JPH0623360B2 - Adhesive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel chlorine-based adhesive resin composition. More specifically, it is an adhesive resin composition excellent in normally dry adhesion and heat seal adhesion to various synthetic polymer materials as well as metals, glass, ceramics, wood base materials, etc., and soluble in an organic solvent at room temperature. Is provided.

[Conventional technology]

In general, a synthetic polymer material, particularly a laminated body composed of a polyolefin and a metal, has been widely noticed as a structural material because it has both the high strength of a metal and the lightweight and inexpensive advantages of a polyolefin. However, a polyolefin generally does not have a polar group in the molecule, and a simple adhesion does not result in a satisfactory adhesive effect, so that it cannot be used as a laminate for practical use. Therefore, it has been attempted to use various adhesive resins for producing a laminate of a polyolefin and a metal. For example, an ethylene-glycidyl acrylate copolymer disclosed in JP-B-46-27527, a polyolefin graft-modified with an unsaturated carboxylic acid or an acid anhydride disclosed in JP-B-52-19288, There are many compounds such as a mixture of an ethylene copolymer containing an unsaturated carboxylic acid or an acid anhydride and an acrylic acid ester-based polymer as disclosed in Japanese Patent Publication No. 57-153064. However, these adhesive resins are two-component copolymers,
Grafts and mixtures which are hardly soluble in organic solvents at room temperature and have sufficient adhesive strength for heat seal adhesion in practice have not been obtained.

Also, various thermoplastic resins and thermosetting resins are used as adhesives or binders for polyolefins.
Among these, a graft or mixture containing a chlorinated polyethylene component which is one of thermoplastic resins soluble in an organic solvent at room temperature is disclosed in JP-B-42-22545 or JP-B-46-39475.
As shown in the publications such as No. etc., impact resistance, heat resistance and other mechanical properties are excellent, but these graft products or mixtures are dissolved in a solvent, and polyolefin and polyolefin or polyolefin and various substances, especially It is not always satisfactory as an adhesive with a metal.
On the other hand, a thermosetting resin having excellent adhesion has a drawback that it is expensive and complicated to use.

[Problems to be solved by the invention]

The present inventors have conducted intensive studies to improve the drawbacks of conventional adhesive resins, and as a result, have always dried and heat-bonded various synthetic polymer materials as well as metals, glass, ceramics, wood base materials and the like. The present invention provides an adhesive resin composition which has excellent seal adhesiveness and is soluble in an organic solvent at room temperature.

[Means for solving problems]

The gist of the present invention is that an unsaturated carboxylic acid monomer having one or more kinds of carboxyl groups selected from carboxylic acids and / or carboxylic anhydrides, and α, β
-An adhesive resin composition comprising a chlorinated product obtained by chlorinating a terpolymer of unsaturated monocarboxylic acid ester and ethylene.

The chlorinated terpolymer used in the present invention comprises an unsaturated carboxylic acid monomer having one or more polar groups selected from carboxylic acids and / or carboxylic anhydrides, and an α, β-unsaturated monomer. Obtained by chlorinating a terpolymer of saturated monocarboxylic acid ester and ethylene,
It is possible to provide adhesive resin compositions that are excellent in room temperature adhesion and heat seal adhesion to various polymeric materials as well as metals, glass, ceramics, wood substrates, etc., and that are soluble in organic solvents at room temperature. It was done.

The above-mentioned chlorination is carried out according to a known technique after charging a chlorination-resistant solvent such as carbon tetrachloride, chloroform, trichloroethylene and the raw materials into a corrosion-resistant pressurizable chlorination container and completely dissolving them, and then pressurizing. Alternatively, under ordinary pressure, chlorine can be blown in to chlorinate by using ultraviolet irradiation or a radical generator as a reaction catalyst.

The present invention will be described in detail below.

The terpolymer used in the present invention is produced by a known method such as a high pressure radical polymerization method, a solution polymerization method or an emulsion polymerization method, and the monomer monomer is selected from those copolymerizable with ethylene. Specific examples of the carboxylic acid and / or carboxylic acid anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, hymic acid anhydride, and the like. The amount of these carboxylic acids and / or carboxylic anhydrides is about 0.01 to 20% by weight, preferably about 0.1 to 10% by weight.
Is. In addition to the above components, the ethylene copolymer used in the present invention further comprises, as a third component, an α, β-unsaturated monocarboxylic acid ester such as methyl acrylate,
Unsaturated vinyl esters such as ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and the like are included, and the amount of the α, β-unsaturated monocarboxylic acid ester is about 1 to 50% by weight, preferably 3%. ~ 35% by weight. Here, the amount of the above-mentioned carboxylic acid and / or carboxylic anhydride is set to about 0.01 to 20% by weight, which means 0.01% by weight.
If it is less than 20% by weight, the polar group content in the composition becomes too small to obtain sufficient adhesiveness. If it exceeds 20% by weight, gelation occurs during chlorination and the chlorination reaction does not proceed. The amount of the α, β-unsaturated monocarboxylic acid ester as the third component is set to about 1 to 50% by weight because the effect of improving the adhesiveness is not observed below 1% and the adhesiveness exceeds 50% by weight. This is because not only the improvement effect of (3) is not observed but also the advantages of the ethylene polymer such as processability, flexibility and mechanical strength are lost. Further, the degree of chlorination of the chlorinated terpolymer of the present invention obtained by chlorinating the above ethylene copolymer is set to 5 to 50% by weight when the organic content is less than 5% by weight at room temperature or in the vicinity thereof. This is because it is sparingly soluble in a solvent, and on the other hand, when it exceeds 50% by weight, the adhesive strength decreases.

