JPH0337287A - Emulsion type adhesive composition and its preparation - Google Patents

Abstract

PURPOSE:To make it possible to adhere a molded item of a highly crystalline resin in a solid state with an arbitrary material by incorporating an adhesive synthetic resin and a hydrogenated product of a specified block copolymer. CONSTITUTION:A water-based emulsion of 100 pts.wt. (solid content) adhesive synthetic resin (A) wherein one or more resins selected from among acrylic, styrenic and vinyl acetate resins are main components and a soln. (B) consisting of 0.05-40 pts.wt. hydrogenated product of a block copolymer (a) consisting of a polyolefin with an inherent viscosity (135 deg.C in tetraline) of 0.10-10dl/g contg. 0.01-20wt.% functional group selected from among carboxylic anhydride, COOH, glycidyl, OH, amide and alkoxysilyl groups and/or an arom. vinyl compd. polymer block contg. 0.01-20wt.% said functional group and an aliph. diene polymer block and an org. solvent (b) are mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition and a method for producing the same. More specifically, the present invention relates to an emulsion-type 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 have been increasingly made of plastics, especially from the viewpoint of weight reduction and economic efficiency. Among them, polyolefins such as polypropylene and polyethylene, and highly crystalline resins such as nylon are becoming more and more popular. Preferably used.

However, since polyolefins, nylon, etc. are highly crystalline, methods that enable adhesion in the form of molded products include surface treatment such as plasma treatment or primer coating before applying the adhesive. has been adopted.

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

[Problem to be solved by the invention]

The purpose of the present invention is to
It is an object of the present invention to provide an emulsion type adhesive composition and a method for producing the same, which can bond a molded article of a highly crystalline resin such as polyolefin or nylon to any material in a solid state.

[Means to solve the problem]

The present inventors have made it possible to bond molded products made of highly crystalline resin such as polyolefin or nylon to each other or to other adherends 2, that is, to any material, without requiring a complicated surface treatment process. We did extensive research on adhesives. As a result, traditional aqueous emulsion adhesives can be modified to contain functionalized polyolefins and/or at least one functionalized polyolefin.
aromatic vinyl compound polymer blocks and at least one
By using an adhesive composition obtained by adding and mixing a hydrogenated block copolymer consisting of aliphatic diene polymer blocks in a specific state, it is possible to produce highly crystalline materials such as polyolefins and nylon, which has been difficult to achieve in the past. The present inventors have discovered that the adhesive strength when adhering a plastic molded product to an arbitrary material is significantly improved, and based on this knowledge, they have completed the present invention.

The present invention has the following tM.

(1) An emulsion type adhesive composition, wherein the resin components in the composition are: (1) 100 parts by weight of an adhesive synthetic resin, and (2) a carboxylic acid anhydride group, a carboxyl group, a glycidyl group, a hydroxyl group, an amide group, and A polyolefin containing 0.01% to 20% by weight of one or more functional groups selected from alkoxysilyl groups, and/or at least one aromatic containing 0.01% to 20% by weight of the functional group. An emulsion type adhesive composition comprising 0.05 parts by weight to 40 parts by weight of a hydrogenated block copolymer comprising a group vinyl compound polymer block and at least one aliphatic diene polymer block.

(2) The adhesive synthetic resin is an adhesive synthetic resin whose main component is one or more resins selected from acrylic resin, styrene resin, and vinyl acetate resin.
The composition described in 1).

(3) A hydrogenated product of a block copolymer consisting of a polyolefin and/or at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block has an intrinsic viscosity (η) (at 135°C (measured in Tetralin) 0.1dj7/r~10dD
The composition according to (1) above, which is a polymer of /tr.

(4) Hydrogenated product of a polyolefin containing a functional group and/or a block copolymer consisting of at least one aromatic vinyl compound polymer block containing a functional group and at least one aliphatic diene polymer block is a polymer containing 70% by weight or less of chlorine in addition to the functional group.

(5) In the method for producing an emulsion-type adhesive composition, (A) an aqueous emulsion of an adhesive synthetic resin is added, based on 100 parts by weight of the synthetic resin in the emulsion, (B) (1) a carboxylic acid anhydride group, 0.01ffi of one or more functional groups selected from carboxyl group, glycidyl group, hydroxyl group, amide group, and alkoxysilyl group
polyolefin containing % to 20% by weight, and/or at least one aromatic vinyl compound polymer block and at least 1 aliphatic diene polymer block containing 0.01% to 20% by weight of the functional group. 0.05 parts by weight to 40 parts by weight of a hydrogenated block copolymer consisting of
1. A method for producing an emulsion-type adhesive composition, which comprises adding a solution consisting of: parts by weight, and (1) an organic solvent.

