JPS62196144A - Cover material for sealing perfume filled glass vessel - 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] Industrial Application Field This invention relates to a container sealing lid material used to seal a glass container filled with spices containing a large amount of flavor components, food or cosmetics containing flavoring agents. .

Conventional technology and its problems Conventionally, the lid material for glass containers for powdered, liquid, or fluid foods has generally been made by providing a thermal adhesive layer made of hot melt resin on one side of aluminum foil. Met.

However, when this lidding material is filled with spices and fragrances such as koshiyo, sansho, and ginger, the hot melt part is eroded by the fragrance components contained in these contents, and the heat sealing strength gradually decreases. decreased to
There was a problem in that the lid naturally peeled off from the mouth of the container, resulting in a loss of commercial value.

In view of the above points, the present invention provides a sealing lid material that has good thermal adhesion to glass containers filled with spices and fragrances and is completely free from erosion by fragrance components. The purpose is to

Means for Solving Problems The lid material for sealing glass containers according to the present invention includes a polyolefin-based material that has good thermal adhesion to glass containers and excellent corrosion resistance to contents containing spices or fragrances on one side of metal foil. A thermal adhesive layer made of resin is provided.

Here, examples of polyolefin resins having the above characteristics include ethylene-containing ff150 to 97 mol%.
carboxyl-modified resin of a saponified ethylene-vinyl acetate copolymer (hereinafter referred to as modified resin <A)], which is obtained by graft polymerizing a carboxylic acid group-containing unsaturated compound to a saponified ethylene-vinyl acetate copolymer of and α, β
- Copolymer with ethylenically unsaturated carboxylic acid α, β-
Content of ethylenically unsaturated carboxylic acid is 5 to 15% by weight
Examples include ionomer resins in which 0.5 to 40% of the carboxylic acid groups are neutralized with metal ions (hereinafter referred to as ionomer resins (B)) and ethylene-acrylic acid copolymer trees.

One example of the thermal adhesive layer is modified resin (A
) and/or an ionomer; other examples of the thermal adhesive layer include those consisting of a modified resin (A>) and an inorganic compound; Examples include those made of ethylene-acrylic acid copolymer resin.

Glass containers for sealed packaging are generally made of soda lime glass. Further, although aluminum foil is usually used as the metal foil, other metal foils may also be used. In the case of aluminum foil, its thickness is 10 to 100
μm, preferably 40 to 60 μm.

When the modified resin (A) is used in combination with the ionomer resin (B), the composition ratio is the modified resin (A>10-9
0% by weight, preferably 30 to 80% by weight, and 5 to 90% by weight, preferably 20 to 70% by weight of the ionomer resin (B), and these components (A) and (B) are processed by, for example, a single screw extruder, 2 A thermal adhesive composition can be obtained by mixing using a axial press ratio machine, a Banbury mixer, a kneader, etc. under a temperature condition of usually 120 to 180°C.

Modified resin (A) which is an example of polyolefin resin
For example, an ethylene-vinyl acetate copolymer having an ethylene content of 50 to 97 mol%, preferably 70 to 92 mol%, is saponified to obtain a hydroxyl group a of 100 to 3000 a/1.
equivalent, preferably 200 to 1000 (+/1 equivalent), and then graft polymerization of a carboxylic acid group-containing unsaturated compound to this saponified product is used. Examples of group-containing unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, etc.The obtained modified resin (A) has an acid concentration of 950% as a whole.
000M 1 equivalent or less, especially 1000 to 10000 (j
/1 equivalent is preferred. The reason why the hydroxyl equivalent value of the saponified product is limited to the range of 100 to 300 h/1 equivalent and the acid equivalent value of the modified resin (A) is limited to the range of 50,000 (1/1 equivalent or less) is that these equivalent values If the temperature is outside the above range, the low-temperature sealing properties of the thermal adhesive layer will deteriorate, and the sealing strength will decrease due to water when foods with a high moisture content are hermetically packaged.

Examples of the α,β-ethylenically unsaturated carboxylic acid of the ionomer resin (B), which is another example of the polyolefin resin, include acrylic acid, methacrylic acid, ethacrylic acid,
Examples include itaconic acid, maleic acid, fumaric acid, and the like. Monoesters and acid anhydrides of dicarboxylic acids such as maleic acid and fumaric acid can also be used as the α,β-ethylenically unsaturated carboxylic acids.

