JPH05214308A - Water-dispersible adhesive - Google Patents

Abstract

PURPOSE:To provide the subject adhesive having good adhesiveness to polyolefins, etc., and having excellent light stability by dispersing a specific chlorinated olefin copolymer and a semicarbazide group-containing compound in an aqueous dispersion medium. CONSTITUTION:(A) 100 pts.wt. of a chlorinated olefin polymer having a chlorine content of 15-40wt.% and produced by bringing an olefinic copolymer composed of (i) 15-90mol.% of propylene repeating units and (ii) 10-85mol.% of 4-6C alpha- olefin repeating units [the sum of the contents of the components (i) and (ii) is 100mol.%] and having an intrinsic viscosity [eta] of 0.5-5.0dl/g measured in decalin at 135 deg.C into contact with molecular oxygen at 70-90 deg.C and (B) 0.05-20 pts.wt. of a semicarbazide group-containing compound are dispersed in an aqueous dispersion medium to provide the objective adhesive containing 5-80wt.% of the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible adhesive, and more particularly to a water-dispersible adhesive having excellent adhesiveness with a polyolefin resin and excellent light resistance.

[0002]

[Background of the Invention] The interior of automobiles is becoming more and more luxurious year by year. ABS resin materials, vinyl chloride resin foams,
For example, a cloth made of polyester or polyamide resin is adhered, or a short fiber made of polyester or polyamide is adhered by flocking for flocking.

In the above-mentioned bonding work, the adhesive is generally applied and dried in an open place. The organic solvent cannot be used because it contaminates the working environment, and the water-dispersed adhesive is used. ing. As such an adhesive, a rubber latex or an acrylic acid ester resin aqueous dispersion has been generally used in the past (for example, JP-A-49-1129).
No. 90, No. 55-160073, No. 60-19998.
4 and 60-244534).

By the way, in automobile interior materials adhered with the above-mentioned adhesives, recently, improvement of heat resistance has been desired. Based on such a demand, instead of a normal ABS resin which is a base material of interior materials, , It is more necessary to use a resin with higher heat resistance than ordinary ABS resin. It is possible to use a heat-resistant ABS resin as such a heat-resistant resin, but when the heat-resistant ABS resin is used, the cost of the interior material increases and the formability deteriorates. So ABS
It is conceivable to use a polypropylene resin, which has physical properties similar to ABS resin and is inexpensive and has good moldability, instead of the resin. However, the polypropylene resin has poor adhesiveness and cannot be adhered by using a rubber latex or an acrylic ester resin water dispersion which has been conventionally used for the ABS resin. Therefore, when using the above-mentioned water dispersion that has been conventionally used as an adhesive, it is necessary to subject the surface of the polypropylene resin substrate to a primer treatment to improve the adhesiveness, and the polypropylene resin is inexpensive. However, the cost is higher than when using heat-resistant ABS resin.

Not only in the field of automobile interior materials using polypropylene resin, but in general, polyolefin resin has poor adhesiveness and ordinary adhesives cannot be used. Therefore, it is possible to perform adhesion without performing primer treatment and use an organic solvent. A water-dispersible adhesive that does not exist is desired. In order to solve the above problems, the present applicant has already applied for an invention of a water-dispersible adhesive containing a chlorinated polyolefin polymer water dispersion as an active ingredient (Japanese Patent Application No. 62-62-62). 33335
No. 3 specification (Japanese Patent Laid-Open No. 174579/1989).
This water-dispersed adhesive has good adhesion between the polyolefin resin and any material, does not require primer treatment on the surface of the polyolefin resin, and does not use an organic solvent, so it is safe and excellent. It is a water-dispersed adhesive having adhesive strength. By using this water-dispersed adhesive, it has become possible to bond a polyolefin resin molded product with any material, which has been difficult in the past.

However, upon further examination of this water-dispersed adhesive, it was found that there is a problem that the adhesive performance may be reduced in a short period of time depending on the usage environment of the molded product after the adhesion.