(6) The adhesive synthetic resin described above is an adhesive synthetic resin whose main component is one or more resins selected from acrylic resins, styrene resins, and vinyl acetate resins.
The manufacturing method described in 5).

(7) A hydrogenated product of a block copolymer consisting of a polyolefin and/or at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block has an intrinsic viscosity [η] (at 135°C). (measured in Tetralin) 0.1 dl/g to 10 dD/g
The manufacturing method according to (5) above, which is a polymer of

(8) Hydrogenated product of a polyolefin containing a functional group and/or a block copolymer consisting of at least one aromatic vinyl compound polymer block containing a functional group and at least one aliphatic diene polymer block is a polymer containing 70% by weight or less of chlorine in addition to the functional group.

The configuration of the present invention will be explained in detail below.

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, a polymerizable vinyl monomer of IN or more is synthesized using a polymerization initiator in the presence of an emulsifier, and if necessary, additives such as a molecular weight regulator, a water-soluble polymer compound, or an inorganic compound. In the presence of - for boat fishing, the polymerization temperature is 3
It is obtained by emulsion polymerization for about 1 hour to 20 hours under conditions of 0° C. to 90° C. and a polymerization pressure of atmospheric pressure to 50 kg/eJG.

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, ethyl acrylate, and butyl acrylate. , acrylic acid esters such as hexyl acrylate, 2-ethylhexyl acrylate, hebutyl acrylate, octyl acrylate, methacrylic acid and methyl methacrylate,
Methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, etc., aromatic monomers such as styrene, a-methylstyrene, vinyltoluene, hydroxystyrene, etc. , 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. One or more types of these monomers are used.

Examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide, hydrogen peroxide, 2,2-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, etc. Radical initiators such as persulfates and their combinations with reducing agents such as sodium thiosulfate and ferrous chloride are 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 type of 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. , a filler, a crosslinking agent, a preservative, etc. may be added.

The aqueous emulsion of the adhesive synthetic resin obtained as described above is used in the present invention, but it is also possible to use a commercially available aqueous emulsion type adhesive as it is.

At that time, there are many types depending on the volume of the vinyl monomer used, but the most suitable one can be selected according to the desired material to be bonded. For example, acrylic water-based emulsion adhesives containing acrylic esters as the main vinyl monomer;
Vinyl acetate-based aqueous emulsion adhesives containing vinyl acetate as the main vinyl monomer and styrene-based aqueous emulsion adhesives containing styrene as the main vinyl monomer are preferably used.

One or more functional groups selected from a carboxylic anhydride group, a carboxyl group, a glycidyl group, a hydroxyl group, an amide group, and an alphoxysilyl group, which is the second resin component of the emulsion type adhesive composition of the present invention. o, ot weight%~2
A block copolymer consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing a polyolefin containing 0ffij1% and/or an o,ot weight% to 20m11% of the functional group. The hydrogenated product (hereinafter sometimes abbreviated as functional group-containing polyolefin, etc.) is a combination of a polyolefin and/or an aromatic vinyl compound polymer block of at least Im, obtained by a known method, and at least It is a resin component in which the above functional group is introduced into a hydrogenated block copolymer (hereinafter sometimes abbreviated as polyolefin etc.) consisting of a 16q aliphatic diene polymer block. Polyolefin of the functional group There are various methods for introducing vinyl monomers having the functional group into polyolefins, etc., but an easy method is to graft-polymerize vinyl monomers having the functional groups to polyolefins, etc. That is, by dissolving polyolefins etc. in an organic solvent, In an aqueous suspension or in a gas phase, in the presence of a radical initiator and, if necessary, a chain transfer agent, the vinyl monomer having the above-mentioned functional group is added to the temperature at 30°C to 200°C. It can be obtained by a known method such as a method of graft polymerization under temperature conditions of

The content of functional groups in the functional group-containing polyolefin, etc. is preferably 0.01% by weight to 20% by weight.

If the content of the functional group deviates from this range, the resulting adhesive composition will have insufficient adhesive strength.

