JPH04215983A - Laminated tube container - Google Patents

Abstract

PURPOSE:To prevent the growth of bacteria and fungi for an extended period of hour by forming the film layer containing an antibacterial zeolite as antibacterial agent on the inner and/or outer surface of the barrier layers of aluminum foil. CONSTITUTION:A laminated tube container 1 which comprises forming an antibacterial zeolite containing film layer 5 on each of an inner surface 2 and an outer surface 3 of the laminated sheet 4 constituting the container; and providing synthetic resin layers 7 and 8 on the inner and outer surfaces of an aluminum foil 6 in the laminated sheet 4, the aluminum foil 6 having a gas-barrier character, whereby the surface beauty and printability of the outer synthetic resin later 8 are improved and whereby the contents of the container are protected by the inner synthetic resin layer 7.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to laminated tube containers. More particularly, the present invention relates to a laminate tube container whose inner and/or outer surface has antibacterial properties.

0002

[Prior Art] Tube containers have conventionally been used for various purposes such as cosmetics, pharmaceuticals, and food products. It is desirable that bacteria and mold do not grow inside.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated tube container that can prevent the growth of bacteria, mold, etc. even when food or the like is stored in the tube container for a long time.

0004

[Means for Solving the Problems] As a result of intensive research in view of the above-mentioned prior art, the present inventors have discovered that if a coating layer containing antibacterial zeolite is provided on the inner surface and/or outer surface of the Surprisingly, they discovered for the first time that it is possible to prevent the growth of bacteria and mold even when food is stored in a container for a long time, leading to the completion of the present invention.

That is, the present invention provides a barrier layer 6 of aluminum foil.
The present invention relates to a laminated tube container having a coating layer 1 containing antibacterial zeolite as an antibacterial agent on its inner surface 2 and/or outer surface 3.

[0006]

[Function] The coating layer containing antibacterial zeolite suppresses the growth of bacteria that adhere to its surface, and keeps the contents and areas that the user does not touch clean.

[0007] Furthermore, antibacterial zeolite has no effect on the human body, nor does it affect usage conditions such as extruding the contents from a laminated tube container.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the laminate tube container of the present invention will be explained with reference to the drawings.

FIG. 1 is a partially cutaway side view showing an embodiment of the laminate tube container of the present invention, and FIG. 2 is a side view of the container shown in FIG.
FIG. 3 is an enlarged sectional view of a main part showing another embodiment of the laminate tube container of the present invention.

The laminate tube container 1 shown in FIG. 1 has an inner surface 2 and an outer surface 3 of a laminate sheet 4 constituting the container.
A coating layer 5 containing antibacterial zeolite is provided on each of the surfaces.

In the container 1 shown in FIG. 1, the coating layer 5 may be provided only on either the inner surface 2 or the outer surface 3, and this can be changed as appropriate depending on the conditions in which the tube container is used.

The laminate sheet 4 shown in FIG. 1 is made by providing synthetic resin layers 7 and 8 on the inner and outer surfaces of an aluminum foil 6, as shown in FIG. The aluminum foil 6 has gas barrier properties, the outer synthetic resin layer 8 improves the beauty of the surface and printability, and the inner synthetic resin layer 7 protects the contents.

In the laminated tube container shown in FIG.
An antibacterial sheet 9 consisting of a coating layer 5 containing antibacterial zeolite particles and a synthetic resin base layer 5a laminated in advance on the back surface thereof is laminated on the inner surface 2 of the laminate sheet 4.

The coating layer 5 is a synthetic resin mixed with antibacterial zeolite particles, as will be described later, and the base layer 5a is a sheet made of the same synthetic resin as the coating layer 5.

By mixing the zeolite particles only in the coating layer 5 in this way, the zeolite particles can be unevenly distributed only on the surface, and an economical and effective antibacterial effect can be obtained. Furthermore, since the "coating layer 5 + base layer 5a" can be made into one antibacterial sheet 9, handling becomes easier.

In the laminate sheet 4, an outer synthetic resin layer 8 is provided on the outer surface of the aluminum foil 6 via an adhesive layer 10, and an adhesive layer 10 and a paper 11 are provided on the inner surface.
An inner synthetic resin layer 7 is provided via the inner synthetic resin layer 7.

[0017] The antibacterial zeolite is extremely safe for the human body, exhibits excellent antibacterial effects against various bacteria and molds for a long period of time, and moreover, has a temperature of about 550°C.
It also has heat resistance that is stable up to The antibacterial zeolite is obtained by ion-exchanging some or all of the ion-exchangeable ions in the zeolite with antibacterial metal ions.

