JPH0337288A - 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, a hydrogenated product of a specified block copolymer and a light stabilizer. CONSTITUTION:A water-based emulsion of 100pts.wt. (hereinbelow described as pts.) (solid content) adhesive synthetic resin (A) wherein a resins selected from among acrylic, styrenic and vinyl acetate resins is a main component and a soln. (B) consisting of 0.05-40pts. hydrogenated product of a block copolymer (a) consisting of a polyolefin with an inherent viscosity (135 deg.C in tetraline) of 0.1-10dl/g contg. 0.01-70wt.% functional group selected from among carboxylic anhydride, COOH, glycidyl, OH, amide and alkoxysilyl groups and Cl and/or an arom. vinyl compd. block and an aliph. diane polymer block and 0.1-20 pts. light stabilizer (b) which is pref. a mixture of an ultraviolet absorber and a hindered amine type radical trapping agent based in 100 pts. resin component of the sum of the components A and (a) and an org. solvent (c) 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 adhesive composition with excellent light resistance 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 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.

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 molded article of a highly crystalline resin such as polyolefin or nylon to any material is significantly improved.

[Problem to be solved by the invention]

By using the adhesive of the prior invention, it has become possible to bond high-crystalline resin molded products with any material, which was difficult in the past. Depending on the environment in which it is used, it has had the problem of poor light resistance to sunlight.

The purpose of the present invention is to
It is possible to bond molded products of highly crystalline resin such as polyolefin and nylon to any material while in a solid state.
Another object of the present invention is to provide an emulsion adhesive composition that has excellent light resistance and a method for producing the same.

[Means to solve the problem]

The present inventors have conducted extensive research into adhesives that solve the problems of the prior invention. As a result, it was found that light resistance was improved by adding a light stabilizer to the adhesive of the prior invention, and that a monomer containing chlorine and capable of radical polymerization was grafted instead of the chlorinated polyolefin. I learned that using polymerized polyolefins can further improve light resistance and storage stability, and that introducing various functional groups instead of chlorine can have similar effects on adhesive properties. The invention has been completed.

The present invention has the following configuration.

(1) An emulsion 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, or an alkoxysilyl group. and/or a polyolefin containing 0.01% to 70% by weight of one or more functional groups selected from chlorine and chlorine.
Hydrogenated block copolymer consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 0.01% to 70% by weight 0.05 to 40 parts by weight An emulsion adhesive composition further comprising: (1) 0.1 to 20 parts by weight of a light stabilizer based on 100 parts by weight of the total resin components (1) and (2).

(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) from 0°1 di/lr to 10 dl/g
The composition according to (1) above, which is a polymer of

(4) A hydrogenated product of a block copolymer consisting of a polyolefin containing a functional group and/or at least one aromatic vinyl compound polymer block containing a functional group and at least one aliphatic diene polymer block. ,
The composition according to (1) above, which is a polymer obtained by graft polymerizing 60% by weight or less of a radically polymerizable monomer in addition to the functional group.

(5) The composition according to (1) above, which uses an ultraviolet absorber and a hindered amine radical scavenger as the light stabilizer.

(6) In the method for producing an emulsion adhesive composition, (A) an aqueous emulsion of an adhesive synthetic resin is added with (B) (2) a carboxylic acid anhydride group, One or more functional groups selected from carboxyl group, glycidyl group, hydroxyl group, amide group, alkoxysilyl group, and chlorine at 0.01
polyolefin containing from % to 70% by weight, and/
or a hydrogenated block copolymer consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 0.01% to 70% by weight of the functional group. 05 parts by weight to 40 parts by weight; and based on 100 parts by weight of the total resin component of (1) and (2), (1) 0.1 parts by weight to 20 parts by weight of a light stabilizer, and (2) an organic solvent. A method for producing an emulsion adhesive composition, which comprises adding a solution.

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

(8) 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). The manufacturing method according to (6) above, wherein the polymer has a molecular weight (measured in tetralin) of 0.1 dj7/g to 10 dl/g.

(9) 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. (6) above, which is a polymer obtained by graft polymerizing 60% by weight or less of a radically polymerizable monomer in addition to the functional group.
The manufacturing method described in.