The polyolefins used in the production of the above-mentioned functional group-containing polyolefins used in the present invention include polyolefins obtained by known methods regardless of their three-dimensional lamination properties;
For example, polypropylene, propylene-α-olefin copolymer, polyethylene, ethylene-α-olefin copolymer, poly4-methylpentene-1,4-methylpentene-1-α-olefin copolymer, etc., and similarly known Hydrogen of a block copolymer obtained by the method obtained by the method of Examples of additives include hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, and hydrogenated styrene-butadiene-styrene block copolymers. In addition, the α-olefin used for copolymerization with propylene etc.
In addition to ethylene, propylene, and 4-methylpentene-1, there are linear olefins such as butene-1, hexene-1, and octene-1, branched chain olefins such as 2-methylpentene-1, butadiene, and isoprene. Examples include dienes such as

Among the above polyolefins, polyolefins, hydrogenated styrene-butadiene-styrene block copolymers, and hydrogenated styrene-isoprene block copolymers are preferably used, especially from the viewpoint of adhesiveness, weather resistance, and heat resistance. , the intrinsic viscosity [η) (measured in tetralin at 135°C, the same applies hereinafter) is 0.1 dl/g to 10 dl/
The polyolefin of g is preferably used. As these polyolefins, those of IN class or higher are used.

As described above, a functional group-containing polyolefin or the like can be obtained by graft polymerizing a vinyl monomer having a functional group to the polyolefin or the like described above. As the vinyl monomer having a functional group used for producing the functional group-containing polyolefin, etc., one or more types of functional groups such as a carboxylic acid anhydride group, a carboxyl group, a glycidyl group, a hydroxyl group, an amide group, an alkoxysilyl group, etc. Examples of vinyl monomers that can be graft polymerized include maleic anhydride, itaconic anhydride, citraconic anhydride, allylconic anhydride,
Vinyl monomers with carboxylic acid anhydride groups such as glutaconic anhydride, nadic anhydride, methyl nadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid , itaconic acid, citraconic acid, allylsuccinic acid, glutaconic acid, nadic acid, methylnadic acid,
Vinyl monomers with carboxyl groups such as tetrahydrophthalic acid and methyltetrahydrophthalic acid; vinyl monomers with glycidyl groups such as glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, methylglycidyl methacrylate, and allyl glycidyl ether. , 2-hydroxyethyl acrylate, methacrylic acid 2
-Hydroxyethyl, hydroxypropyl acrylate,
Vinyl monomers having a hydroxyl group such as hydroxypropyl methacrylate, vinyl monomers having an amide group such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyldimethylethoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-
Examples include vinyl 1-mer having an alkoxy group such as acryloxypropylmethyldimethoxysilane. These monomers are used in an amount of 1.1 or more. In addition to the vinyl monomers having these functional groups, monomers such as styrene, acrylonitrile, acrylic esters, methacrylic esters, It is also possible to use vinyl acetate etc. in combination. These monomers that can be used in combination can be used simultaneously with a monomer having a functional group to perform graft copolymerization.
It is also possible to carry out graft polymerization in the presence of a radical initiator before or after graft polymerization of a monomer having a functional group.

As the radical initiator used in the production of functional group-containing polyolefin, etc., the same radical initiators as those used in the production of the adhesive synthetic resin emulsion mentioned above can be mentioned, but organic peroxides are particularly preferred. Yes. 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 functional group-containing polyolefin, etc., which is the second resin component of the emulsion-type adhesive composition of the present invention, can be obtained as described above. It is also a preferred embodiment of the present invention to contain chlorine in an amount of .

If the chlorine content exceeds 70% by weight, the adhesive strength will decrease. The introduction of chlorine may be carried out either before or after the graft polymerization step of introducing a functional group into polyolefin or the like, or it may be carried out during the graft polymerization. Chlorine can be introduced in a state in which polyolefin or functional group-containing polyolefin is dissolved in a solvent such as tetrachloroethane, in an aqueous suspension, or
Under reaction temperature 30℃ ~ 120℃, pressure is atmospheric pressure ~ 10k
The reaction is usually carried out for 1 to 10 hours by adding chlorine gas under the conditions of g/cseG and, if necessary, using means to increase reaction efficiency such as using a radical initiator or irradiating ultraviolet rays.
A known method such as carrying out a chlorination reaction can be used.

