JPS6296576A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. having excellent (initial) adhesion, workability and heat resistance, by adding a chlorinated polyolefin to a blend of a particular acrylic ester copolymer emulsion, etc., with a chloroprene latex, an alkaline catalyst, etc. CONSTITUTION:100pts. (by wt.; the same shall apply hereinafter) tackifier resin (e.g., rosin) is dissolved in 20-60pts. org. solvent, followed by addition of 2-10pts. surfactant. 200-500pts. acrylic ester emulsion, methyl methacrylate/ butadiene copolymer latex or styrene-butadiene copolymer latex is continuously and gradually added thereto at a high temp. with rapid stirring, thereby obtaining a compound (A) having excellent adhesion. 0.1-20pts. chlorinated polyolefin is incorporated in a blend of 100pts. (on a solid basis; the same shall apply hereinafter) component A with 10-300pts. chloroprene latex, 10-200pts. emulsion of an acrylic ester copolymer composed mainly of an acrylic ester and a vinyl halide compd., 0.1-10pts. alkaline catalyst, and 0.1-20 heat-reactive phenolic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to adhesion of automobile interior materials. More specifically, it relates to adhesion of parts of molded objects such as molded ceilings, molded doors, pillars, rear trays, etc. Automotive interior materials usually use plastic, metal, hardboard, resin board, cardboard, etc. as the molded substrate, and foamed urethane, foamed polyethylene, or foamed material overlaid with vinyl chloride sheet or cloth, etc. as the cushion and insulation layer. Although polypropylene and the like are used, the present invention relates to a water-based emulsion type adhesive for bonding a molded substrate and a plastic foam to form a composite material.

[Conventional technology]

The adhesive used to convert plastic foam into a composite material has no safety and health issues or environmental pollution issues in the manufacturing factory.
It has a wide adhesion tolerance for various automobile interior materials, the adhesive layer has excellent heat resistance, moisture resistance, and durability, and furthermore, the cushioning properties and texture inherent to plastic foam are not impaired by the penetration of the adhesive. things are required.

Conventionally, solvent-based adhesives such as urethane-based, chloroprene-based, and AkuIJO nitrile-butadiene rubber-based adhesives have been mainly used as adhesives for automobile interior materials (hereinafter referred to as composite materials). It is made of composite material. However, with solvent-based adhesives, the solvent scatters during work, which poses occupational safety and health problems in factories and the risk of fire, and is also developing into a pollution problem due to environmental pollution. Demand for adhesive development is increasing.

Also, there are problems with the physical properties of conventional adhesives.

Adhesives have elasticity, but they lack the heat resistance required for composite materials, and often cause peeling. On the other hand, when bonding is performed under insufficient drying conditions, adhesives and organic solvents can cause damage to the plastic foam layer. As a result of the resin penetrating into the foam and hardening inside the foam, the original cushioning properties and texture of the foam are lost.

In the case of vinyl chloride sheet skin materials, there is a problem in that the penetration of organic solvents causes blistering and floppy phenomena in the vinyl chloride sheets, resulting in a significant decrease in commercial value.

On the other hand, pressure-sensitive acrylic emulsion adhesives have begun to be commercially available based on the recent needs for solvent-free adhesives.
Further improvements are required in terms of adhesion to various plastic foams, heat resistance, workability, etc., and it has not yet been put into practical use.

[Problem that the invention seeks to solve]

As for the above-mentioned solvent-removal type adhesive, the present inventor has already published Japanese Patent Application Laid-open No. 1986-56.
As described in the specification of No. 80451 and the specification of Japanese Patent Application No. 181134/1980, the emul 7-I is based on an acrylic acid copolymer emulsion containing an acrylic acid ester and a vinyl halide compound as the main components.

Heat resistance, moisture resistance, and durability achieved through the combined use of alkaline catalysts and tackifier resin desversion.

We have already developed a water-based emulsion type adhesive that has good texture and texture. However, practical problems arose in aspects such as the shift to deep drawing of composite materials, the emergence of various plastic foams, the increase in heat-resistant adhesive strength requirements, and adaptability to existing adhesive equipment, and improvements were forced. Ta.