(lO) The production method according to (6) above, wherein an ultraviolet absorber and a hindered amine radical scavenger are used as the light stabilizer.

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, 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 - for boat fishing, the polymerization temperature is 3.
0℃~90℃, polymerization pressure is atmospheric pressure~50 kg/c
It is obtained by emulsion polymerization under dG conditions for about 1 to 20 hours.

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, heptyl 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, α-methylstyrene, vinyltoluene, hydroxystyrene, etc. ,1,3-
Dienes such as butadiene, isoprene, chloroprene, 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 polymerization initiators 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 vinyl monomer volume used, depending on the arbitrary material to be bonded.

Just choose the most suitable one. 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. Aqueous emulsion type adhesives are preferably used.

The second resin component of the emulsion adhesive composition of the present invention contains one or more functional groups selected from carboxylic anhydride groups, carboxyl groups, glycidyl groups, hydroxyl groups, amide groups, alkoxysilyl groups, and chlorine. 0.01% by weight
consisting of a polyolefin containing ~70% by weight, and/or at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 0.01% to 70% by weight of the functional group. Hydrogenated block copolymers (hereinafter sometimes abbreviated as functional group-containing polyolefins, etc.) are polyolefins and/or at least one polyolefin obtained by a known method.
A hydrogenated product of a block copolymer (hereinafter sometimes abbreviated as polyolefin, etc.) consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block has the above-mentioned functional groups. This is a resin component that incorporates. There are various methods for introducing the functional group other than chlorine into polyolefin, etc., but an easy method is to graft-polymerize a vinyl monomer having the functional group to polyolefin or the like. That is, a vinyl monomer having the above-mentioned functional group is prepared by dissolving a polyolefin 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. A method of graft polymerization under temperature conditions of 30° C. to 200° C., or a method of adding a polymer and carrying out graft polymerization under a temperature condition of 30° C. to 200° C., or a method of adding a radical initiator,
It can be obtained by a known method such as a method in which a vinyl monomer having a functional group as described above is fed to an extruder and graft polymerized. In addition, chlorine can be introduced into polyolefins etc. in a state in which the polyolefins etc. are dissolved in a solvent such as tetrachloroethane, in an aqueous suspension, or in a gas phase at a reaction temperature of 3.
Under conditions of 0°C to 120°C and a pressure of atmospheric pressure to 10 kg/dG, chlorine gas is added, and if necessary, means to increase reaction efficiency such as the use of a radical initiator or ultraviolet irradiation are used. A known method such as carrying out a chlorination reaction for 1 to 10 hours is used.

It is possible to introduce not only one type of functional group but also two or more types, and a combination of chlorine and a functional group other than chlorine is particularly preferred from the viewpoint of adhesiveness and storage stability. On this occasion,
The introduction of chlorine may be carried out either before or after the graft polymerization step in which a functional group other than chlorine is introduced into the polyolefin or the like, or it may be carried out during the graft polymerization. In addition, when a chlorination reaction is performed before introducing a functional group other than chlorine into polyolefin, etc., an active group capable of reacting with chlorine, such as mercapto, is used instead of a vinyl monomer having a functional group other than chlorine. In the presence of an acid acceptor or a radical initiator, a compound having a group, an amino group, etc. and the aforementioned functional group, specifically γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. It is also possible to conduct a reaction to introduce functional groups other than chlorine.

The content of functional groups in the functional group-containing polyolefin etc. is preferably 0.01% by weight to 70% by weight.

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

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 stereoregularity;
For example, polypropylene, propylene-α-olefin copolymer, polyethylene, ethylene-α-olefin copolymer, poly4-methylpentene-1,4-methylpentene-1-α-olefin copolymer, etc. Hydrogenation of a block copolymer having at least one polymer block of an aromatic vinyl compound such as styrene or α-methylstyrene, and at least one polymer block of an aliphatic diene such as butadiene or isoprene, obtained by the method. Specific examples include hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and hydrogenated styrene-butadiene-styrene block copolymer. 7. In addition to ethylene, propylene, and 4-methylpentene-1, the α-olefins used for copolymerization with propylene and the like include linear olefins such as butene-1, hexene-1, and octene-1. , 2-methylpentene-1, and other branched olefins; and butadiene, isoprene, and other dienes.