The reason why the content of α, β-ethylenically unsaturated carboxylic acid in the ionomer resin (B) is limited to 5 to 15% by weight is that if it is less than 5% by weight, the melting point of the resin is too high and the heat sealability at low temperatures is poor. Not only that, but the adhesion to glass containers deteriorates, and on the other hand, if it exceeds 15% by weight, the melting point of the resin is too low, resulting in weak adhesion immediately after heat sealing, which tends to result in products with poor adhesion. be.

As the metal ions for neutralization, 1.2 and trivalent metal ions are used. Particularly preferred are divalent Zn ions.

The reason why the degree of neutralization of α, β-type ethylenically unsaturated carboxylic acid by metal ions is limited to 0.5 to 40% is that 0
．． If it is less than 5%, the advantages of ionic copolymer resins, such as good low-temperature heat sealability, hot sealability, and oil resistance, will not be fully exhibited, and if it exceeds 40%, the moisture absorption rate will be high and the saturated water content will be low. This is because it becomes high.

When the modified resin (A) is used in combination with an inorganic compound, the proportion of the inorganic compound is 30% by weight or less, usually 0.
The amount is 1 to 10% by weight, preferably 1 to 5% by weight, and a thermal adhesive composition can be obtained by mixing both under the same conditions as above.

Examples of inorganic compounds include magnesium, calcium,
Examples include oxides, hydroxides, carbonates and sulfates of aluminum, titanium and silicon, talc, clay, feldspar powder, mica, pallite and the like, with calcium carbonate and talc being particularly preferred. The average particle size of the inorganic compound used is 0.1 to 50 μm, preferably 0.5 to 30 μm.
It is m.

Ethylene-acrylic acid copolymer resin (hereinafter referred to as EAA), which is yet another example of polyolefin resin
Commercially available products such as those manufactured by DuPont Mitsui Polychemicals Co., Ltd. are used.

To provide a thermal adhesive layer on one side of a metal foil, a film formed from the above-mentioned thermal adhesive is applied to one side of the metal foil via an adhesive such as a two-component reactive adhesive based on polyester-isocyanate. They may be bonded together, or they may be bonded via an anchor coat layer by extruding a melted thermal adhesive onto one side of the metal foil using an extruder.

The thickness of the thermal adhesive layer is usually 10 to 150 μm, preferably 30 to 60 μm, and if necessary, a resin film such as polyethylene or polypropylene may be interposed between the layer and the metal foil. This improves the cushioning properties during heat sealing. Further, an anticorrosive coating layer may be provided between the gold a foil and the thermal adhesive layer. Note that the other side of the metal foil is printed as required, and furthermore, an anticorrosive coating layer is provided on this surface. Paper may also be attached to the other side of the metal foil via an adhesive layer or a polyethylene layer. A lid made of metal foil and a thermal adhesive layer is continuously hammered and formed into a shape and size that covers the mouth of a glass container.

The accompanying drawings show specific examples of the lid material according to the present invention. First, the lid material shown in Figure 1 is aluminum foil (1).
A thermal adhesive layer (2) is provided on one side via an adhesive layer (3), and an anticorrosive coating layer (4) is provided on the other side.

In addition, the lid shown in Figure 2 uses aluminum foil (1) to prevent corrosion of the aluminum foil (1) by the contents of the container.
An anti-corrosion coating layer (6) is provided on one side of the aluminum foil (1), a thermal adhesive layer (2) is provided on the surface via an adhesive layer (3), and a printed H is provided on the other side of the aluminum foil (1). (5) is provided, and an anticorrosion coating layer (4) is further provided on the surface thereof.

Furthermore, the lid material shown in Fig. 3 has an anchor coat B (7) and a polyethylene layer (8) on one side of the aluminum foil (1).
A thermal adhesive layer (2) is provided therebetween, and paper (10) is pasted on many sides with polyethylene layers (9) interposed therebetween.

Functions and Effects of the Invention Since the present invention is constructed as described above, even in a glass container filled with contents containing spices or fragrances, the lid material has excellent thermal adhesion to the glass container and is highly adhesive to the fragrance ingredients. There is no risk of erosion. Therefore, by using the lid material according to the present invention, the contents containing a large amount of fragrance components can be preserved for a long period of time.

Example Next, examples of the present invention will be described together with comparative examples.

Example 1 Modified resin (A) was obtained by graft polymerizing acrylic acid to a saponified product of an ethylene-vinyl acetate copolymer with an ethylene content of 87 mol% as a polyolefin resin for forming a thermal adhesive layer. Hydroxyl equivalent: 49
0a/1 equivalent and 12880 (1/1 equivalent) carboxyl modified product were used.