That is, is the adhesive composition described in JP-A-56-80451 a foamed urea? It was found that although good adhesion properties were obtained when adhering to other materials, it lacked adaptability to foamed polyethylene, foamed polypropylene, etc., which have recently begun to be used as composite materials. In addition, from the viewpoint of workability, the adhesion tolerance range is limited due to the limited adhesion conditions that require semi-drying after applying the adhesive and bonding the plastic foam while the adhesive layer retains its tackiness. narrow,
A problem arose in that it was not compatible with the bonding process in existing bonding equipment.

On the other hand, the adhesive composition described in Japanese Patent Application No. 60-181134 is 1 foamed urethane and polyethylene.

Although it has excellent adhesion and adhesion tolerance to various plastic foams such as polypropylene, deep-drawn molded products using foamed polyethylene or single-foamed polypropylene as a cushioning material (such as those seen in recent molded doors) When applied to severe adhesion of door springs, the deepest concave part caused a peeling phenomenon (lifting) in the heat resistance test at 90±2°C, and the adhesive composition lacked practicality in terms of heat resistance. As long as a foam treated with a synthetic rubber or urethane resin is used, the heat resistance is satisfied, but this leads to an increase in processing costs, which poses a practical problem.

[Means for solving problems]

The purpose of the present invention is to solve occupational safety and health problems, environmental pollution problems, etc. by using a water-based emulsion type adhesive composition, and without impairing the original cushioning properties and texture of plastic foam. Adhesiveness and adhesion tolerance to various types of glass foam.

In other words, the present invention aims to provide an adhesive composition that maintains good workability and the heat resistance that a composite material should have, especially adhesive strength at high temperatures in a high-temperature atmosphere when bonding deep-drawn products. be.

In order to achieve this objective, the inventors of the present invention have made extensive studies and have included a tackifying resin. Acrylic acid ester copolymer emulsion, methyl methacrylate-butadiene copolymer latex.

or a styrene-butadiene copolymer latex compound, chloroprene latex, an acrylic ester copolymer emulsion containing an acrylic ester and a vinyl halide compound as main components, and an alkaline catalyst;
We have discovered that it is extremely effective to further combine chlorinated polyolefin with a mixture of heat-reactive phenolic resin.

The present invention has now been completed.

That is, the present invention contains (1) a tackifying resin. 100 parts by weight of acrylic acid ester copolymer emulsion, methyl methacrylate-butadiene copolymer latex, or styrene-butadiene copolymer latex compound as solid content.

■Chloroprene latex as solid content 10-300
Weight part.

(2) 10 to 200 parts by weight of an acrylic acid copolymer emulsion containing an acrylic acid ester and a vinyl halide compound as the main components, as a solid content.

■0.1 to 10 parts by weight of alkaline catalyst as solid content.

■Heat-reactive phenolic resin as solid content 0.1-20
Weight part.

(2) An adhesive composition containing 0.1 to 20 parts by weight of chlorinated polyolefin as a solid content.

Acrylic copolymer emulsion (hereinafter referred to as acrylic emulsion) containing the tackifier resin used in the present invention (hereinafter referred to as acrylic emulsion), methyl methacrylate-butadiene copolymer latex (hereinafter referred to as MBR latex), styrene-butadiene copolymer latex (hereinafter referred to as SBR latex) A method for producing a compound is, for example, by adding a small amount of surfactant to a tackifying resin solution dissolved in an organic solvent, and gradually forming an acrylic emulsion, MBR latex, or SBR latex under high temperature and high speed stirring conditions. One method is to continuously add . The compounds thus obtained usually have a viscosity of 100 to 10,000 cps, preferably 50-0 to 1,000 cps.

Solids content 40-70%, preferably 50-60%.

It is a compound with excellent adhesiveness with a pH of 7 to 8.

The tackifying resins used in this compound include rosin-based tackifying resins typified by natural or polymerized rosins, modified rosins, glycerin esters of hydrogenated rosins, triethylene glycol esters, and pentaerythritol esters, and α-pinene.