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. , intrinsic viscosity [η) (measured in tetralin at 135°C, same hereinafter) is 0. 1dl/lr~10dII/g
Polyolefins such as: are preferably used. One or more types of these polyolefins are used.

As described above, a functional group-containing polyolefin or the like can be obtained by subjecting the above-mentioned polyolefin or the like to a chlorination reaction or graft polymerization with a vinyl monomer having a functional group. Vinyl monomers having functional groups other than chlorine used in the production of polyolefins containing functional groups include functional groups such as carboxylic anhydride groups, carboxyl groups, glycidyl groups, hydroxyl groups, amide groups, and alkoxysilyl groups. Vinyl monomers having one or more types that can be graft-polymerized include maleic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, glutaconic anhydride, nadic anhydride, and methylnadic anhydride. , vinyl monomers having carboxylic acid anhydride groups such as tetrahydrophdaric anhydride, methyltetrahydrophthalic anhydride, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, glutacone Acids, vinyl monomers with carboxyl groups such as nadic acid, methylnadic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, methylglycidyl methacrylate, allyl glycidyl ether Vinyl monomers with glycidyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc., vinyl monomers with hydroxyl groups such as acrylamide, N-methylolacrylamide , vinyl monomers having an amide group such as N-butoxymethylacrylamide, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethylethoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane, allyltrimethoxysilane Ethoxysilane, γ-
Contains an alkoxy group such as methacryloxytrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, etc. Vinyl monomers, etc.

One or more types of these monomers are used. In addition to vinyl monomers or chlorine having these functional groups, 60
It is also a preferred embodiment of the present invention to introduce other monomers, such as acrylic esters and methacrylic esters, into polyolefins etc. by graft polymerization in a content of less than % by weight. be. These monomers that can be introduced can be used simultaneously during the chlorination reaction or during the graft polymerization of monomers having functional groups other than chlorine, or can be used for graft polymerization during the chlorination reaction or the graft polymerization of monomers having functional groups other than chlorine. It is also possible to carry out graft polymerization in the presence of a radical initiator before or after graft polymerization of the monomers.

As the radical initiator used in the production of functional group-containing polyolefin, etc., there may be mentioned those similar to those used in the production of the adhesive synthetic resin emulsion described above, but organic peroxides are particularly preferred. . Specifically, benzoyl peroxide, dicumyl peroxide, di-t
-butyl peroxide, lauroyl peroxide,
2,5 dimethyl-2,5-di(t-butylperoxy)
Examples include hexyne-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane.

The functional group-containing polyolefin, which is the second resin component of the emulsion adhesive composition of the present invention, is obtained as described above.

The emulsion adhesive composition of the present invention essentially requires the above two components as a synthetic resin component, and the proportion of each component used is such that the 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 adhesive composition of the present invention is an aqueous emulsion that essentially contains a light stabilizer in addition to the synthetic resin component having the composition described above.

As the light stabilizer used in the present invention, known light stabilizers having functions of preventing photodeterioration of polymer compounds, such as ultraviolet absorption, radical scavenging, and excitation energy absorption, can be used. To give specific examples, examples of the ultraviolet absorber include phenyl salicylate, pt-butyl salicylate, p-octylphenyl salicylate, phenyl-3-phenyl salicylate, 2.6-dimethylphenyl salicylate, and 2.6-dimethyl phenyl-5-butyl salicylate, 2,6-dimethyl-4-octadecylphenyl salicylate, 2,6-dimethylphenyl 4-dodecyloxysalicylate, 2-dodecyl 4-methylphenyl salicylate, p-octylphenyl-5-octylsalicylate) , satsushilates such as pt-butylphenyl-4-dodecyclooxysalicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4
-hydroxy-2-methoxyphenyl)methane, 2.2
'Dihydroxy-4-methoxybenzophenone, 2.2
'-dihydroxy-4,4'-dimethoxybenzophenone, 2.2',4.4'-tetrahydroxybenzophenone, 4-dodecyloxy2-hydroxybenzophenone, 2-hydroxy-4-methoxy-2'-
Benzophenones such as carboxybenzophenone, 2-
(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'
, 5'-bis(α.