[0007]

OBJECT OF THE INVENTION It is an object of the present invention to provide a water-dispersible adhesive which has good adhesiveness to a polyolefin resin and is less likely to deteriorate in adhesive performance even after long-term use.

[0008]

SUMMARY OF THE INVENTION The water-dispersible adhesive of the present invention has a propylene repeating unit (a) content of 15 to 90 mol% and an C-C6 α-olefin repeating unit (b) content of 10%.
~ 85 mol% [total content of (a) and (b) is 100 mol%]
And the olefin copolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.5 to 5.0 dl / g was chlorinated to a chlorine content of 5 to 40% by weight. An olefin polymer and an aqueous dispersion containing 0.05 to 20 parts by weight of a compound having a semicarbazide group per 100 parts by weight of the chlorinated olefin polymer in an aqueous dispersion medium, and The aqueous dispersion contains a chlorinated olefin polymer in an amount of 5 to 80% by weight.

Since the water-dispersible adhesive of the present invention contains a specified amount of a chlorinated olefin polymer and a compound having a semicarbazide group, the light resistance of the adhesive is improved. Therefore, the water-dispersible adhesive of the present invention is unlikely to deteriorate in its adhesive performance even when used for a long period of time.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Next, the water-dispersible adhesive of the present invention will be specifically described. The water-dispersible adhesive of the present invention comprises an aqueous dispersion medium, a chlorinated olefin polymer contained in the aqueous dispersion medium, and a compound having a semicarbazide group. This chlorinated olefin polymer is a chlorinated product of an olefin copolymer composed of a propylene repeating unit (a) and a C4 to α6 olefin repeating unit (b).

Olefin Polymer As the α-olefin repeating unit (b) which is a repeating unit forming an olefin polymer with the propylene repeating unit (a) in the present invention, for example, 1-butene, 1-pentene, 4- Methyl-1-pentene, 3-methyl-1-pentene and
A repeating unit derived from an α-olefin having 4 to 6 carbon atoms such as 1-hexene can be mentioned. The olefin-based polymer may have a repeating unit derived from an α-olefin having 4 to 6 carbon atoms alone or in combination of two or more kinds.

Further, the olefin polymer is a conjugated diene such as butadiene and isoprene; 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene within a range that does not impair the effects of the present invention. Non-conjugated dienes such as -2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene and 2,5-norbonadier;
(Meth) acrylic acid, (meth) acrylic acid salt, (meth)
Acrylic ester, vinyl acetate, vinyl alcohol,
Polar vinyl monomers such as 1-undecylenic acid, 1-undecenol and maleic anhydride; repeat units derived from aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene and indene May be. When the conjugated diene or non-conjugated diene is contained as the α-olefin copolymerization component, the content is usually 3 mol% or less, preferably 0.3 mol%.
It is below. Further, the olefin-based polymer can contain a repeating unit derived from ethylene in an amount of 30 mol% or less in all copolymerization components.

Further, as the olefin polymer, a polymer obtained by graft-copolymerizing a polymerizable unsaturated compound such as acrylic acid, methacrylic acid or maleic anhydride to the olefin polymer composed of the above repeating units is used. May be. In the olefin polymer, the content of the propylene repeating unit (a) needs to be 15 to 90 mol%, and the content of the propylene repeating unit (a) is 2 or more.
It is preferably from 0 to 85 mol%. Also, carbon number 4
Content of the α-olefin repeating unit (b) of
The content of the α-olefin repeating unit (b) is preferably 15 to 80 mol%. In the present invention, the total content of the propylene repeating unit and (a) the α-olefin repeating unit having 4 to 6 carbon atoms (b) is 100 mol%.

When the content of the α-olefin repeating unit (b) exceeds 85 mol% (that is, when the content of the propylene repeating unit (a) is less than 15 mol%), the olefin polymer is The chlorinated olefin-based polymer obtained by chlorinating is insufficient in heat resistance adhesion, while
When the content of the α-olefin repeating unit (b) is less than 10 mol% (that is, when the content of the propylene repeating unit (a) is more than 90 mol%), a high chlorine content is required to impart adhesiveness. The content becomes necessary, and it tends to be inferior in terms of heat resistance and adhesiveness with polyolefin.