Examples include alkylphenol resins, general formula silene resins, etc. Among these, rosin resins having a softening point of 90 to 125° C. are particularly preferred from the viewpoint of adhesion to various plastic foams.

As the surfactant used in this compound, any anionic or nonionic surfactant used in the emulsion polymerization of ordinary emulsions can be used, but it is preferable to use a surfactant with excellent emulsifying power and low foaming. HLB12～
Fourteen polyoxyethylene alkyl ether types are mentioned.

As for the organic solvent used in this compound, basically any solvent that can dissolve the tackifying resin can be used, but due to the odor of the compound and the dryness of the adhesive coating layer, toluene, n-hexane, Examples include n-hebutabecyclohexane and ethyl alcohol, and it is desirable to use one or more of these in combination.

The acrylic emulsions used in this compound include ethyl acrylate, butyl acrylate, 2-
Main ingredients include ethylhexyl acrylate, styrene, and methyl methacrylate.

Vinyl compounds such as acrylonitrile and functional groups
It is an emulsion copolymerized with acrylic acid, methacrylic acid, itaconic acid, acrylamide, methylol acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc., and has a normal glass transition temperature (RY) of 1.

～-40℃, preferably O～-30℃, viscosity 100-1
0000 cps, preferably 100-1000 cps
.

Solids content 40-70%, preferably 40-60%.

Acrylic emulsions of PI (6 to 9) are mentioned.

Acrylic acid as functional monomer in a ratio of 6/4.

Copolymerized with methacrylic acid, itaconic acid, acrylamide, methylol acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. Glass transition temperature (TI) 0 to -30°C viscosity 50 to 10
000 cps, preferably 50 to 500 cps, solids content of 40 to 60%, and pH of 6 to 9.

Acrylic acid, methacrylic acid, as functional group monomers in
Glass transition temperature (
T5') Viscosity at O~-30℃ 50~10000 cps
, preferably 50-500 cps, solids content 40-60%
, SBR latex with a pH of 6 to 9.

The mixing ratio of each of the above is 2 to 10 parts by weight of surfactant and 20 to 604 t of organic solvent to 100 parts by weight of tackifying resin.
The preferred range is f[m, 200 to 500 parts by weight of acrylic emulsion 3F, MBR latex or SBR latex.

Particularly preferably, the amount of surfactant used is 4 to 6 parts by weight in view of compound production and storage stability, and the amount of organic solvent used is 30 to 40 parts by weight, taking into consideration the viscosity of the tackifying resin solution and the odor of the compound product.

The amount of acrylic Emashif 9, MBR latex, and SBR latex to be used is desirably in the range of 300 to 400 parts by weight in view of compound product viscosity and adhesive performance.

In the present invention, the reason why the compound containing the tackifying resin is used as a paste resin is that when an adhesive composition is obtained using the tackifying resin alone and subjected to a heat resistance test, even if the resin has a high softening point, The purpose of this is to use the cohesive strength of acrylic or synthetic rubber latex to compensate for the phenomenon that even when using acrylic or synthetic rubber latex, it begins to soften as the temperature rises and the desired adhesive strength cannot be obtained when heated.

To give a specific example of manufacturing this compound, an organic solvent, a surfactant, and a tackifying resin are placed in a closed pot equipped with a stirrer, and the dissolved material is completely dissolved while stirring at room temperature or 70 to 80°C. The acrylic emulsion, MBR latex, or SBR latex was gradually added continuously under high-speed stirring conditions while maintaining the temperature at a warm temperature of 50 to 60°C.
A stable compound with a thickness of 0.2-0.25μ is obtained.

The chloroprene latex used in the present invention is:
Currently, the solid content of cloth is 40-70%.

Preferably 50-60%, viscosity 10-10000cps
, preferably l C1-500 cps, PH7-1
No. 3 unmodified or carboxyl group-modified type chloroprene latex is mentioned.