α′-dimethylbenzyl)phenyl]benzotriazole, 2-(2′-hydroxy-3′ 5′-di-t-butylphenyl)benzotriazole, 2-(2
'-Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(
2'-hydroxy-3'5'-di-t-amyl)benzotriazole,2-(2'-hydroxy-5
'-t-octylphenyl)benzotriazole, 2
．． 2'-Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] Methyl-3-(3-t-butyl-5-(2H -benzotriazol-2-yl)4
-Hydroxyphenyl]propionate/polyethylene glycol condensate, 2-(2-hydroxy-3-allyl-5-methylphenyl)benzotriazole/dibutyl maleate copolymer, 2-(2-hydroxy-3-allyl-5-methyl) benzotriazole-based products such as phenyl)benzotriazole/dicyclohexyl maleate copolymer,
Ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, butyl-2-cyano-3-methyl-
Cyanoacrylates such as 3-(p-methoxyphenyl)acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'
-Various ultraviolet absorbers such as oxalic acid anilide such as ethyl oxalic acid bisanilide. In addition, as a radical scavenger, 4-benzoyloxy-2,2゜6.6-titramethylpiperidine, bis(2,2゜6.
6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-
hydroxybenzyl)-2n-butylmalonate bis(1
,2,2,6,6=pentamethyl-4-piperidyl),
Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, bis(2,2゜6.6-tetramethyl-4-piperidyl)◆di(tridecyl)-1,2,3,
4-Butanetetracarboxylate, tris(2,2,
6,6-tetramethyl-4-piperidyl) mono(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-
piperidyl) di(tridecyl)-1゜2.3.4-butanetetracarboxylate, tris(1,2,2,6
, 6-tetramethyl-4piperidyl) mono(tridecyl)-1,2,3°4-tetracarboxylate, 3.
9-bis[1゜1-dimethyl-2-[tris(2,2,
6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy]ethyl]-2,4,8,
10-tetraoxaspiro(5,5)undecane, 3.
9-bis[1,1-dimethyl-2-[tris(1,2,
2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy]ethyl)-2,4,
8,10-tetraoxaspiro(5,5)undecane,
N-(2,2,6°6-tetramethyl-4-piperidyl)dodecylsuccinimide, 1-2(-hydroxyethyl-2°2.6.6-tetramethyl-4-piperisinol/dimethyl succinate) Condensate, 2-t-octylamino-4,6-dichlorotriazine/N,N'-bis(2
, 2,6,6-tetramethys-4-bisulidyl)hexamethylenediamine polycondensate, 1°6-bis(2,2,6
, 6-tetramethyl-4-piperidylamino)hexane/dibromoethane, and other hindered amine-based radical scavengers. Further, as a quencher that absorbs excitation energy, nickel dibutyl-dithiocarbamate, nickel-bis(octylphenyl)sulfide, (2,2'-thio-bis(4-t-octylaminol)))-n-butylamine- Nickel, (2,2
' -thio-bis(4-t-octylphenolate)
] -] Nickel-based quenchers such as 2-hexylamine-nickel 2.2'-thio-bis(4-t-octylphenolate)-triethanolamine-nickel, and the like. One or more types of these light stabilizers can be used, but particularly preferred results can be obtained by using a combination of an ultraviolet absorber and a hindered amine radical scavenger.

The amount of the light stabilizer used is 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the resin component, which is the total of the adhesive synthetic resin component and the functional group-containing polyolefin. If the amount used is less than 0.1 part by weight, the improvement in photostability will be insufficient, and if it exceeds 20 parts by weight, the adhesiveness will decrease.

The emulsion adhesive composition of the present invention requires the above-mentioned resin component and light stabilizer, and the following method is shown as a manufacturing method.

That is, it can be obtained by adding a solution consisting of (B) (2) a functional group-containing polyolefin, etc., (2) a light stabilizer, and (2) an organic solvent to the aqueous emulsion of (A) (2) adhesive synthetic resin described above. If no organic solvent is used, the resulting adhesive will have insufficient adhesive strength. There is no particular limit to the amount of organic solvent used 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. Regarding the light stabilizer, there are two methods: adding the light stabilizer first into the aqueous emulsion of (A), or adding the light stabilizer after adding the components from the solution of (B), excluding the light stabilizer, to (A). Although this method is also possible,
The method of adding the above-mentioned (B) in a dissolved form in the solution is
Preferable in terms of dispersibility.