In addition, when the above chlorination reaction is performed before introducing a functional group into a polyolefin, etc., an active group capable of reacting with chlorine, such as a mercapto group or an amino group, is used instead of the vinyl monomer that converts the functional group into H. Compounds having the functional groups described above, specifically γ-mercaptopropyltrimethoxysilane, γ
It is also possible to introduce a functional group by conducting a reaction using -aminopropyltriethoxysilane or the like in the presence of an acid acceptor or a radical initiator.

The emulsion-type adhesive composition of the present invention requires the above two components as synthetic resin components, and the proportion of each component used is such that functional group-containing polyolefin, etc. is used per 100 parts by weight of the adhesive synthetic resin component. It is necessary that the amount is 0.05 parts by weight to 40 parts by weight. If the proportion of the functional group-containing polyolefin or the like used is outside the above range, the adhesive strength of the resulting adhesive composition will decrease.

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

That is, it is obtained by adding a solution consisting of (B) (1) a functional group-containing polyolefin, etc., and (2) an organic solvent to the aqueous emulsion of the adhesive synthetic resin (A) described above. If no organic solvent is used, the resulting adhesive will have insufficient adhesive strength. The amount of organic solvent used is not particularly limited as long as it dissolves the functional group-containing polyolefin, but for boat fishing it is about 2 to 30 times the weight of the functional group-containing polyolefin.

Any organic solvent can be used as long as it dissolves the above-mentioned functional group-containing polyolefin, but examples include aromatic hydrocarbons such as toluene and xylene,
Examples include chlorinated hydrocarbons such as trichloroethylene, dichloroethane, and trichloroethane, aliphatic hydrocarbons such as heptane, octane, and decane, and furthermore ketones and esters, and one or more of these may be used.

In addition, synthetic resins such as petroleum resins and amino resins may be added to this solution in an amount that does not impede the performance of the adhesive composition of the present invention, and an aqueous solution of a surfactant may be further added. After mixing, it is also possible to add it to the aqueous emulsion of the adhesive synthetic resin.

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 composition 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 the emulsion state stably even after adding the solution.

In this way, the emulsion type adhesive composition of the present invention is obtained, but from the viewpoint of workability, the concentration of the resin component in the adhesive composition is about 10% by weight to 65% by weight, and the viscosity is about 100 cps to 3.
The range is preferably about 0.0OOcps. In addition, if a relatively large amount of organic solvent is used during production, it is also possible to remove the desired amount of organic solvent by distilling the resulting emulsion under reduced pressure at a temperature of about room temperature to 80°C. be.

The emulsion type 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 or nylon, and for surface decoration such as flocking of the molded products. Used for adhesion. As for the method of adhesion, a known method similar to that used for conventional water-based emulsion adhesives is used.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The present invention is not equally limited by these Examples. The adhesiveness was confirmed by a heavy adhesion test and a flocking test.

(1) Heavy adhesion test ■ Test material Polypropylene injection molded piece (length 1ocIIS width 2cm
m+, thickness 3 m days) and polyacrylonitrile fiber woven fabric (length 10 (J8, width 2 csa)).

■ Adhesion Using the above injection molded piece and woven fabric, the adhesive composition was applied with a brush to a 2 cm square area on one end of each, and then both coated sides and uncoated sides were overlapped and bonded. . Subsequently, it was dried at 80° C. for 30 minutes and then left at room temperature for 24 hours.

■ Measurement of adhesive strength Using a Tensilon type tensile tester at room temperature, each end of the unbonded test material was pulled in a 180 degree direction at 20 steps/min to measure the peel strength.
(Unit: kgr/unit) (2) Flocking test ■ Test material Polypropylene injection molded piece (10 units long, 10 cm wide)
, thickness 3 m-), and nylon pile (thickness 3 denier, length 1++n).

'■ Flocking: Apply 150 to 300 tons of adhesive composition to the above injection molded piece.
r/td coating, and the nylon pile was flocked by applying a voltage of 70 KV using an electrostatic flocking machine. 30 consecutively
After drying at 80° C. for minutes, it was left to stand at room temperature for 24 hours.

(2) Adhesion At room temperature, a load of 200 g was applied to the flocked surface using a cutter, and the cutter was further rotated to check for peeling of the adhesive composition from the injection molded piece.

(Example 1) Isotactic polypropylene with an intrinsic viscosity (η) of 2.5 d and Q/sr was dissolved in xylene, and dicumyl peroxide was used as a radical initiator to graft polymerize it at 125°C. After graft polymerizing maleic anhydride to polypropylene, acetone was added to precipitate the polymer.