As such an olefin polymer,
Specifically, propylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 3-methyl-1-pentene copolymer, propylene / 1-butene / ethylene copolymer , Propylene / 1-butene / 1-undecylenic acid copolymer, propylene / 4-methyl-1-pentene / 1-
Undecylenic acid copolymer, propylene / 1-butene / 1-undecenol copolymer, propylene / 4-methyl-1-pentene / 1-undecene copolymer, propylene / 1-butene /
(Anhydrous) maleic acid copolymer, propylene / 1-butene /
(Anhydrous) itaconic acid copolymer, propylene / 1-butene /
Ethylene / (anhydrous) maleic acid copolymer, propylene /
1-butene / styrene copolymer, propylene / 3-methyl-1
-Butene / styrene copolymer, propylene / 4-methyl-1-
Examples thereof include a pentene / styrene copolymer and a propylene / 3-methyl-1-pentene / styrene copolymer. Among these, propylene / 1-butene copolymer and propylene / 1-butene / ethylene copolymer are particularly desirable.

The intrinsic viscosity [η] of these olefinic polymers measured at 135 ° C. in decalin was 0.5.
˜5.0 dl / g, preferably 0.8 to 4.0 dl / g. Intrinsic viscosity [η] of olefin polymer is 0.5 dl /
If it is less than g, the cohesive force of the adhesive is insufficient, so that the basic adhesiveness is insufficient, and if it exceeds 5.0 dl / g, the emulsifying property is lowered.
In addition, the molecular weight distribution (Mw / M
n, the value measured by the GPC method) is usually 1 to 20,
It is preferably in the range of 1 to 15. Molecular weight distribution (Mw /
When Mn) exceeds 20, the adhesive strength tends to decrease due to an increase in the content of low molecular weight substances in the olefin polymer.

Further, the crystallinity of the olefin polymer is usually in the range of 0 to 50%, preferably 0 to 50%.
Within the range of 30%. Further, if the crystallinity exceeds 50%, it is necessary to increase the chlorination rate to more than 40% by weight in order to impart good dispersibility to the aqueous dispersion medium.
The olefin-based polymer is likely to deteriorate, and the adhesiveness with the polyolefin tends to be further reduced.

Such a polyolefin polymer is produced, for example, by copolymerizing the above-mentioned propylene and α-olefins using a vanadium catalyst or a titanium catalyst containing magnesium, titanium, halogen or the like as a component. be able to. Chlorinated olefin-based polymer In the present invention, these olefin-based chlorinated products are used. The chlorine content introduced into the polyolefin-based polymer is in the range of 5 to 40% by weight in terms of the weight percentage of chlorine contained in the obtained chlorinated olefin-based polymer. Further, those having a chlorine content of 5 to 30% by weight are preferable, and those having a chlorine content of 6 to 28% by weight are particularly preferable. The adhesive performance of the water-dispersible adhesive of the present invention to the adherend is often dependent on this chlorine content. For example, when the material to be adhered is a general olefin polymer, sufficient adhesive strength is often not obtained unless the chlorine content is relatively high. On the other hand, when the chlorine-containing polymer or aromatic polymer is used, In some cases, sufficient adhesion is obtained even with a rather low chlorine content. Then, in order to develop good adhesiveness for various adherends, it is necessary to use a chlorinated olefin polymer having a chlorine content within the above range. That is, chlorinated products with relatively low chlorine content (chlorinated olefin-based polymers)
Heat-resistant adhesiveness under high temperature atmosphere that chlorine content of chlorine-containing polymer and / or aromatic polymer is less than 5% by weight Is reduced. Also, the chlorine content is 40% by weight
Using a chlorinated olefin-based polymer that exceeds more than not only reduces the adhesion with general polyolefins,
The heat resistant adhesiveness of the adhesive also decreases.