Preferably, a type having a fast crystallization rate and excellent cohesive force is desirable. The purpose of using the chloroprene latex is to improve adhesive strength at room temperature and heat by utilizing the crystallinity of the polymer, and to improve adhesiveness to various plastic foams.

The blending ratio of real roloprene latex is in the range of 10 to 300 parts by weight based on 100 parts by weight of the solid content of the acrylic emulsion, MBR latex, or SBR latex compound. Preferably it is in the range of 20 to 150 parts by weight. When the amount is less than 20 parts by weight, no improvement in heat resistance is observed.

If the amount is more than 300 parts by weight, pressure sensitivity will be impaired.

Adhesion to various plastics decreases, making it impractical.

In the 0 acrylic ester copolymer emulsion used in the present invention, the acrylic ester is preferably 80.0 to 99.9% by weight of the total monomer components, and the vinyl halide compound is preferably 0.1 to 20.0% by weight. . Preferred examples of the acrylic ester include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Preferred vinyl halide compounds that can be copolymerized with acrylic esters include chlorine compounds such as 2-chloroethyl acrylate, 2-chloroethyl vinyl ether, and vinyl chloroacetate from the viewpoint of copolymerizability with acrylic esters. It will be done. What is the most preferable combination of these?

Copolymerizability in emulsion polymerization A combination of ethyl acrylate and 2-chloroethyl vinyl ether is preferred from the viewpoint of stability during single polymerization and adhesive properties.

The amount of 2-chloroethyl vinyl ether used is preferably in the range of 0.1 to 20% by weight based on the total monomers. A particularly preferable usage amount is in the range of 0.1 to 5% by weight based on the total monomers from the viewpoint of stability and cost during copolymerization.

The copolymerization of the acrylic ester and the vinyl halide compound can be carried out by a common emulsion polymerization method.

For example, a mixed monomer of an acrylic acid ester and a vinyl halide compound to which a chain transfer agent such as lauryl mercaptan or dodecyl mercaptan is added.

An emulsifying monomer that has been emulsified and dispersed in an aqueous solution of an emulsifier such as sodium laurate or polyoxyethylene lauryl ether is charged into a polymerization tank that has been purged with nitrogen in advance, and a polymerization initiator such as potassium persulfate or ammonium persulfate is added.
By performing stirring polymerization at a temperature of 0°C, an acrylic ester copolymer emulsion with a polymerization rate of nearly 100% can be obtained.

During the polymerization of this acrylic acid copolymer emulsion, as necessary, vinyl F compounds such as styrene, methyl methacrylate, acrylonitrile, and functional group monomers such as acrylic acid, methacrylic acid, itaconic acid, acrylamide, and methylol acrylamide are used. , hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. may be used in combination.

As mentioned above (specifically, as an acrylic ester copolymer emulsion obtained by emulsion polymerization).

Solid content 40-70%, viscosity 50-1000 cps.

Examples include emulsions with PHtoo~11.0.

The purpose of using the acrylic ester copolymer emulsion is to improve the adhesive strength during heat by using an alkaline catalyst as described later.

The blending ratio of this acrylic ester copolymer emulsion is acrylic emulsion, MBR latex or SB
The amount ranges from 10 to 200 parts by weight based on 100 parts by weight of the solid content of the R latex compound. Preferably 30~
The range is 100 parts by weight.

When it is less than 10 parts by weight, no improvement in heat resistance is observed, and when it is more than 200 parts by weight, pressure sensitivity is impaired and adhesion to various plastics is reduced.

Lacks practicality.

Examples of the alkaline catalyst (2) used in the present invention include organic alkaline catalysts such as ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenetetramine, and sodium hydroxide.

Potassium hydroxide, potassium carbonate, sodium carbonate.

These are inorganic alkaline catalysts such as potassium hydrogen carbonate and sodium hydrogen carbonate, and at least one kind of alkaline catalyst selected from these is used.