Subsequently, filtration and acetone washing were repeated 21'i'i'i' times, followed by drying under reduced pressure to obtain carboxylic anhydride group-containing polypropylene. After further dissolving the carboxylic anhydride group-containing polypropylene in chlorobenzene at 110°C, chlorine gas was supplied at the same temperature to perform a chlorination reaction.

After the reaction was completed, methanol was added to precipitate the polymer. Subsequently, after repeating filtration and methanol washing twice,
The mixture was dried under reduced pressure to obtain a chlorinated polypropylene containing carboxylic anhydride groups having a carboxylic anhydride group content of 2.9 ffI% and a chlorine content of 30.0% by weight.

Obtained carboxylic anhydride group-containing chlorinated polypropylene 1
2 g was added and dissolved in 150 ml of xylene. Next, 80 g of water was added to 400 g of a commercially available acrylic-styrene copolymer resin and aqueous emulsion type adhesive (manufactured by Kanebo NSC, trade name Yodozol AA57, resin component 40% by weight). A xylene solution of the carboxylic acid anhydride group-containing chlorinated polypropylene was added to an aqueous emulsion of the adhesive synthetic resin to which the above carboxylic anhydride group-containing chlorinated polypropylene was added to obtain an emulsion-type adhesive composition of the present invention. When the adhesive composition obtained was subjected to a heavy adhesion test, the peel strength was 2.35 kgf/cg.
It was e. Further, when a flocking test was conducted, no peeling of the adhesive composition was observed, and the adhesiveness was good.

(Comparative Example 1) In Example 1, a commercially available acrylic-styrene copolymer resin water-based emulsion adhesive was used as it was without adding the xylene solution of chlorinated polypropylene containing carboxylic anhydride groups, and the other conditions were as follows. A heavy adhesion test and a flocking test were conducted in the same manner as in Example 1.

(Comparative Example 2.3 and Example 2.3) The same procedure as in Example 1 was carried out except that the ratio of the carboxylic anhydride group-containing chlorinated polypropylene to the adhesive synthetic resin component was changed as shown in the table. An adhesive composition was obtained, and a heavy adhesion test and a flocking test were conducted.

(Comparative Example 4) Same as Example 1 except that only a xylene solution of chlorinated polypropylene containing a carboxylic anhydride group was used as the adhesive composition without using the acrylic-styrene copolymer resin water-based emulsion adhesive. A heavy adhesion test and a flocking test were conducted.

(Comparative Example 5) Powder of chlorinated polypropylene containing carboxylic anhydride group, which was ground in Example 1 using a grinder at a temperature of -40°C without dissolving the chlorinated polypropylene containing carboxylic anhydride group in xylene. An adhesive composition was obtained in the same manner except that 12 g was added and mixed into an aqueous emulsion of an adhesive synthetic resin in which water was added to an acrylic-styrene copolymer resin-based aqueous emulsion type adhesive, and the adhesive composition was subjected to a heavy adhesion test and flocking. We conducted a test.

(Comparative Examples 6-7, Examples 4-6) In Example 1, instead of the carboxylic anhydride group-containing chlorinated polypropylene, the intrinsic viscosity [η] was 2.0 dN/g.
, carboxyl group-containing propylene-ethylene random copolymers with different carboxyl group contents as shown in the table, obtained by graft polymerizing various amounts of maleic acid to a propylene-ethylene random copolymer with an ethylene content of 35% by weight. An adhesive composition was obtained in the same manner except that the polymer was used, and a heavy adhesion test and a flocking test were conducted.

(Example 7) In Example 1, instead of the carboxylic anhydride group-containing chlorinated polypropylene, the intrinsic viscosity [η] was 3.5 dfl/
1 of isotactic poly-4-methylpentene-1 was dissolved in toluene and graft polymerized with maleic anhydride at 145° C. using Dicumi 2 liver oxide as a radical initiator, followed by n-butyl acrylate. A carboxylic anhydride-containing n-butyl acrylate modified poly 4-methylpentene with a carboxylic anhydride content of 2.2% by weight and a carboxylic acid anhydride content of 20% by weight, obtained by graft polymerization of An adhesive composition was obtained in the same manner except that 10 times more than -1 was used, and a heavy adhesion test and a flocking test were conducted.

