JPS59158253A - Laminate for packing - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to base materials such as metal, plastic film, paper, etc.
The present invention relates to a packaging laminate in which resin composition layers containing an ethylene-vinyl acetate copolymer or an acid-modified product thereof as a main component are laminated, and an adhesive layer made of an acid-modified polyolefin and an organic silicon compound is further applied. More specifically, it is a packaging laminate that has high adhesion to containers made of glass or ceramic materials by high-frequency sealing or heat sealing, and has excellent content resistance (water, juice, soy sauce, etc.). Regarding.

It is currently known to use sotomelt adhesives to seal containers made of glass or ceramic materials. However, although this method provides sufficient adhesive strength when the content is solid, it has the disadvantage that adhesive strength decreases over time when the content is liquid.

On the other hand, a method of attaching an organic silicon compound, etc. to the container side is also known (Japanese Patent Application Laid-open No. 151608/1983), but in this method, the organic silicon compound, etc. is applied to the glass container or ceramic container in advance using a special device. This raises problems in terms of economy, workability, etc.

In order to improve these conventional drawbacks, the present inventors conducted extensive research and found that ethylene-vinyl acetate copolymer (hereinafter referred to as EVA
) or an acid-modified product thereof (hereinafter referred to as the resin composition) is laminated, and further acid-modified polyolefin and organic silicon having a hydroxyl group, a hydrolyzable group, or an acid-reactive group are laminated. A laminate coated with an adhesive made of a compound (hereinafter referred to as the adhesive) has high adhesion to glass containers or ceramic containers by high frequency sealing or heat sealing, and has high resistance to contents (
The present invention was completed based on the discovery that the present invention is superior to water, juice, soy sauce, etc.).

Examples of the base material used in the present invention include metals such as aluminum, iron, tin, nickel, and copper, plastic films such as polyester, nylon, polyolefin, and polyvinyl chloride, and paper, and these may be appropriately combined. It doesn't matter.

-The relevant tree Ill? The composition is as follows (1)
group, (IJ) group, (nl)ff#, and (IV) group.

(1) EVA (vinyl acetate content 10-35% by weight)
) (n) Acid-modified EVA (vinyl acetate content 5-35%) (III) Polyethylene (low density, medium density, high density, linear low density) Acid-modified polyethylene, ethylene-α olefin Polymer, acidic polypropylene, isotactic polypropylene, acid-modified polypropylene (IV) rosin, rosin-modified product, terpene resin, terpene-modified product)! [The mixing ratio of each group of resin, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, alicyclic hydrocarbon resin, and ketone resin is group (1), 0 to 95% by weight, group (11), 50 to 100% by weight. %, (ITI) group, 0 to 30% by weight, (I
Group V) can be selected from 0 to 30% by weight.

Next, the said adhesive consists of groups (A) and (B), and the acid-modified polyolefins of group (A) include acid-modified polyethylene, ethylene-α olefin acid-modified products, and acid-modified polypropylene. Examples include acid-modified products of propylene-α-olefinic acid, and acid-modified products of ethylene-vinyl acetate copolymer. Among these, ethylene-α
Ethylene-butene-1 copolymer is most suitable as the olefinic acid modified product. The ethylene content of the ethylene-butene-1 copolymer is 40 to 85 mol%, preferably 5
It is 5 to 85 mol%.

In addition, examples of unsaturated carboxylic acids or anhydrides thereof to be graft-polymerized to the ethylene-butene-I copolymer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, citraconic anhydride, and anhydride. Examples include itaconic acid. Among these, it is most preferable to use maleic anhydride.

As a method for grafting the x thi L/ y 7 phthene-1 copolymer and the unsaturated carboxylic acid or its anhydride, various known methods can be employed. For example, this can be carried out by adding a radical generator to both in the presence or absence of a solvent and heating the mixture at a high temperature. The amount of the graft monomer of the ethylene-butene-1 copolymer to be grafted is 0.01 to 5% by weight, preferably 0.05 to 2% by weight.
Weight%. The acid-modified polyolefin is a composition dissolved in a solvent such as a monoaromatic hydrocarbon such as toluene, xylene, heptane, or octane, or an aliphatic hydrocarbon, and is stable at room temperature.