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

In addition, synthetic resins such as petroleum resins and amino resins, and stabilizers other than light stabilizers may be added to this solution in amounts that do not impede the performance of the adhesive composition of the present invention. It is also possible to further add a surfactant or an aqueous solution thereof, mix it, and then 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 aqueous emulsion type adhesive in advance, it is possible to maintain a stable emulsion state even after the solution is added.

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 adhesive composition is set to 1.
Approximately 0% to 65% by weight, viscosity is 100cps to 30%
．． It is preferable to set it in the range of about 000 cps. Also,
If a relatively large amount of organic solvent is used during manufacturing,
It is also possible to remove a desired amount of the organic solvent by distilling the obtained emulsion under reduced pressure at a temperature of about room temperature to 80°C.

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 or nylon, and for surface decoration such as flocking of the molded products. used for. 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 limited in any way by this example. The initial adhesion was confirmed by a heavy adhesion test, and the light resistance was confirmed by a flocking double-light test using the methods described below.

(1) Heavy adhesion test ■ Test material Polypropylene injection molded piece (height 10cm IIIS width 2
011% thickness 3Ws) and polyacrylonitrile fiber woven fabric (length 10 cm, width 2 cm).

■ Adhesion Using the injection molded piece and the woven fabric described above, apply the adhesive composition to a 2 x square area of one end with a brush, and then overlap both coated sides and uncoated sides. Glued. 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
/min to measure the peel strength.
(Unit = kgrlc11) (2) Flocking double light test ■ Test material Polypropylene injection molded piece (10 cm long, 10 cm wide
111 (thickness: 3 mm), and nylon pile (thickness: 3 denyl, length: 1 mm) colored in Seiple color using a dye.

■ Flocking: Apply 150 to 300 tons of adhesive composition to the above injection molded piece.
r/rd was applied, 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.

■ Light resistance A high-temperature ultraviolet fade meter (
Light irradiation was carried out at 83° C. for 400 hours using a vacuum cleaner (manufactured by Suga Test Instruments Co., Ltd.). After the light irradiation was completed, the degree of discoloration of the flocked surface was determined based on the gray scale.

(JIS L 0804) (Significant discoloration) Grade 1←--→Grade 5 (No discoloration) In addition, the flocked area was scratched with a fingernail to check for peeling of the pile.

(Example 1) After dissolving isotactic polypropylene with an intrinsic viscosity [η] of 3.0 djF/g in chlorobenzene at 110°C,
A chlorination reaction was carried out by supplying chlorine gas at the same temperature. After the reaction was completed, methanol was added to precipitate the polymer.

Subsequently, filtration and methanol washing were repeated twice, followed by drying under reduced pressure to obtain chlorinated polypropylene. After dissolving the chlorinated polypropylene in xylene, n-butyl acrylate was graft-polymerized at 80°C using benzoyl peroxide as a radical initiator to form chlorine-containing ff12.
0.5% by weight, n-butyl acrylate content is 35.0
% by weight of functional group-containing polypropylene was obtained.

16 g of the obtained functional group-containing polypropylene was added to 150 ml of xylene and dissolved therein, and methyl-3-[3-t-butyl-5-, an ultraviolet absorber, was added as a light stabilizer.
(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate/polyethylene glycol condensate (manufactured by Ciba Geigy, trade name: TINUVIN)
213) 5-3 g s and a hindered amine light stabilizer, bis(1,2,2,6,6-pentamethyl 4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name Sanol LS 765) 2.6 g was added and dissolved.

Subsequently, a commercially available acrylic/styrene copolymer resin-based aqueous emulsion adhesive (manufactured by Kanebo NSC, trade name Yodozol AA57, resin component 40% by weight) 400
An emulsion adhesive composition of the present invention was obtained by adding and mixing the functional group-containing polypropylene and a xylene solution of a light stabilizer to an aqueous emulsion of an adhesive synthetic resin prepared by adding 80 g of water to g and 80 g of water. When the adhesive composition obtained was subjected to a heavy adhesion test, the peel strength was 2. 30kgr/c
It was s. Further, when a flocking light test was conducted, the degree of discoloration was 4.5 grade, no peeling of the pile was observed in the nail scratch test, and the light resistance was also good.