(Example 8) In Example 1, instead of the carboxylic anhydride group-containing chlorinated polypropylene, a hydrogenated styrene-isoprene block copolymer (manufactured by Shell Chemical Co., Ltd., trade name Kraton G1701) was dissolved in xylene, and then the radical A styrene-isoprene block copolymer containing carboxylic anhydride groups with a carboxylic anhydride group content of 2.6% by weight, obtained by graft polymerizing maleic anhydride at 125°C using dicumyl peroxide as an initiator. An adhesive composition was obtained in the same manner except that 8 g of hydrogenated material was used,
A heavy adhesion test and a flocking test were conducted.

(Example 9) After dissolving a propylene-ethylene random copolymer with an intrinsic viscosity [η] of 2.6 dfl/lr and an ethylene content of 40 ffI% in xylene, benzoyl peroxide was used as a radical initiator, and 80% After graft-polymerizing γ-methacryloxypropylmethyldimethoxysilane at ℃, maleic anhydride was further graft-polymerized to give an alkoxysilyl group content of 0.7% by weight and a carboxylic anhydride group content of 1.2% by weight. A propylene-ethylene random copolymer containing % of alkoxysilyl groups and carboxylic anhydride groups was obtained.

12 g of the obtained functional group-containing propylene-ethylene random copolymer was added to 150 ml of xylene and dissolved therein. Next, 10 g of water was added to 400 g of a commercially available ethylene/vinyl acetate copolymer resin water-based emulsion adhesive (manufactured by Hoechst Gosho Co., Ltd., trade name Movinyl 085E, resin content 55% by weight).
To an aqueous emulsion of adhesive synthetic resin to which 0 g was added,
A xylene solution of the functional group-containing propylene-ethylene random copolymer was added and mixed to obtain an adhesive composition.

Using the obtained adhesive composition, a heavy adhesion test and a flocking test were conducted in the same manner as in Example 1.

(Comparative Example 8) In Example 9, a commercially available ethylene/vinyl acetate copolymer resin-based aqueous emulsion adhesive was prepared without adding a xylene solution of a propylene-ethylene random copolymer containing an alkoxysilyl group and a carboxylic acid anhydride group. A heavy adhesion test and a flocking test were conducted using the product as it was.

(Practice 91110) After dissolving a propylene-butene-1 random copolymer with an intrinsic viscosity [η] of 3.0 dl/z and a butene-1 content of 2.0% by weight in xylene, dicumyl peroxide was radically initiated. After graft polymerizing glycidyl methacrylate under graft polymerization conditions at 130° C., a chlorination reaction was further carried out in the same manner as in Example 1, and the resulting glycidyl group content was 1. A glycidyl group-containing chlorinated propylene-butene-1 copolymer with a chlorine content of 2% by weight and a chlorine content of 18.0% by weight was obtained.

The obtained glycidyl group-containing chlorinated propylene-butene-
1 copolymer was dissolved in 150 ml of toluene. Next, a commercially available acrylic/styrene copolymer resin water-based emulsion type adhesive M (manufactured by Saiden Kagaku TT, trade name Cypinol FX-4, resin component 35% by weight) was added to 450K and 50% water.
A toluene solution of the glycidyl group-containing chlorinated propylene-butene-1 octapolymer was added and mixed to an aqueous emulsion of the adhesive synthetic resin to which g was added to obtain an emulsion type adhesive composition. The obtained adhesive composition was subjected to a heavy adhesion test and a flocking test in the same manner as in Example 1.

(Comparative Example 9) In Example 10, without adding the toluene solution of the glycidyl group-containing chlorinated propylene-butene-1 copolymer,
A heavy adhesion test and a flocking test were conducted in the same manner as in Example 10, except that a commercially available acrylic-styrene copolymer resin water-based emulsion adhesive was used as is.

(Example 11) In Example 10, 2-hydroxyethyl methacrylate was used in place of glycidyl methacrylate for graft polymerization, and then a chlorination reaction was performed to obtain a polymer with a hydroxyl group content of Hydroxyl group-containing chlorinated propylene-butene-1 copolymer 10 with a chlorine content of 0.7% by weight and 5.0% by weight
．． An adhesive composition was obtained in the same manner except that the following was used in place of the glycidyl methacrylate group-containing chlorinated propylene-butene-1 copolymer, and a heavy adhesion test and a flocking test were conducted.