The organosilicon compounds of group (B) include those having a hydroxyl group or a hydrolyzable group and an acid-reactive group. The term "hydrolyzable group" herein refers to a group that can become a hydroxyl group by hydrolysis, and includes an alkoxyl group, an acyloxy group, a halogen, etc., and the term "acid-reactive group" refers to a group such as a vinyl group,
It is a group having an alkenyl group such as 7 /L/ IJ /l/ group, an amino group, an epoxy group, a hydroxyl group, a mercapto group, an isocyanate group, etc. Hydroxyl or hydrolyzable groups are directly bonded to silicon, acid-reactive groups are alkenyl groups, epoxy groups, etc. may be directly bonded to silicon, but others are alkylene groups, Those bonded to silicon via a hydrocarbon group such as an arylene group are preferred. Among these, preferred are organosilicon compounds represented by the general formula (where R is a group containing an acid-reactive group, and R' is a hydroxyl group or a hydrolyzable group).

Specifically, γ-aminopropyltriethoxysilane,
γ-aminotripropoxysilane, γ-aminopropylmethyljethoxysilane, aminoethyltriethoxysilane, δ-aminobutyltriethoxysilane, δ-aminobutylphenyldiethoxysilane, N-β-aminoedyl-γ-aminopropyltriethoxysilane Methoxysilane, N-γ
-Aminopropyl-γ~aminopropyltriethoxysilane, N-γ-aminoisobutylene-T-aminopropyltriethoxysilane, aminoalkylalkoxysilane, epoxyethyltriethoxysilane, epoxyethyltriethoxysilane, γ-glycyltriethoxysilane, etc. Epoxyalkoxysilanes such as cidoxypropyltrimethoxysilane, 1°2-epoxybutyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, alkenylalkoxysilanes such as vinyltris(β-methoxyethoxy)silane, alkenylacetoxysilanes such as vinyltriacetoxysilane,
Examples include N-bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane.

Among these, vinyl tris (β-methoxyethoxy)
Most preferably, silane is used. The organosilicon compound is dissolved in a solvent such as an aromatic hydrocarbon such as toluene, xylene, heptane, octane, etc.

The mixing ratio of group (A) and group (B) is 10 to 90% by weight to 9 to 10% by weight, preferably 25 to 75% by weight to 75 to 25% by weight. be. In addition, when one of the two groups is 100x90, both have poor content resistance.

The laminate according to the present invention has a base material typified by aluminum foil,
One layer of the tree III composition can be easily formed by extrusion lamination or dry lamination, and then the adhesive is applied to a gravure printing machine, a dry laminate coating machine, an anchor coating agent coating device of an extrusion laminator, and the like. It can be easily obtained by coating by a conventionally known method such as a gravure coating method using a general lacquer coater or a roll coater.

The laminate according to the present invention 6 has high adhesion to glass containers and ceramic containers by introducing the resin composition and the adhesive, and has good resistance to contents (water, juice, soy sauce, etc.). can provide excellent sealed packaging containers. .

Next, examples and comparative examples will be shown.

<Example-I> Low-density polyethylene (2i+) was extruded and laminated on aluminum foil (30μ) in advance, and acid-modified products of F and VA (Modison, Mitsubishi Yuka, and A) were added to the base material.
Kiku) 70% heavy weight, ethylene-α olefin copolymer (
Tafmar P-0180, Ei Petrochemical Industry Co., Ltd. 10
A resin composition consisting of 20% by weight of an alicyclic hydrocarbon resin (Alcon P-90, manufactured by Arayo Kagaku Kogyo O1) was mixed and laminated to a thickness of 25p by extrusion lamination.

In the method, a reaction product of 0.3 mi% of maleic anhydride and 99.7% by weight of ethylene-butene-1 copolymer was adjusted to a 0.5% solution with a mixed solution of toluene and n-heptano, and further, Vinyltris(β-methoxyethoxy)silane was adjusted to a 0.5% solution with n-hebutane. The two are mixed in a 1:1 ratio, and the resulting adhesive is applied to the resin composition described above to a thickness of about 0.1 μm using a gravure coating method,
A laminate was obtained by evaporation drying.