(Comparative Example 1) An adhesive composition was prepared in the same manner as in Example 1 except that a xylene solution containing only functional group-containing polypropylene obtained without adding a light stabilizer was added to an aqueous emulsion of an adhesive synthetic resin. The adhesive composition was subjected to a heavy adhesion test and a flocking light test in the same manner as in Example 1.

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

(Comparative Example 2) In Example 1, commercially available acrylic
A heavy adhesion test and a flocking light test were conducted in the same manner as in Example 1, except that the styrene copolymer resin-based aqueous emulsion adhesive was used as is.

(Comparative Example 3) Same as Example 1 except that only a xylene solution of functional group-containing polypropylene and a light stabilizer was used as the adhesive composition without using the acrylic-styrene copolymer resin water-based emulsion adhesive. A heavy adhesion test and a flocking light test were conducted.

(Comparative Example 4) In Example 1, 16 g of functional group-containing polypropylene powder was pulverized using a pulverizer at a temperature of -40°C without dissolving the functional group-containing polypropylene in xylene.
It was added and mixed into an aqueous emulsion of adhesive synthetic resin. Subsequently, an adhesive composition was obtained in the same manner as in Example 1 except for adding a light stabilizer, and a heavy adhesion test and a flocking double light test were conducted.

(Comparative Example 5.6 and Example 2.3) Adhesive compositions were obtained in the same manner as in Joseuri 1, except that the ratio of the light stabilizer to the synthetic resin component was changed as shown in the table. Then, a heavy adhesion test and a flocking double light test were conducted.

(Comparative Example 7.8 and Examples 4 to 6) In Example 1, instead of the functional group-containing polypropylene, a propylene-ethylene random copolymer with an intrinsic viscosity [η] of 2.0 dfl/g and an ethylene content of 35% by weight was used. Adhesive compositions were prepared in the same manner except for using functional group-containing propylene-ethylene random copolymers with different carboxyl group contents as shown in the table, which were obtained by graft polymerizing various amounts of maleic acid onto the polymer. A heavy adhesion test and a flocking double-light test were conducted on the product.

(Example 7) In Example 1, instead of the functional group-containing polypropylene, isotactic poly-4-methylpentene-1 having an intrinsic viscosity [η] of 3.5 dl/g was dissolved in xylene and used as a radical initiator. using dicumyl peroxide,
After graft polymerizing maleic anhydride at 145°C, a chlorination reaction was subsequently performed in the same manner as in Example 1, and the carboxylic anhydride group content was 2.0% by weight.
, 12 g of functional group-containing poly-4-methylpentene-1 with a chlorine content of 25.0% by weight was used, the amount of ultraviolet absorber used was 4.0 g, and 2-(3, 5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2
, 6,6-pentamethyl-4-piperidyl) (manufactured by Ciba Geigy, trade name TINUVIN 144).
An adhesive composition was obtained in the same manner except that 0 g was used, and a heavy adhesion test and a flocking double light test were conducted.

(Comparative Example 9) In Example 7, a xylene solution of only functional group-containing poly-4-methylpentene-1 obtained without adding a light stabilizer was
An adhesive composition was obtained in the same manner except that it was added to the aqueous emulsion of the adhesive synthetic resin. The adhesive composition was subjected to a heavy adhesion test and a flocking double light test in the same manner as in Example 7.

(Example 8) After dissolving a propylene-ethylene random copolymer with an intrinsic viscosity [η] of 2.6 dfI/g and an ethylene content of 40% by weight in xylene, benzoyl peroxide was used as a radical initiator, and 80% After graft-polymerizing maleic anhydride at ℃, γ-methacryloxypropylmethyldimethoxysilane was further graft-polymerized to give a carboxylic anhydride group content of 1.2% by weight and an alkoxysilyl group content of 0.7% by weight. % functional group-containing propylene-ethylene random copolymer was obtained.