As shown in FIG. 1, a 50 μm thick aluminum foil (1) having an anti-corrosion coating layer (4) on one side is coated with a 50 μm thick thermal adhesive layer (2) made of the above modified resin (A) on the other side.
) were bonded together via the adhesive layer (3) to create a lid material.

The obtained lid material was punched out using a punching press into a predetermined shape and size corresponding to the opening of a glass container. During press working, there was no blocking of the thermal adhesive layer (2) of the lid material, and the molding process could be performed smoothly.

Next, a glass container is filled with koshiyo, and the lid material is heated and pressurized for 2 seconds at a temperature of 170° C. and a pressure of 160 kg/piece for 2 seconds, and the lid material is heated directly to the mouth of the glass container. The container was sealed with adhesive.

Example 2 Ionomer resin (B) as polyolefin resin
: An ethylene/methacrylic acid copolymer with a methacrylic acid content of 10% by weight and 10% of the methacrylic acid groups neutralized with Zn was used, and other operations were carried out as in Example 1.
I did the same thing.

Example 3 EAA was used as the polyolefin resin, and other operations were performed in the same manner as in Example 1.

Comparative Example Kosho was hermetically packaged in a glass container in the same manner as in Example 1 using a lid material made of aluminum foil with a thickness of 501 m and a thermal adhesive layer made of hot-melt resin on one side.

Heat-sealing strength test After the glass containers encapsulating the porridge obtained in the Examples and Comparative Examples were left under predetermined conditions, the heat-sealing strength of the lid material was measured.

The measurement results are shown in Table 1. The heat-sealing strength was determined by forming a tongue-like part with a width of 15 mm on the lid material joined to the mouth part, and measuring the maximum load when the base of the tongue-like part peeled off from the heat-sealing part by pulling it directly upward. It is expressed by

(Margin below) As is clear from Table 1, the lid material of the example has a larger heat seal than the lid material of the comparative example even after being left for a long period of time under both room temperature and high temperature and high humidity conditions. Can maintain strength. Therefore, compared to the lid material of the comparative example, the lid material of the example has extremely good thermal adhesion to the glass container filled with contents containing spices and fragrances, and there is no risk of corrosion by the fragrance ingredients. It can be seen that the above contents can be stored for a long period of time.

[Brief explanation of drawings]

Fig. 1 is a partially enlarged cross-sectional view showing a specific example of the product of the present invention;
The figure is a partially enlarged sectional view showing another specific example of the product of the present invention, and FIG. 3 is a partially enlarged sectional view showing still another specific example of the product of the present invention. (1)... Aluminum foil, (2)... Thermal adhesive layer, (3)... Adhesive layer, (4) (6)... Anti-corrosion coating layer, (5)... Printing layer, (7)...anchor coat layer, (8)(9)...polyethylene layer, (10)...
··paper. Patent applicant Showa Aluminum Co., Ltd. ■ (April 70, 1988 1. Indication of the case Patent Application No. 37871 of 1988 2, Title of invention Sealing lid material for glass containers filled with fragrances 3, amendments Relationship with the case filed by the patent applicant Address: 6-224 Kaizan-cho, Sakai City Name: Showa Aluminum Co., Ltd. 4, Agent

Claims (4)

[Claims] (1) A thermal adhesive layer made of a polyolefin resin that has good thermal adhesion to glass containers and excellent corrosion resistance to contents containing spices or fragrances is provided on one side of the metal foil. Lid material for sealing glass containers. (2) The thermal adhesive layer has an ethylene content of 50 to 97 mol%
A carboxyl-modified resin (A) of a saponified ethylene-vinyl acetate copolymer obtained by graft polymerizing a carboxylic acid group-containing unsaturated compound to a saponified ethylene-vinyl acetate copolymer, and/or ethylene and α, β - Copolymer with ethylenically unsaturated carboxylic acid, the content of α,β-ethylenically unsaturated carboxylic acid is 5 to 15% by weight, and 0.5 to 40% of the carboxylic acid groups are neutralized with metal ions. The lid material according to claim 1, which is made of the ionomer resin (B). (3) The thermal adhesive layer has an ethylene content of 50 to 97 mol%
A patent claim consisting of a carboxyl-modified resin (A) of a saponified ethylene-vinyl acetate copolymer obtained by graft polymerizing a carboxylic acid group-containing unsaturated compound to a saponified ethylene-vinyl acetate copolymer, and an inorganic compound. range 1
Lid material as described in section. (4) The lid material according to claim 1, wherein the thermal adhesive layer is made of an ethylene-acrylic acid copolymer resin.