The chlorinated product of the olefin polymer can be produced by the following exemplified method. The first method is a method in which an olefin polymer is pulverized into fine particles, and the fine particles are brought into an aqueous suspension state and brought into contact with molecular chlorine at a temperature of about 70 to 90 ° C. The second method is to use an olefin polymer, carbon tetrachloride, tetrachloroethylene,
This is a method in which a uniform solution is prepared by dissolving it in a chlorine-stable solvent such as chloroform and chlorobenzene, and in this state, the olefin polymer and molecular chlorine are brought into contact with each other. In addition, the third method is to use N-chloroacetamide, N-chlorosuccinimide, and a chlorine compound such as 1,3-dichloro-5,5-dimethylhydantoin as an olefin polymer by using a roll or a Banbury mixer. It is a method of uniformly kneading in the mixture, and then heating the obtained kneaded product to a temperature at which chlorine is liberated. Among these, it is particularly preferable to employ the chlorination method in an aqueous suspension state or a solution state. When the halogenation reaction is carried out in a solution state, it is more preferable to carry out the halogenation reaction in the presence of water or a radical initiator or under the irradiation of ultraviolet rays and / or visible rays because the chlorination reaction proceeds efficiently. is there. The degree of chlorination can be adjusted by appropriately selecting the amount of molecular chlorine or other chlorinating agent used, the reaction time, the reaction temperature and the like.

In the present invention, the chlorinated olefin polymer has a crystallinity of usually 45% or less, further 30%.
It is preferable to use a chlorinated olefin-based polymer of 10%. The intrinsic viscosity [η] of the chlorinated olefin polymer is usually in the same range as that of the raw material olefin polymer, but is preferably 0.6 to 4.0 dl.
/ g.

Light Stabilizer The water-dispersible adhesive of the present invention contains a compound having a semicarbazide group. By compounding this compound having a semicarbazide group, the semicarbazide group acts as an actinic ray protective group having a shielding effect in the ultraviolet region, and thus the light resistance stability of the adhesive of the present invention is improved. Specific examples of the compound having this semicarbazide group include
1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,6-hexamethylenebis (N, N-diethylsemicarbazide), xylylene-bis (dimethylsemicarbazide), isophorone-bis (dimethylsemicarbazide) and 1, Examples thereof include 1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-p-phenylene) disemicarbazide. Among these, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) is a particularly desirable compound.
The compounds having these semicarbazide groups can be used alone or in combination.

The compound having a semicarbazide group is 0.05 to 20 parts by weight, preferably 0.1 to 18 parts by weight, and more preferably 0 to 100 parts by weight of the chlorinated olefin polymer (resin solid content). Used in an amount of 0.1 to 10 parts by weight. If the amount used is less than 0.05 parts by weight, the improvement of the light resistance stability is insufficient, and if it exceeds 20 parts by weight, the adhesive strength of the adhesive of the present invention decreases.

Water Dispersion The chlorinated olefin polymer and the compound having a semicarbazide group are contained in an aqueous dispersion medium.
Although water is used as the aqueous dispersion medium, a small amount of a hydrophilic organic compound such as alcohol may be contained in the aqueous dispersion medium.

The water-dispersible adhesive of the present invention contains the chlorinated olefin polymer in a solid content of 5 to 80% by weight, preferably 15 to 70% by weight. And
The compound having a semicarbazide group has a solid content of 0.1.
It is contained in the aqueous dispersion medium in an amount of 1 to 20 parts by weight.
Since both of them have low solubility in the aqueous dispersion medium, most of them are usually dispersed in the aqueous dispersion medium in a granular form. The particle size of this dispersion can be arbitrarily selected within a range where it is stable in water, but it is generally 0.01 μm to 30 μm, preferably 0.1 μm.
It is about 05 μm to 10 μm.