From a performance standpoint, a combination of organic and inorganic alkaline catalysts is desirable. The most preferred alkaline catalyst combination is hexamethylenetetramine and sodium carbonate. Moreover, this aluminum is particularly effective in imparting heat resistance and moisture resistance. The present alkaline catalyst is usually preferably used in the form of an aqueous solution of both.

The mixing ratio of the alkaline catalyst is based on 100 parts by weight of the solid content of the 2-acrylic emulsion, MBR latex, or SBR latex compound.

The solid content is in the range of 0.1 to 10 parts by weight. The most preferable blending ratio is in the range of 1 to 5 parts by weight.

If it is less than 0.1 parts by weight, no significant effect will be seen on heat resistance or moisture resistance, and if it is more than 10 parts by weight, there will be no problem with adhesive performance, but since it is used as an aqueous solution, the adhesive composition The solid content viscosity of the product decreases significantly, causing problems in terms of workability and lacking in practicality.

The heat-reactive phenolic resin used in the present invention includes:
Examples include oil-soluble alkylphenols used as compounding agents for synthetic rubbers such as SBR, NBR, and chloroprene, and in particular, resol-type heat-reactive or thermosetting p-tert-butylphenol is preferred from the standpoint of imparting heat resistance.

The purpose of blending the resin is to maintain adhesion when adhering the composite material and to improve adhesive strength and adhesive strength under heat through a crosslinking reaction with chloroprene latex in a high-temperature atmosphere.

The blending ratio of the heat-reactive phenolic resin is 0.1 to 20 parts by weight based on 100 parts by weight of the solid content of the acrylic emulsion, MBR Ufnox, or HaSDR Latenox combined.
Parts by weight range. Preferably it is in the range of 0.5 to 10 parts by weight. If it is less than 0.1 part by weight, no significant improvement in adhesive strength during heating will be obtained, and if it is more than 20 parts by weight, a crosslinking reaction will occur when the adhesive is applied and dried under heat, resulting in a decrease in adhesive strength and various Adhesion to plastic foam is impaired, posing a practical problem.

When formulating this resin, it is usually in the form of a lump, so it is best to dissolve it in an organic solvent such as toluene.

Examples of the chlorinated polyolefin used in the present invention include chlorinated polypropylenes currently available in toluene solution type and powder form having a solid content of 20 to 100% and a chlorine content of 10 to 45%.

As a particularly preferred chlorinated polyolefin, a powdered product with a high degree of polymerization having a chlorine content of 30% is effective in improving adhesion to various plastic foams, especially foamed polypropylene.

The blending ratio of the chlorinated polyolefin is in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the solid content of the acrylic emulsion, MBR latex, and SBR latex compound.

Preferably it is in the range of 0.5 to 5 parts by weight.

Especially if it is less than 0.1 part by weight, foamed polyethylene,
No remarkable effect was observed in improving the adhesion with foamed polypropylene and the adhesion strength under heat, and 20. If there are more than i slip part,
Since the chlorinated polyolefin resin itself is thermoplastic, its adhesive strength decreases when heated, which poses a practical problem. When using powdered chlorinated polyolefin, it is preferable to use one dissolved in an organic solvent such as toluene.

This adhesive composition may optionally contain a water-soluble polymer such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, or carboxymethyl cellulose, or a thickener such as sodium polyacrylate or a nonionic surfactant, as well as an anti-aging agent. , an antifoaming agent, a leveling agent, a silane coupling agent, a coloring agent, etc. may be added.

As described above, the adhesive composition of the present invention maintains an adhesion tolerance range, that is, good workability, when adhering composite materials, has excellent adhesion to various glass foams, and has good cushioning properties and texture. It maintains heat resistance without impairing the heat resistance, especially the adhesion strength in high-temperature atmospheres when adhering deep-drawn objects, ensuring safety and health.

It also has extremely high practical value from the standpoint of environmental pollution.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

In the following, parts and percentages are based on weight unless otherwise specified.

Example 1 Acrylic emulsion compound (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Structbond 5169EE).

