was obtained in the same manner except that 12 g (chlorine content: 40.5% by weight) was used. An adhesion test was conducted on the obtained adhesive composition in the same manner as in Example 7.

(Comparative Example 14) In Example 7, a commercially available ethylene/vinyl acetate copolymer resin water-based emulsion adhesive was used as it was without adding a xylene solution of modified chlorinated ethylene-propylene rubber, and the other conditions were as follows. An adhesion test was conducted in the same manner as in Example 7.

(Example 8) In Example 1, instead of the n-butyl acrylate modified chlorinated propylene homopolymer, a material with an intrinsic viscosity (η) of 0 was used.
．． 256j/g, methyl methacrylate content obtained by graft copolymerizing methyl methacrylate and n-butyl acrylate to chlorinated polyethylene with a chlorine content of 62.5ffi%, and acrylic acid containing methyl methacrylate content of 25fJ1%. An emulsion adhesive composition was obtained in the same manner except that 12 g of modified chlorinated polyethylene having an n-butyl content of 15% by weight was used, and an adhesion test was conducted.

(Comparative Example 15) In Example 8, in place of the modified chlorinated polyethylene, methyl methacrylate and unmodified fi-polyethylene (with an intrinsic viscosity (η) of 0.25 dj) in which acrylic 11n-butyl was not graft-polymerized were used. An adhesive composition was obtained in the same manner except that !/!?, chlorine content: 62.5% by weight) 129 was used, and an adhesion test was conducted.

2. Polypropylene injection molded piece and nylon pile 1) Test material A polypropylene injection molded piece measuring 101cm long, 2cm wide and 3cm thick, and a nylon pile of 3 denier and 1m long 2) Adhesive propylene tUt extrusion molding Glue on the piece 150-2009
/Apply at the foot and electrostatically flock nylon pile. then 8
After drying at 0°C for 30 minutes, it is left at room temperature for 2.4 hours.

3) Measurement of adhesive strength The flocked surface was rotated with a cutter under a load of 200 g, and the presence or absence of adhesive peeling from the polypropylene injection molded piece was checked.

(Example 9) As a result of applying and testing the adhesives of Examples 1 to 8 described above, no peeling of the adhesive occurred. In addition, similar results were obtained for the paper that had been produced for 2 months.

(Effects of the Invention) The emulsion adhesive composition of the present invention has good storage stability, almost no decrease in adhesive strength, and! It is possible to make a solid molded product made of a highly crystalline resin such as polyolefin or nylon in close contact with any material without requiring a complicated surface treatment process.

As is clear from the examples, when an adhesive test was conducted two months after manufacture, the peel strength was higher when the emulsion adhesive composition of the present invention was used than when the adhesive of the prior invention was used. The storage stability is significantly higher than that of
reference).

In addition, when obtained under conditions outside the scope of the present invention,
When an adhesive composition having a composition outside the range of the present invention is used, it lacks storage stability, or the peel strength is already extremely low in an adhesion test immediately after production (Comparative Examples 2 to 10).
(see 12.14).

Claims (1)

[Scope of Claims] 1. An emulsion adhesive composition, wherein the resin component in the adhesive composition is (1) 100 parts by weight of an adhesive synthetic resin, and (2) a chlorine content of 10 to 70% by weight. Acrylic ester and/or methacrylic ester is graft polymerized to chlorinated polyolefin.
Or an emulsion adhesive composition comprising 0.05 to 40 parts by weight of a modified chlorinated polyolefin having a methacrylic acid ester content of 5 to 60% by weight. 2. The emulsion adhesive composition according to claim 1, wherein the adhesive synthetic resin is an adhesive synthetic resin whose main component is an acrylic resin. 3. The chlorinated polyolefin is chlorinated polypropylene,
The emulsion four-adhesive composition according to claim 1, which is at least one selected from chlorinated propylene-α-olefin copolymer, chlorinated polyethylene, and chlorinated ethylene-α-olefin copolymer. 4. The chlorinated polyolefin has an intrinsic viscosity [η] (135
The emulsion adhesive according to claim 1 or 3, which is a chlorinated crystalline propylene homopolymer and/or a chlorinated crystalline propylene-α-olefin copolymer at a concentration of 0.01 to 2 dl/g (measured in tetralin at a temperature of 0.01 to 2 dl/g). Composition. 5. A Aqueous emulsion containing 100 parts by weight of an adhesive synthetic resin B (1) Acrylic ester made by graft polymerizing acrylic ester and/or methacrylic ester to a chlorinated polyolefin with a chlorine content of 10 to 70% by weight Acid ester and/or methacrylic ester content 5~
60% by weight modified chlorinated polyolefin 0.05-40
1. A method for producing an emulsion adhesive composition, which comprises adding a solution consisting of parts by weight, and (2) an organic solvent. 6. The method for producing an emulsion adhesive composition according to claim 5, wherein the adhesive synthetic resin is a resin whose main component is an acrylic resin. 7. The chlorinated polyolefin is chlorinated polypropylene,
6. The method for producing an emulsion adhesive composition according to claim 5, wherein the emulsion adhesive composition is at least one selected from a chlorinated propylene-α-olefin copolymer, a chlorinated polyethylene, and a chlorinated ethylene-α-olefin copolymer. 8. The chlorinated polyolefin has an intrinsic viscosity [η] (135
The emulsion adhesive according to claim 5 or 7, which is a chlorinated crystalline propylene homopolymer and/or a chlorinated crystalline propylene-α-olefin copolymer at a concentration of 0.01 to 2 dl/g (measured in tetralin at a temperature of 0.01 to 2 dl/g). Method for producing the composition.