The water-dispersible adhesive of the present invention contains the chlorinated olefin polymer and the semicarbazide light-resistant stabilizer as essential components as described above, but other polymer components and antioxidants may be used as long as the adhesiveness is not impaired. It contains additives such as UV absorbers, hydrochloric acid absorbers, dehydrochlorination agents, pigments, dyes, fillers (materials), nucleating agents (materials), antiblocking agents, slip agents, antistatic agents and flame retardants. But it doesn't matter.

As the polymer to be blended with the chlorinated olefin polymer, other than the olefin polymer before chlorination,
Examples of the rubber component include ethylene / α-olefin copolymer, ethylene / α-olefin / diene copolymer rubber, polyisobutylene, butyl rubber, styrene / butadiene copolymer rubber, nitrile rubber and silicone rubber.

As the antioxidant, 2,6-di-tert-butyl is used.
-p-cresol, o-tert-butyl-p-cresol, tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, β-naphthylamine and p-phenylenediamine Etc. can be illustrated. As the ultraviolet absorber, 2,4-dihydroxybenzohenone, 2- (2'-dihydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy- Examples include 3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, bis (2,2 ′, 6,6′-tetramethyl-4-piperidine) sebacate, and the like.

Examples of hydrochloric acid absorbents and dehydrochlorinating agents include epoxy soybean oil, higher fatty acids such as stearic acid, and unsaturated higher fatty acid metal salts (eg, dibutyltin malate, tribromophosphate, tetrasodium). Examples thereof include diamyl pyrophosphate, 4'-tert-butylphenyl salicylate, disodium-o-phosphate; alkali metal pyrophosphate, o-phosphate or phosphite).

In order to disperse the above chlorinated olefin polymer or the composition containing it in water, it is preferable to add an emulsifier. Further, a thickener for increasing the viscosity of the emulsion, or an antifoaming agent for suppressing foaming during emulsification may be added. A surfactant is used as the emulsifier, and examples thereof include an alkylnaphthalene sulfonate, a Na salt of a naphthalene sulfonic acid formaldehyde condensate, and a Na of a cresol-schaferic acid formaldehyde condensate.
Salt, alkyl diphenyl ether disulfonic acid Na salt,
Lignin sulfonic acid Ca salt, melanin resin sulfonic acid N
Sulfonic acid or carvone such as a salt, special polyacrylic acid salt, gluconate, olefin / maleate copolymer, carboxymethyl cellulose Na salt, metal soap (Zn, Al, Na, K salt) and stearic acid triethanolamine salt Acid type anionic surfactant; fatty acid monoglyceride, sorbitan fatty acid partial ester, sugar fatty acid partial ester, polyglycerin fatty acid partial ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester, Polyoxyethylene sorbitol fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene fatty amine, polyoxyethylene (hardened) castor oil, polyoxyethylene Nonionic surfactants such as glycol glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, hydroxyethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone and methyl cellulose; and cations such as alkylammonium chloride, trimethylalkylammonium bromide and alkylpyridinium chloride. Ionic surfactants; amphoteric surfactants such as dimethylalkyl betaine and alkylglycine, and the like.

The amount of the emulsifier added is usually 0.1 to 50 parts by weight, preferably 0.2, based on 100 parts by weight of the resin solid content.
It is about 45 parts by weight. Examples of the thickener include water-soluble polymers such as carboxymethyl cellulose, methyl cellulose, sodium polyphosphate, polyvinyl alcohol, sodium polyacrylate, ammonia milk casein, vinyl alcohol / methacrylic acid copolymer, starch and protein. The thickener can be added generally up to 200 parts by weight with respect to 100 parts by weight of the resin solid content, but is preferably 100 parts by weight or less.

As a method for dispersing the chlorinated olefin polymer and the compound having a semicarbazide group (these may be a composition) in an aqueous dispersion medium, the chlorinated olefin polymer and the compound having a semicarbazide group ( (Semicarbazide light resistance stabilizer) and then dispersed in water, and a method in which a chlorinated olefin polymer is dispersed in water and then an aqueous dispersion of a semicarbazide light resistance stabilizer is mixed.

