JPS592454B2 - adhesive resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a resin composition having good adhesive strength.

More specifically, the present invention relates to a resin composition comprising a saponified ethylene-vinyl acetate copolymer (hereinafter referred to as saponified EVA) or a saponified EVA, an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), and a polyamine. Its purpose is to produce organic polymer materials, metals, inorganic materials,
The object of the present invention is to obtain a resin composition that has excellent adhesion to various materials such as cellulose-based natural materials, and also has excellent melt flowability and moldability.

Films, made from saturated polyester, among others
The object of the present invention is to obtain a resin composition that has excellent adhesion to sheets and various molded products, and also has excellent melt flowability and molding processability. Conventionally, an enormous number of techniques have been proposed for adhesives containing EVA or its saponified product as one component.

They can be roughly divided into the following three categories. 1.EVA
or multilayer films, sheets, and containers with a single layer of its saponified product2; use of EVA or its saponified product as a coating agent for paper, metal, glass, etc.;3 use of EVA or its saponified product as an adhesive for fibers, etc. Although we have shown sufficiently satisfactory performance for certain materials and applications, it cannot be said that some materials still have satisfactory performance. condition.

One of these is the adhesion of polyester. Conventionally, polyester resin has excellent mechanical strength, water resistance, and gas barrier properties, and has been widely used as a laminate film for food packaging and retort pouches.

On the other hand, since polyester resins have poor adhesive properties, hot melt adhesives, film adhesives, and the like cannot be used for adhesion, and methods such as polyurethane dry lamination have had to be used. However, this method does not have sufficient adhesive strength and uses a solvent, which causes air pollution and
There are many other problems, such as the risk of explosion, and the resulting film has a solvent odor. Furthermore, in order to improve adhesion, a method of hydrolyzing the polyester surface with alkali is also known, but this method also requires large-scale equipment for hydrolysis, and a large increase in price can be avoided. Nakatsuta. As described above, hot melt adhesives and film adhesives for polyester are currently not well known, and their appearance has been awaited.

The present inventors have conducted extensive research in order to further improve the adhesive performance of EVA or its saponified product, and to make it effective on more materials. The present inventors have discovered that by mixing polyamines in a specific ratio, a composition with improved adhesive performance to many materials can be obtained. It was discovered that this adhesive has significantly higher adhesion performance than saturated polyester, which exhibited only insufficient adhesion performance, and the present invention was achieved based on this discovery.

The present invention will be explained in detail below.

The EVA used in the present invention is produced by either a high-pressure radical polymerization method, a solution or emulsion polymerization method, and has a vinyl acetate content of 1 to 6.
0% by weight, melt index 0.1-5009/1
Preferably, the time is 0 minutes.

Further, as the saponified EVA, it is preferable to saponify the above-mentioned EVA by 5 to 100 mol%.

The saponification reaction may be carried out using an acid or an alkali as a catalyst according to a known saponification method. Next, the polyamine used in the present invention is represented by the general formula (excluding polyethyleneimine, which is a polymer of ethyleneimine obtained by polymerizing ethyleneimine with an acid catalyst), and has a boiling point of It is desirable that the temperature is 200°C or higher. in particular,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine,
Examples include aminoethylpiperazine and diethylenediaminopiperazine.

There is no problem even if a plurality of these polyamines are used in combination. The quantitative ratio of EVA saponified product or EVA saponified product and EVA to polyamine is determined by comprehensively considering its melt viscosity, processability, mechanical strength, and other factors in relation to the specific use of the resin composition. It can be decided.

Specifically, the polyamine is EVA saponified product or EVA
1 to 20 parts by weight of saponified material and EVAlOO
Parts by weight are preferred.

This is because within this range, a resin composition with improved adhesiveness can be obtained and has physical properties and properties that can be used in extrusion coating resins, films, and adhesives. Next, as the mixing and kneading method, a method of melt-kneading with a single-screw or twin-screw extruder, a method of kneading with a roll, a Banbury mixer, etc. are used.

The kneading temperature is determined in relation to the melting point of EVA or its saponified product, the decomposition temperature, and the boiling point of the polyamine. Specifically, the temperature is preferably 120°C or more and 200°C or less. The kneading time may be selected so as to provide a uniformly mixed resin composition. As another mixing method, a method using a solvent can also be applied.

For example, EVA saponified product or EVA saponified product and EVA saponified product
VA is dissolved in a solvent that is a good solvent for VA and has good compatibility with polyamine, and the solution and polyamine are mixed to form a uniform solution.

There is also a method in which the solvent is then removed to obtain a uniformly mixed resin composition. As described above, the composition of the present invention is particularly effective as an adhesive between polyester and polyester or between polyester and other materials.

Furthermore, the composition of the present invention can also be used in applications where EVA or its saponified product has conventionally been used as an adhesive. In other words, it can be applied to many applications, such as surface treatment of inorganic materials such as glass, coating and adhesives for cellulosic materials such as paper and fibers, metal coating agents, and adhesive materials for organic polymer materials. This has the effect of further increasing adhesive strength to many materials such as.

The composition of the present invention can be used effectively in any form such as film, pellet or powder.

Also, of course, other materials (especially polyester)
By coating the material, it can be used as a film or even as a multilayer film (sheet).
Depending on the type of use, known additives such as heat stabilizers, antioxidants, anti-protective agents, slip agents, antistatic agents, colorants, etc. may be added. As described above, the composition of the present invention is particularly useful as a material for adhesives for polyester, and its contribution to industries including packaging materials is extremely large. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way.

Examples 1-2, Comparative Examples 1-3 Using a 3-inch roll, pentaethylenehexamine (hereinafter abbreviated as PEHA) and EV
Compositions were produced in which the proportions of the saponified substances were varied.

As EVA saponification product, vinyl acetate content is 28wt%
, Melt Index (hereinafter abbreviated as MI) 189/10
EVA having a Vicat softening point of 43° C. was saponified to 80 mol % with sodium hydroxide.

After melting the EVA saponified product, PEHA was added and 130
The mixture was kneaded at ℃ for 5 minutes.

This composition was made into a 100P film, sandwiched between a 0.1 fin film of polyethylene terephthalate (hereinafter abbreviated as PET) and a 271Jm aluminum plate, and heated to 150°C.
, 0.1K'/pe for 5 minutes, and the 18
The 0 degree peel strength was measured. The results are shown in Table 1.

Examples 3 to 4, Comparative Example Similar tests were conducted in Example 1 except that the polyamine was replaced with aminoethylpiperazine (hereinafter abbreviated as AEP).

The results are shown in Table-2.

Claims (1)

[Claims] 1. Polyamine (with the exception of polyethylene, which is a polymer of ethyleneimine) per 100 parts by weight of saponified ethylene-vinyl acetate copolymer or saponified ethylene-vinyl acetate copolymer and ethylene-vinyl acetate copolymer. An adhesive resin composition containing 1 to 20 parts by weight of (excluding imine). 2
Polyamines are represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Excluding polyethyleneimine, which is a polymer of ethyleneimine.) The boiling point is 200℃ or higher. Claim 1 which is
Compositions as described in Section. 3. The saponified ethylene-vinyl acetate copolymer has a melt index of 0.1-500 g/10 minutes and contains 1-60% by weight of vinyl acetate. The composition according to claim 1 or 2, wherein the copolymer is saponified in mol%. 4 0.1 to 500 g of ethylene-vinyl acetate copolymer
/10 minutes melt index, 1-60% by weight
4. The composition according to claim 1, 2 or 3, wherein the copolymer contains vinyl acetate.