If necessary, a stabilizer, a lubricant, a surfactant, an inorganic filler, a foaming agent, a pigment, an anti-coloring agent and the like may be added to and mixed with the adhesive resin composition of the present invention.

[Action]

As a base material adhered with the adhesive resin composition of the present invention, various synthetic polymer materials, for example, olefin polymers such as polyethylene, ethylene-unsaturated ester copolymer, polypropylene, ethylene-propylene copolymer, and styrene-based materials. Polymers, vinyl chloride polymers, polyesters, polyamides, nylons, ethylene-vinyl acetate copolymers or saponified products thereof, and metals such as aluminum, iron, nickel, zinc, copper and chromium, glass, ceramics, wood, etc. It is possible.

As a method for producing a metal-metal or metal-polyolefin laminate using the adhesive resin composition of the present invention, any technique such as a known lamination method or coating method or a combination method of both can be applied. . Further, in the production of the film or sheet, an extruder coating method, a dry laminating method, a coextrusion molding method and the like can be applied. Also, a method of applying the adhesive resin composition of the present invention to the surface of a metal, a polyolefin film or sheet, glass or the like, and heating and adhering the same, a metal or a polyolefin film or sheet, a glass or the like surface A method of coating the adhesive resin composition of the invention with a powder or a solution, followed by heating and drying to bond, and a method of interposing the adhesive resin composition of the present invention or a solution thereof between these substrates and thermocompression bonding. and so on. The solvent used at this time may be any solvent that can dissolve or disperse the components of the present invention into a coating solution, and for example, one kind of toluene, xylene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, alcohols or the like or It is possible to combine two or more kinds.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Chlorination Method and Adhesion Test Method 3 kg of the terpolymer described in Tables 1 to 3 was charged together with 70 carbon tetrachloride into a glass-lined reaction vessel,
After sufficiently dissolving at 100 ° C. under a pressure of 1.5 kg / cm ^2, a predetermined amount of gaseous chlorine was blown from the bottom of the reaction vessel while irradiating with ultraviolet rays to carry out a chlorination reaction.

Adhesion test against aluminum is aluminum foil (20μ) / adhesive resin (3μ) / aluminum foil (20μ)
μ) configuration using a heat sealer at 120-150 ° C for 1 second,
It was pressure-bonded under the condition of ² kg / cm ² and evaluated at an angle of 180 ° and a pulling speed of 30 mm / min. Adhesion between aluminum and polyethylene in the adhesion test is aluminum foil (20μ) / adhesive resin (3μ) / polyethylene film (30μ) using a heat sealer at 70-110 ° C, 1 second, 1kg / cm ² conditions. It was crimped and evaluated at an angle of 180 ° and a pulling speed of 30 mm / min.
The adhesion between aluminum and polypropylene in the adhesion test uses a heat sealer consisting of aluminum foil (20μ) / adhesive resin (3μ) / polypropylene film (50μ).
It was crimped under the conditions of 90 to 120 ° C., 1 second and 1 kg / cm ² , and evaluated at an angle of 180 ° and a pulling speed of 30 mm / min.

The aluminum foil used in the above test was manufactured by Showa Aluminum Co., Ltd., the polyethylene film was a high-density polyethylene film manufactured by Okura Industry Co., Ltd., and the polypropylene film was an untreated polypropylene film manufactured by Toyobo Co., Ltd., respectively. Using.

Examples 1 to 4 and Comparative Examples 1 to 2 A chlorinated ethylene-ethyl acrylate-maleic anhydride copolymer having a chlorination degree of 10 ± 0.5% was used to apply a predetermined amount of a 20% toluene solution to a substrate, and the temperature was adjusted to 80 ° C. After drying for about 30 minutes, the respective substrates were laminated with a heat sealer to perform an adhesion test. The results are shown in Table 1.

The contents of ethylene, ethyl acrylate, and maleic anhydride are shown in the table. As comparative examples, chlorinated products of ethylene-ethyl acrylate copolymer and chlorinated products of high-pressure low-density polyethylene were used. The solution viscosity is a value measured at 20 ° C. using a B type viscometer of a 20% toluene solution.

Examples 5 to 8 and Comparative Examples 3 to 4 The results were shown in Table 2 according to Examples 1 to 4 except that the degree of chlorination was 20 ± 0.5%.

Examples 9 to 12 and Comparative Examples 5 to 6 The results were shown in Table 3 according to Examples 1 to 4 except that the degree of chlorination was 30 ± 0.5%.

From the above results, it became clear that the adhesive resin composition of the present invention has high adhesive strength.

Claims (3)

[Claims] 1. From an unsaturated carboxylic acid monomer having one or more carboxyl groups selected from carboxylic acids and / or carboxylic anhydrides, an α, β-unsaturated monocarboxylic acid ester and ethylene An adhesive resin composition containing a chlorinated product obtained by chlorinating the ternary copolymer. 2. The terpolymer is characterized by containing 0.01 to 20% by weight of a carboxylic acid and / or carboxylic acid anhydride and 1 to 50% by weight of an α, β-unsaturated monocarboxylic acid ester. The adhesive resin composition according to claim (1). 3. The chlorine content of the chlorinated terpolymer is 3 to 50.
The adhesive resin composition according to claim (1) or (2), characterized in that the content is% by weight.