(Example 12) After dissolving isotactic polypropylene with an intrinsic viscosity [η] of 4.5 dl/g in xylene, acrylamide was grafted under graft polymerization conditions at 80°C using benzoyl peroxide as a radical initiator. Polymerized. After the reaction was completed, acetone was added to precipitate the polymer. Subsequently, filtration and acetone washing were performed twice, followed by drying under reduced pressure to obtain amide group-containing polypropylene. After dissolving the amide group-containing polypropylene in chlorobenzene at 120°C, chlorine gas was supplied at the same temperature to perform a chlorination reaction. After the reaction was completed, methanol was added to precipitate the polymer. Subsequently, the polymer was filtered, washed twice with methanol, and then dried under reduced pressure to obtain an amide group-containing chlorinated polypropylene having an amide group content of 2.2% by weight and a chlorine content of 41.0% by weight. Example 1 except that 8 g of the amide group-containing chlorinated polypropylene was used in place of the glycidyl group-containing chlorinated propylene-butene-1 copolymer.
An emulsion type adhesive composition was obtained in the same manner as in Example 0, and a heavy adhesion test and a flocking test were conducted.

〔Effect of the invention〕

The emulsion-type adhesive composition of the present invention can bond solid-state molded products made of highly crystalline resins such as polyolefin and nylon to any material without requiring a complicated surface treatment process. .

As is clear from the examples described above, the peel strength in the heavy adhesion test ranged from 0.65) tgf/cs to 2.35k when the emulsion type adhesive composition of the present invention was used.
gf/cm, which is 4 to 15 times higher than that of a known emulsion adhesive that does not contain the functional group-containing polyolefin according to the present invention.

Furthermore, when an adhesive composition obtained under conditions outside the scope of the present invention or an adhesive composition having a composition outside the scope of the present invention is used, the peel strength is significantly reduced.

Claims (1)

[Scope of Claims] 1. An emulsion type adhesive composition, in which the resin components include (1) 100 parts by weight of an adhesive synthetic resin, and (2) a carboxylic acid anhydride group, a carboxyl group, A polyolefin containing 0.01% to 20% by weight of one or more functional groups selected from a glycidyl group, a hydroxyl group, an amide group, and an alkoxysilyl group, and/or containing 0.0% of the functional group.
0.05 to 40 parts by weight of a hydrogenated block copolymer consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 1 to 20 parts by weight An emulsion type adhesive composition comprising , and. 2. The composition according to claim 1, wherein the adhesive synthetic resin is an adhesive synthetic resin whose main component is one or more resins selected from acrylic resins, styrene resins, and vinyl acetate resins. 3. A hydrogenated product of a block copolymer consisting of a polyolefin and/or at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block has an intrinsic viscosity [η] (tetralin at 135°C). 2. A composition according to claim 1, wherein the composition is 0.1 dl/g to 10 dl/g. 4. A hydrogenated product of a polyolefin containing a functional group and/or a block copolymer consisting of at least one aromatic vinyl compound polymer block containing a functional group and at least one aliphatic diene polymer block The composition according to claim 1, which is a polymer containing 70% by weight or less of chlorine in addition to the functional group. 5. In the method for producing an emulsion-type adhesive composition, (A) an aqueous emulsion of an adhesive synthetic resin, based on 100 parts by weight of the synthetic resin in the emulsion, (B) (1) a carboxylic acid anhydride group, a carboxyl 0.01% by weight of one or more functional groups selected from the group consisting of:
Consisting of a polyolefin containing ~20% by weight, and/or at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 0.01% to 20% by weight of the functional group. 0.05 parts by weight to 40 parts by weight of hydrogenated block copolymer,
and (2) an organic solvent. 6. The manufacturing method according to claim 5, wherein the adhesive synthetic resin is an adhesive synthetic resin whose main component is one or more resins selected from acrylic resins, styrene resins, and vinyl acetate resins. 7. Hydrogenated polyolefins and/or block copolymers consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block have an intrinsic viscosity [η] (tetralin at 135°C). 6. The manufacturing method according to claim 5, wherein the polymer has a concentration of 0.1 dl/g to 10 dl/g (measured in 100 dl/g). 8. A hydrogenated product of a polyolefin containing a functional group and/or a block copolymer consisting of at least one aromatic vinyl compound polymer block containing a functional group and at least one aliphatic diene polymer block The method according to claim 5, which is a polymer containing 70% by weight or less of chlorine in addition to the functional group.