Specifically, a method of directly dispersing a composition containing a chlorinated olefin polymer in water in a powder state, raising the temperature to melt the composition containing a chlorinated olefin polymer, and immersing the composition in water under high stirring. Examples thereof include a method of dispersing and a method of chlorinating an olefin polymer in an aqueous suspension state to form an aqueous dispersion, but any method can be adopted.

In particular, the water-dispersible adhesive of the present invention contains a chlorinated olefin polymer and a compound having a semicarbazide group or a composition containing them in an amount of 10 to 50% by weight in an organic solvent such as benzene or toluene. Dissolved in water and added to water with a hydrophilic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol and an emulsifier,
It is preferable to produce the emulsion by stirring with a homomixer or the like to obtain an emulsion, and then removing the organic solvent and hydrophilic solvent under reduced pressure with an evaporator or the like. The organic solvent may remain in the thus obtained aqueous dispersion as long as it is not dangerous.

Acrylic ester-based polymer An aqueous dispersion containing the above-mentioned chlorinated olefin-based polymer and a compound having a semicarbazide group can be used alone as an adhesive, but this aqueous dispersion is conventionally used as an adhesive. By mixing the used acrylic acid ester-based polymer, the adhesive effect can be further enhanced. The acrylic ester polymer is usually mixed in the form of an aqueous dispersion.

Such an acrylic acid ester polymer aqueous dispersion may be an aqueous dispersion of a polymer containing a (meth) acrylic acid ester repeating unit, for example, an acrylic acid ester and / or a methacrylic acid ester. 50 to 98.5 parts by weight, ethylenically unsaturated acid 0.5 to 5 parts by weight, N-methylolacrylamide and / or its alkoxylated derivative 1 to 10 parts by weight, and other vinyl type copolymerizable with them. Acrylic ester polymer emulsion (see JP-A-55-160073) obtained by polymerizing 0 to 55 parts by weight of a monomer in an aqueous medium, 30 to 70 parts by weight of vinyl chloride monomer, and 1 to 3 carbon atoms. 10-55 parts by weight of alkyl acrylate ester of alcohol, 10-50 parts by weight of vinyl acetate monomer, and vinyl monomer containing carboxyl group. 10 parts by weight, and an epoxy group, a hydroxyl group, N- methylol amide group, vinyl monomers having a crosslinkable functional group such as N- alkoxymethyl amide 0
Resin emulsions obtained by emulsion-copolymerizing 5 to 5 parts by weight (see JP-A-49-112990) and the like can be mentioned.

Further, such an acrylic ester polymer aqueous dispersion may be a commercially available product, and preferred examples of the commercially available product are styrene / acrylonitrile / ethylhexyl acrylate / ethyl acrylate / acryl. Acid-n-butyl copolymer (molar ratio 35/35 /
13/15/7) aqueous dispersion (trade name: iodosol, manufactured by Kanebo NSC Co., Ltd.).

When using these acrylic ester polymer aqueous dispersions, the chlorinated olefin polymer-containing composition and the water dispersion (A) of the compound having a semicarbazide group and the acrylic ester polymer are used. The blending ratio of the water dispersion (B) is 10 to 100% by weight of (A), preferably 20 to 100% by weight, particularly preferably 20 to 95% by weight, and (B) 0 to 90% by weight, preferably 0 to 100% by weight. 80% by weight, particularly preferably 5 to 80% by weight.

Usage of Adhesive The water-dispersible adhesive of the present invention is applied to the adhesive surface in the same manner as the conventional water-dispersed adhesive, and dried by heating if necessary for adhesion. The water-dispersible adhesive of the present invention is suitable for adhering polyolefin resins such as polyethylene resin and polypropylene resin, which have been difficult to adhere to in the past, and is effective for adhering polyolefin resins or polyolefin resins and other materials. Other materials include any material such as cloth, fibers, plastic, paper, metal, and the like.