Acrylic emulsion monomer composition: butyl acrylate / 2-ethylhexyl acrylate / methyl acrylate / methacrylic acid / 1ert - amount of 8%, solid content 50%, PH 8, viscosity 3000 cps) 100 parts of chloroprene latex (manufactured by Denki Kagaku Kogyo ■) , product name LA
-50, solid content 50%) 100 parts, acrylic ester copolymer emulsion (manufactured by Mitsui Toatsu Chemical ■, trade name Structpond 5X-102, solid content 50%, PH2.0
, viscosity 150 cps, ethyl acrylate and 2-chloroethyl vinyl ether copolymerization ratio 95:5) 40 parts, 10 parts concentrated aqueous solution of alkaline catalyst (1 part 2 mixture of hexamethylenetetramine and sodium carbonate), 10 parts thermal reaction type. Phenol resin (manufactured by Gunei Kagaku ■).

20 parts toluene solution 1 of product name PS-2655
0 parts and 5 parts of a toluene solution of 20 parts of chlorinated polyolefin (manufactured by Yamaba Kokusaku Pulp ■, trade name S-83) were blended and mixed with stirring to obtain an adhesive composition of the present invention.

Using this adhesive composition, a composite material was prepared under the conditions shown below, and the material was subjected to physical property tests as shown below, and the results are shown in Table 1.

1) Adhesion conditions a) Molded body substrate...3jI
I + thickness resin board (flat board made of composite material of fiber and phenolic resin) Plastic foam: ■Urethane foam (polyether type) with vinyl chloride overlaid as a surface material ■Polyethylene foam 0 polypropylene foam・・・）Application ・・・・・・・・・・・・・・・・・・
...Using Hitachi spray gun model AS-30-10.

Uniform application on the resin board surface 2) Coating fee ・・・・・・・・・・・・・・・・・・・・・
・・50 parts Adhesive solid content: 15 (1/rrl e) Drying ・・・・・・・・・・・ Song・・・・・・Permanent resin coated with adhesive in a hot air dryer at 100℃ (Dry for 2 minutes inside) Open time...Song/Song for 1 minute. However, the adhesion tolerance (removal from the dryer, 0 hours until bonding) will be described separately.

g) Adhesion ・・・・・・・・・・・・・・・・・・
...1 minute after open time.

Various plastic foams Paste the body together, 0.5 kg　/aj at clamping pressure Crimp for 10 seconds and Composite materials for physical property testing It was created.

h) Health care ・・・・・・・・・・・・・・・・・・
... After curing at room temperature for 3 days, it was subjected to various physical property tests. however.

Regarding initial adhesive strength measurement After 10 minutes of gluing It was measured.

2) Physical property test A) Adhesion to various plastic foams After 1 minute, forcefully peel off the resin board and plastic foam adhesive layer with your fingertips, observe the adhesion state, and display the results as shown below. Shown in 1.

○・・・・・・Complete matrix failure Δ of glass foam
・・・・・・Partial destruction of the matrix of plastic foam×・
...Peeling opening from the interface of the plastic foam) Adhesion tolerance As a way to check the adhesion tolerance, each plastic foam was pasted together after 5 minutes of open time.

One minute after adhesion, the resin board and plastic foam adhesive layer were forcibly peeled off using a fingertip, and the adhesion state was observed and displayed as shown below. The results are shown in Table 1.

O...Complete matrix destruction of plastic foam Δ・
・・・・・・′ 〃 Partial destruction of the matrix×・・
... Peeling from the interface C) Initial adhesion Cut the composite material into 125 pieces and 25 m pieces, peel off the 50-meter foam from the edge, and after 10 minutes of adhesion, hold the plastic foam and resin board in a 180° direction. 2 with a tensile tester
The average peel strength was expressed in kQ/2 s m, and the peeling state was observed, and the percentage of matrix failure of the plastic foam was expressed in %. (100 indicates complete matrix failure) 2) Normal adhesive force A sample of the same size as the initial adhesive force measurement was taken, and after 3 days of curing, the adhesive force was measured according to the initial adhesive force measurement method, and bonded using the same method. The force and peeling state are displayed.