1) Combine the above laminate with a glass plate at a temperature of 200℃ and a pressure of 3kg/
ad.

Heat sealed for 1 second, peeling speed 100f
1/mjn, 15 mm Tjl, and 180° peeling adhesive strength was measured. Furthermore, the heat-sealed products under the above conditions were immersed in water, juice, soy sauce, and sake, and the heat-sealed strength after 60 minutes was measured. These results are shown in Table-1.

<Example-2> EVA (NUC) was used instead of the resin composition of Example-1.
3190i Nippon Unicar R[) 60% by weight, polyethylene (Sumi Rikisen L-405, manufactured by Sumitomo Chemical 611) 1
0-steel, ethylene-α olefin copolymer (Tafmer P-0180, manufactured by Mitsui Petrochemical Industries, Ltd.) 10-steel, alicyclic hydrocarbon resin (Alcon P-90, manufactured by Arayo Chemical Industries, Ltd.)
The same procedure was carried out except that a resin composition mixed at a ratio of 20% by weight (manufactured by Kawasaki Co., Ltd.) was used. The results are shown in Table-1.

<Comparative Example-1> The same procedure was carried out as in Example-1 except that the adhesive was not used. The results are shown in Table-1.

<Comparative Example-2> The same procedure was carried out except that the adhesive of Example-2 was not used. The results are shown in Table-1.

<Comparative Example-3> The same procedure was carried out as in Example-1 except that polyethylene was used instead of the 4&l 1lli composition. The results are shown in Table-1.

<Comparative Example-4> The same procedure was carried out as in Comparative Example-3 except that the adhesive concerned was not used. The results are shown in Table-1.

<Comparative Example-5> The same procedure was carried out as in Example-1 except that polypropylene was used instead of the resin composition. The results are shown in Table-1.

<Comparative Example-6> The same procedure was carried out as in Comparative IF Example 2-5 except that the adhesive was not used. The results are shown in Table-1.

<Comparative Example-7> The same procedure was carried out as in Example-1 except that only EVA (Ultrasen 541, manufactured by Toyo Soda Kogyo Co., Ltd.) was used instead of the 461 fatty silk composition.The results are shown in Table-1. Shown below.

<Comparative Example-8> The same procedure was carried out as in Comparative Examples-7 except that the adhesive concerned was not used. The results are shown in Table-1.

<Examples 3 to 5> Using the adhesive of Example 1, the mixing ratio of acid-modified polyolefin and organosilicon compound was changed to make the content resistant to water.
The same thing happened outside. The results are shown in Table-2.

Comparative Examples-9 to 10> Comparative Examples-9 to 1o are the cases in which the adhesive of Example-1 contains 0% by weight of acid-modified polyolefin and 0% by weight of organosilicon compound.
It is shown in Table-2.

<Example 6> Example 6 was carried out in the same manner as in Example 1 except that the organosilicon compound was replaced with vinyltriethoxysilane and the content resistant material was replaced with water.

The results are shown in Table-3.

<Example-7> The same procedure was carried out as in Example-6 except that the organic silicon compound was replaced with vinyltrimethoxysilane. The results are shown in Table-3.

<Example-8> The same procedure as in Example-6 was carried out except that the organosilicon compound was replaced with T-glycidoxypropyltrimethoxysilane. The results are shown in Table-3.

<Example 9> The same procedure as in Example 6 was carried out except that the organosilicon compound was replaced with γ-methacryloxypropyltrimethoxysilane.

The results are shown in Table-3.

Table-1 Table-2 Table-3

[Brief explanation of the drawing]

Figure 1 shows a cross section of the laminate of the present invention, where 1 is a base material, 2 is a resin composition layer, and 3 is an adhesive layer.

Claims (1)

[Claims] A base material such as metal, plastic, or paper [1, a composition layer 2 whose main component is an ethylene-vinyl acetate copolymer or an acid-modified product thereof, and an acid-modified polyolefin and a hydroxyl group or a hydrolyzable group or an acid reaction A packaging laminate comprising an adhesive layer 3 obtained by mixing an organic silicon compound having a chemical group.