As the cloth or fiber, natural fibers such as cotton and hemp, glass fiber and carbon fiber,
Inorganic fibers such as asbestos fibers and metal fibers, regenerated fibers such as viscose rayon and cupra, semi-synthetic fibers such as di- and tri-acetate fibers, nylon 6 fibers, nylon 66 fibers, polyester (polyethylene terephthalate) fibers , Aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers, and cloth, short fibers and long fibers of synthetic fibers such as insolubilized or sparingly soluble polyvinyl alcohol fibers. In the case of short fibers, it can be applied to adhesion by flocking.

Examples of plastics include polyvinyl chloride resin, ABS resin, polyester resin, polyamide resin, polycarbonate resin, and epoxy resin, in addition to polyolefin resin, and their shapes include sheets, films, and other molded products. It becomes the target of adhesion. The adhesive of the present invention is suitable for adhering polyolefin resins, but can be used for other materials.

[0041]

EFFECT OF THE INVENTION The adhesive of the present invention exhibits good adhesiveness to a polyolefin resin without treatment such as primer treatment. Moreover, the adhesive of the present invention is water-dispersible, does not require the use of an organic solvent, and is excellent in safety. Further, even when used for a long period of time, its excellent adhesive performance is hardly deteriorated.

[0042]

EXAMPLES Hereinafter, the water-dispersible adhesive of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0043]

Example 1 A propylene / 1-butene (70/30 mol%) copolymer having an intrinsic viscosity [η] of 2.0 dl / g was chlorinated by a conventional method. As a result of analysis by the oxyfuel combustion method, the chlorine content was 21% by weight. Toluene solution 40 in which 20% by weight of this chlorinated product is dissolved in toluene
0 g, ion-exchanged water 300 g, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) (compound having a semicarbazide group, trade name: HN-130, manufactured by Nippon Hydrazine Industry Co., Ltd., simply referred to as “semicarbazide light resistance Stabilizer "
2.4 g, isopropyl alcohol 180 g, oleic acid 2.2 g, potassium hydroxide 0.1 g.
5 g was charged into a reactor having a capacity of 1.5 liter and stirred for 5 minutes using a homomixer to obtain an emulsion.

Then, isopropyl alcohol and toluene were distilled off while heating under reduced pressure with an evaporator,
An aqueous dispersion (water-dispersible adhesive) having a solid content of 21% by weight was obtained. The water-dispersed adhesive obtained as described above by spraying on the surface of an injection plate made of polypropylene (trade name: J-640, manufactured by Mitsui Petrochemical Industry Co., Ltd.) is adjusted to 200 g / m ^2. After application, a cloth was placed on this and lightly pressed by hand, and then dried in an air oven at 100 ° C. for 30 minutes.

After 1 hour of drying, 5 using a tensile tester
When a 180 ° C. peel test was conducted at a pulling speed of 0 mm / min, a peel strength of 2.9 kg / 4 cm was exhibited. Separately, after applying a water-dispersed adhesive to the surface of a polypropylene injection plate, use a simple flocking device made by ERNST ROEDERSTEIN GM BH to plant short fibers made of nylon 6 with a length of 1.0 mm and 3 denier. Then, it was further dried in an air oven at 80 ° C. for 30 minutes to prepare a plurality of test pieces.

This test piece was held in a fade meter at a black panel temperature of 83 ° C. The flocked portions of the test piece held for 200 hours and the test piece held for 400 hours were scratched with nails, and the presence or absence of peeling of the pile was confirmed. Both of the test pieces had no peeling of the pile and showed good light resistance stability. The results are shown in Table 1.

[0047]

Example 2 An aqueous dispersion of the chlorinated polyolefin polymer prepared in Example 1 was mixed with styrene / acrylonitrile /
Ethyl hexyl acrylate / ethyl acrylate / n-butyl acrylate copolymer (molar ratio 35/35/13 /
15/7) water dispersion (trade name: Yodozole, Kanebo)
NSC Co., Ltd.) was added so that the solid content ratio was 60/40 (weight ratio), and a peeling test and a light resistance test were performed in the same manner as in Example 1.