Obtained functional group-containing propylene-ethylene random copolymer 12. was added to 150 ml of xylene and dissolved, and 2-(2'
-Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole (manufactured by Adeka Argus Chemical Co., Ltd., trade name MARK LA-36) 4.0
g, and a hindered amine light stabilizer (1,
2,2,6゜6-pentamethyl-4-piperidyl/tridecyl mixture)-1,2,3,4-butanetetracarboxylate (manufactured by Adeka Argus Chemical Co., Ltd., trade name: MARK)
2.0 g of LA-62) was added and dissolved.

Next, 100 g of water was added to 400 g of a commercially available ethylene/vinyl acetate copolymer resin-based aqueous emulsion adhesive (manufactured by Hoechst Gosho Co., Ltd., trade name Movinyl 085E, resin content 55% by weight) to prepare an aqueous adhesive synthetic resin. A xylene solution of the functional group-containing propylene-ethylene random copolymer was added to the emulsion and mixed to obtain an adhesive composition.

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

(Comparative Example 10) The procedure was carried out in the same manner as in Run N8 except that a xylene solution containing only the functional group-containing propylene-ethylene random copolymer obtained without adding a light stabilizer was added to the aqueous emulsion of the adhesive synthetic resin. An adhesive composition was obtained. The adhesive composition was subjected to a heavy adhesion test and a flocking double light test in the same manner as in Example 8.

(Comparative Example 11) In Example 8, the commercially available ethylene/vinyl acetate copolymer resin-based aqueous emulsion adhesive was used as it was without adding the functional group-containing propylene-ethylene random copolymer and the xylene solution of the light stabilizer. The others were as in Example 8.
Similarly, a heavy adhesion test and a flocking double light test were conducted.

(Example 9) After dissolving a propylene-butene-1 random copolymer with an intrinsic viscosity [η] of 3.0 dl/g and a butene-1 content of 2.0% by weight in xylene, dicumyl peroxide was radically dissolved. After graft polymerizing glycidyl methacrylate as an initiator under graft polymerization conditions at 130°C, a chlorination reaction was further performed in the same manner as in Example 1, and the glycidyl group content was 1. A functional group-containing propylene-butene-1 copolymer with a chlorine content of 18.0% by weight and a chlorine content of 18.0% by weight was obtained.

Obtained functional group-containing propylene-butene-1 copolymer 1
3g: was dissolved in 150ml of toluene, and as a light stabilizer, 3.4g of the ultraviolet absorber used in Example 8 and 1.3g of the hindered amine light stabilizer used in Example 7 were added.
7g was added and dissolved.

Next, 55 g of water was added to 450 g of a commercially available acrylic-styrene copolymer resin water-based emulsion adhesive (manufactured by Saiden Chemical Co., Ltd., trade name Cypinol FX-4, resin component 35% by weight).
To an aqueous emulsion of adhesive synthetic resin to which 0 g was added,
A toluene solution of the functional group-containing propylene-butene-1 copolymer and a light stabilizer were added and mixed to obtain an emulsion adhesive composition. The adhesive composition was subjected to a heavy adhesion test and a flocking double light test in the same manner as in Example 1.

(Comparative Example 12) In Example 9, except that a toluene solution of only the functional group-containing propylene-butene-1 copolymer obtained without adding a light stabilizer was added to the aqueous emulsion of the adhesive synthetic resin. An adhesive composition was obtained in the same manner. The adhesive composition was subjected to a heavy adhesion test and a flocking double light test in the same manner as in Example 9.

(Comparative Example 13) In Example 9, functional group-containing propylene-butene-1
Without addition of toluene solution of copolymer and light stabilizer,
A heavy adhesion test and a flocking double light test were conducted in the same manner as in Example 9 except that a commercially available acrylic-styrene copolymer resin water-based emulsion adhesive was used as is.

(Example 10) In Example 9, after performing the chlorination reaction first, graft polymerization was performed using 2-hydroxyethyl methacrylate instead of glycidyl methacrylate, and the hydroxyl group content was 0.7. An adhesive composition was obtained in the same manner except that a functional group-containing propylene-butene-1 copolymer Log having a chlorine content of 8.0% by weight was used as the functional group-containing polyolefin. Tests and hair transplantation were carried out in both optical tests.