e) Heat-resistant adhesive strength A sample of the same size as the initial adhesive strength measurement was taken from the composite material after curing for 3 days, and 110 copies were attached to a constant temperature tensile tester at 2°C. After reaching the specified temperature, the sample was left for 15 minutes. Measurement was performed at the same temperature according to the initial adhesive strength measurement method, and the adhesive strength and peeling state were expressed in the same manner. (* Change the measurement temperature to normal 9
The temperature was set higher than 2° C. in consideration of the shrinkage stress applied during the heating of bonding the deep-drawn compacts, and the temperature conditions were severe. ) Example 2 MBR latex compound (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Structbond XA-7520°, solid content 50%,
PH8, viscosity 3000 cps, zero gin deactivation imparting resin content 20%, organic solvent content 8%), LA-50 as the chloroprene latex used in Example 1,
100 parts of acrylic acid ester copolymer emulsion, Structbond 5X-102, 40 parts, a 10 part concentration aqueous solution of an alkaline catalyst (a 1 part 2 mixture of hexamethylenetetramine and sodium carbonate) (hereinafter referred to as 10% alkaline catalyst aqueous solution). ) 10 parts, a 20% toluene solution of PS-2655 as a heat-reactive phenolic resin (hereinafter 2
0% PS-2655) toluene solution) and 5 parts of a 20% toluene solution of 5-83 as a chlorinated polyolefin (hereinafter referred to as 20% S-83 toluene solution) were mixed by stirring. An inventive adhesive composition was obtained.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 3 SBR Latenok Conbound (manufactured by Mitsui Toatsu Kagaku α, trade name Structbond 3522. Solid content 50%, PH
8.0, viscosity 3000 cps, 20% o-gin tackifying resin content, 8% organic solvent content) 100 parts of the chloroprene latex used in Example 1 and LA-50
, 100 parts, Structbond 5X-102 as an acrylic acid ester copolymer emulsion, 40 parts, 10 parts, alkaline catalyst aqueous solution 10 parts, 20% PS-2655
10 parts of a toluene solution and 5 parts of a 20% 5-83 toluene solution were blended and mixed with stirring to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 4 3522.100 parts of Structbond as an SBR latex compound, 20 parts of LA-50 as the chloroprene latex used in Example 1, and Structobond SX as an acrylic acid ester copolymer emulsion
-102, 40 parts, 10 parts alkaline catalyst aqueous solution 10 parts, 20% Ps-2655 toluene solution 10 parts, 20% 5
-83 5 parts of toluene solution was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 5 As an SBR latex compound, 3522.100 parts of Structbond, 300 parts of LA-50 as the chloroprene latex used in Example 1, and 40 parts of Structbond 5X-102 as an acrylic acid ester copolymer emulsion, 10 % alkaline catalyst aqueous solution 1
0 parts, 20% PS-2655) 10 parts of toluene solution, 2
Five parts of a 0% 5-83 toluene solution was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 6 As an SBR latex compound, Structobond 3522.100 parts, 100 parts of LA-50 as the chloroprene latex used in Example 1, and Structobond 5 as an acrylic acid ester copolymer emulsion were used.
X-102, 10 parts, 10% alkaline catalyst aqueous solution 10
parts, 20% PS-2655) 10 parts of toluene solution, 20%
5 parts of 5-83 toluene solution were blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 7 3522.100 parts of Structbond as an SBR latex compound, 100 parts of LA-50° as the chloroprene latex used in Example 1, and Structbond S as an acrylic acid ester copolymer emulsion
X-102, 200 parts, 10% alkaline catalyst aqueous solution 1
0 parts, 20% PS-2655 toluene solution 10 parts, 20
% 5-83 toluene solution was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results were shown as N-IK.

Example 8 As an SBR latex compound, Structobond 3522.100 parts, LA-50° 100 parts as the chloroprene latex used in Example 1, and Structobond 5 as an acrylic acid ester copolymer emulsion were used.
X-102, 40 parts, 10% alkaline catalyst aqueous solution 0.
5 parts, 20% PS-2655) toluene solution 10 parts, 20
%5-83 toluene solution was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 9 LA-50, Zo was used as the chloroprene latex used in Example 1 in 3522.100 parts of Structbond as an SBR latex compound.