The peel strength was 4.5 kg / 4 cm, and there was no peeling of the piles of the test pieces held in the fade meter for 200 hours and 400 hours. The results are shown in Table 1.

[0049]

Comparative Example 1 As shown in Table 1, an aqueous dispersion was obtained in the same manner as in Example 1 except that the semicarbazide light resistance stabilizer was not added. A test and a light fastness test were performed. The results are shown in Table 1.

[0050]

Comparative Example 2 As shown in Table 1 in Example 2, an aqueous dispersion was obtained in the same manner as in Example 1 except that the semicarbazide light-resistant stabilizer was not added. A test and a light fastness test were performed. The results are shown in Table 1.

[0051]

Comparative Example 3 In Example 2, as shown in Table 1, bis (2,2′6,6′-tetramethyl-), which is a light stabilizer other than the semicarbazide type light stabilizer, instead of the semicarbazide type light stabilizer.
4-piperidine) sebacate (trade name: SANOL LS-7)
No. 70, manufactured by Sankyo Co., Ltd.) was used to obtain an aqueous dispersion in the same manner. Using this, a peeling test and a light resistance test were performed in the same manner as in Example 1. The results are shown in Table 1.

[0052]

Comparative Example 4 In Example 2, as shown in Table 1, an aqueous dispersion of an α-olefin polymer before being chlorinated without using a chlorinated polyolefin polymer and a semicarbazide light resistance stabilizer. Then, a peeling test and a light resistance test were performed in the same manner as in Example 1 using the above. The results are shown in Table 1.
Shown in.

[0053]

Comparative Example 5 As shown in Table 1 in Example 2, an aqueous dispersion of an α-olefin polymer before being chlorinated was obtained without using the chlorinated polyolefin polymer, and this was used. Then, a peeling test and a light resistance test were performed in the same manner as in Example 1. The results are shown in Table 1.

[0054]

Examples 3 and 4 Water dispersion was carried out in the same manner as in Example 2 except that the composition ratio of the chlorinated olefin polymer / acrylic acid ester polymer / semicarbazide light stabilizer was changed as shown in Table 1. A mold adhesive was obtained, and using this, a peeling test and a light resistance test were conducted in the same manner as in Example 1. The results are shown in Table 1.

[0055]

[Table 1]

Front page continued (72) Inventor Koji Yoshii, 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Initiator Inagaki Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Mitsui Petrochemical Co., Ltd. (72) Inventor Masashi Iwakiri 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (72) Inventor, Sato Toyohashi Kasuga Town, Nishikasugai County, Aichi Prefecture 1 Ochiai, Nagahata, Toyoda Gosei Co., Ltd.

Claims (3)

[Claims] 1. The content of propylene repeating unit (a) is 15 to 90 mol%, and the content of α-olefin repeating unit (b) having 4 to 6 carbon atoms is 10 to 85 mol% [(a) and ( The total content of b) is 100 mol%] and 1 in decalin
A chlorinated olefin-based polymer obtained by chlorinating an olefin copolymer having an intrinsic viscosity [η] measured at 35 ° C. of 0.5 to 5.0 dl / g in a chlorine content of 5 to 40% by weight. , Based on 100 parts by weight of the chlorinated olefin-based polymer
5 to 20 parts by weight of a compound having a semicarbazide group is an aqueous dispersion containing an aqueous dispersion medium, and the chlorinated olefin polymer is 5 to 80% by weight in the aqueous dispersion.
An aqueous dispersion-type adhesive, characterized in that it is contained in an amount of. 2. The α-olefin repeating unit (b) having 4 to 6 carbon atoms comprises 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene and 1-hexene. The water-dispersible adhesive according to claim 1, which is a repeating unit derived from at least one α-olefin selected from the group. 3. The water-dispersible adhesive according to claim 1 or 2, wherein the water-dispersible adhesive further contains an acrylic acid ester polymer.