(Implementation f!i411) After spraying isotactic polypropylene with an intrinsic viscosity [η] of 4.5 dN/g onto xylene, acrylamide was added under graft polymerization conditions at 80°C using benzoyl peroxide as a radical initiator. Graft polymerization was carried out. 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 functional group-containing polypropylene having an amide group content of 2.2% by weight and a chlorine content of 41.0% by weight. An emulsion adhesive composition was obtained in the same manner as in Example 9 except that 15 g of the functional group-containing polypropylene was used in place of the functional group-containing propylene-butene-1 copolymer, and a heavy adhesion test was conducted. A hair transplantation double light test was conducted.

(Example 12) In Example 1, instead of the functional group-containing polypropylene, a hydrogenated styrene-isoprene block copolymer (manufactured by Shell Chemical Co., Ltd., trade name: Kraton G1701) was dissolved in xylene, and then dichloromethane was added as a radical initiator. 14 g of a hydrogenated functional group-containing styrene-isoprene block copolymer with a carboxylic anhydride group content of 2.6% by weight, obtained by graft polymerizing maleic anhydride using Milperoxide at 125°C. An adhesive composition was obtained in the same manner except that the adhesive composition was used, and a heavy adhesion test and flocking light resistance evaluation were conducted.

〔Effect of the invention〕

The emulsion 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. It has extremely good light resistance.

As is clear from the examples described above, the peel strength in the surface adhesion test ranged from 0.70 kgf/cse to 2.35) cg when the emulsion adhesive composition of the present invention was used.
f/am, and the degree of discoloration in the flocked light test was 4.
It is grade 0 to grade 4.5, has no peeling of piles, and is significantly superior in initial adhesion and light resistance compared to known emulsion adhesives that do not contain the functional group-containing polyolefin or light stabilizer according to the present invention. ing.

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 initial adhesion and/or light resistance may significantly deteriorate. descend.

Claims (1)

[Scope of Claims] 1. An emulsion adhesive composition, wherein the resin components in the composition include (1) 100 parts by weight of an adhesive synthetic resin, and (2) a carboxylic acid anhydride group, a carboxyl group, and a glycidyl group. polyolefin containing 0.01% to 70% by weight of one or more functional groups selected from the group consisting of hydroxyl group, amide group, alkoxysilyl group, and chlorine, and/or containing 0.01% to 70% by weight 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 70% by weight, An emulsion adhesive composition further comprising: (3) 0.1 to 20 parts by weight of a light stabilizer based on 100 parts by weight of the total resin components of (1) and (2). 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 polymer has an average molecular weight of 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 obtained by graft-polymerizing 60% by weight or less of a radically polymerizable monomer in addition to the functional group. 5. The composition according to claim 1, which uses an ultraviolet absorber and a hindered amine radical scavenger as the light stabilizer. 6. In the method for producing an emulsion adhesive composition, (A) an aqueous emulsion of an adhesive synthetic resin is added to (B) (2) a carboxylic acid anhydride group based on 100 parts by weight of the (1) synthetic resin in the emulsion. , carboxyl group, glycidyl group, hydroxyl group, amide group, alkoxysilyl group, and chlorine.
polyolefin containing from % to 70% by weight, and/
or a hydrogenated block copolymer consisting of at least one aromatic vinyl compound polymer block and at least one aliphatic diene polymer block containing 0.01% to 70% by weight of the functional group. 05 parts by weight to 40 parts by weight, and (3) 0.1 parts by weight to 20 parts by weight of a light stabilizer, and (4) an organic A method for producing an emulsion adhesive composition, comprising adding a solution consisting of a solvent. 7. The manufacturing method according to claim 6, 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. 8. 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). 7. The production method according to claim 6, wherein the polymer has a polymer content of 0.1 dl/g to 10 dl/g. 9. 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 7. The production method according to claim 6, which is a polymer obtained by graft polymerizing 60% by weight or less of a radically polymerizable monomer in addition to the functional group. 10. The production method according to claim 6, wherein an ultraviolet absorber and a hindered amine radical scavenger are used as the light stabilizer.