40 parts of Stoyctbond 5X-102 as an acrylic acid ester copolymer emulsion, 50 parts of a 10% aqueous alkaline catalyst solution, 10 parts of a 20% PS-2655 toluene solution, 5 parts of a 20% 5-83 toluene solution The adhesive composition of the present invention was obtained by stirring and mixing.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 10 As an SBR latex compound, Structobond 3522.100 parts, LA-50,100 parts as the chloroprene latex used in Example 1, and Structobond 5 as an acrylic acid ester copolymer emulsion were used.
X-102, 40 parts, 10% alkaline catalyst aqueous solution 1o
parts, 20% PS-2655) 0.25 parts of toluene solution, 2
Five parts of a 0% 5-83 toluene solution was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 11 As an SBR latex compound, Structobond 3522.100 parts, 100 parts of LA-50 as the chloroprene latex used in Example 1, and Structobond 5 as an acrylic acid ester copolymer emulsion were used.
X-102, 40 parts, 10% alkaline catalyst aqueous solution 10
parts, 20% PS-2655 toluene solution 50 parts, 20%
5 parts of 5-83 Torrone solution were blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 12 SBR latex container (as a land, 3522.100 parts of Structbond, 50.100 parts of LA-as the chloroprene latex used in Example 1, 102.40 parts of Structbond 5X as an acrylic acid ester copolymer emulsion) , 10% alkaline catalyst aqueous solution 1
0 parts, 20% PS-2655 toluene solution 10 parts, 20
%5-83 toluene-soluble i was blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Example 13 As an SBR latex compound, Structobond 3522.100 parts, 100 parts of LA-50 as the chloroprene latex used in Example 1, and Structobond 5 as an acrylic acid ester copolymer emulsion were used.
X-102, 40 parts, 10% alkaline catalyst water soluble gxo
parts, 20% PS-2655 toluene solution 10 parts, 20%
50 parts of 5-83 Torrone solution were blended and stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Comparative Example 1 As an acrylic ester copolymer emulsion, 100 parts of Structbond 5X-102 and 10 parts of a 10% alkaline catalyst aqueous solution were used as a tackifying resin aqueous desversion (manufactured by Arayo Kagaku Kogyo ■, trade name: Super Ester E).
720. The adhesive composition of the present invention was obtained by blending 30 parts (solid content: 50%) and stirring and mixing.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

Comparative Example 2 As an acrylic ester copolymer emulsion, 10 parts of a 10% aqueous alkaline catalyst solution was blended with 100 parts of Structbond 5X-102, and the mixture was stirred and mixed to obtain an adhesive composition of the present invention.

It was subjected to the same test as in Example 1, and the results are shown in Table-1.

〔Effect of the invention〕

As is clear from Table 1, the adhesive composition of the present invention has excellent adhesion tolerance, adhesion to various plastic foams, and initial adhesion when adhering composite materials, and is particularly suitable for deep drawing products. Excellent heat resistance.

Furthermore, it is extremely significant in terms of environmental pollution and occupational safety and health, as it poses very little danger.

Claims (1)

[Scope of Claims] (a) 100 parts by weight of an acrylic ester copolymer emulsion, methyl methacrylate-butadiene copolymer latex or styrene-butadiene copolymer latex compound containing a tackifying resin as solid content; (b) Chloroprene latex as a solid content of 10 to 3
00 parts by weight, (c) 10 to 200 parts by weight of an acrylic ester copolymer emulsion mainly composed of an acrylic ester and a vinyl halide compound as a solid content, (d) 0.1 to 200 parts by weight of an alkaline catalyst as a solid content 10 parts by weight. (e) Heat-reactive phenol resin as a solid content of 0.1~
20 parts by weight, (f) 0.1 to 2 chlorinated polyolefin as solid content
An adhesive composition comprising: 0 parts by weight.