Examples of ions that can be exchanged in the zeolite include sodium ions, calcium ions, potassium ions, magnesium ions, and iron ions.

Specific examples of the antibacterial metal ions include:
Examples include metal ions such as silver, copper, and zinc. Further, some of the ion-exchangeable ions in the antibacterial zeolite used in the present invention may be ion-exchanged with ammonium ions. The coating layer 5 containing antibacterial zeolite containing ammonium ions is
This is particularly preferred because it is less likely to change color over time.

When silver ions are used as antibacterial metal ions, the content of silver ions in the antibacterial zeolite is 0.
．． 1 to 15% (weight%, the same applies hereinafter), especially 0.
It is preferably 1 to 5%. Further, when copper ions or zinc ions are used as antibacterial metal ions, the content of copper ions or zinc ions in the antibacterial zeolite is preferably 0.1 to 8%. If the content of the antibacterial metal ions is less than the above range,
The antibacterial activity tends to become too small, and if it exceeds the above range, the antibacterial effect remains the same, but it tends to be economically disadvantageous.

[0021] When ammonium ions are contained in the antibacterial zeolite, the content of ammonium ions in the antibacterial zeolite is preferably 0.5 to 5%, preferably 0.5 to 2%. , is suitable from the standpoint of effectively preventing antibacterial zeolite from discoloring.

[0022] As the zeolite used for the antibacterial zeolite in the present invention, both natural zeolite and synthetic zeolite can be used.

The zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and has the general formula:
/nO・Al2 O3 ・YSiO2・ZH2 O(
In the formula, M represents an ion exchangeable ion, usually 1
It is a compound represented by a valent or divalent metal ion, n is the valence of the metal ion, X and Y are the molar ratio of metal oxide and silica, respectively, and Z is the number of crystal water. Specific examples of such zeolites include synthetic zeolites such as A-type zeolite, X-type zeolite, and Y-type zeolite; natural zeolites such as mordenite, clinoptilolite, chabasite, and erionite.

[0024] SiO2 of these exemplified zeolites
/Al2O3 molar ratio and ion exchange capacity are A
Type zeolite has a molar ratio of 2.0, 7 milliequivalents/g,
The molar ratio of type zeolite is 2.5, 6.4 meq/
g, Y type zeolite molar ratio 4.0, 5 meq/
g, mordenite molar ratio 10.0, 2.6 meq/g, clinoptilolite molar ratio 10.0, 2.6
milliequivalent/g, chabasite has a molar ratio of 4.0 and 5 milliequivalents/g, and erionite has a molar ratio of 6.0 and 3.8 milliequivalents/g, which is sufficient for ion exchange with antibacterial metal ions. It has a large capacity. Among these, S has good dispersibility with the resin that forms the coating layer and facilitates ion exchange reactions.
A with an iO2/Al2O3 molar ratio of 4.5 or less
Preferably, type zeolite, X-type zeolite, Y-type zeolite, and chabasite are not limited to these.

[0025] As for zeolite, the average particle size is 0.5
~10 μm, preferably 2 to 3 μm, and a maximum particle size of 25 μm or less, preferably 10 μm or less is preferable because the atomization state is good when it is included in a spray, for example.

Next, an example of a method for producing the antibacterial zeolite used in the present invention will be explained.

[0027] An aqueous solution of salts containing antibacterial metal ions is prepared in advance, and zeolite is added to the mixed aqueous solution containing antibacterial metal ions (silver ions, copper ions, zinc ions) and, if necessary, ammonium ions. The antibacterial metal ions are brought into contact with each other to replace ion exchangeable ions in the zeolite with the antibacterial metal ions. The conditions for contacting are a temperature of 10 to 70°C, preferably 40 to 60°C, and a time of 3
~24 hours, preferably 10-24 hours, and the process is batchwise or continuous (e.g. column process). In addition, the pH of the mixed aqueous solution is 3 to 1 in order to prevent silver oxide etc. from precipitating on the zeolite surface or into the pores.
0, preferably 5-7. Further, each ion in the mixed aqueous solution is usually supplied in the form of a salt. Silver ions include silver nitrate and silver sulfate; copper ions include copper(II) nitrate and copper sulfate; zinc ions include zinc(II) nitrate and zinc sulfate; and ammonium ions include ammonium nitrate, ammonium sulfate, and ammonium acetate. Each is supplied in the form of salt.

The content of antibacterial metal ions and ammonium ions in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution. For example, when the zeolite contains silver ions and ammonium ions, the ammonium ion concentration in the mixed aqueous solution is 0.85 to 3.
1 mol/L, silver ion concentration 0.002 to 0.1
By adjusting the amount to 5 mol/L, it is possible to obtain the desired zeolite having an ammonium ion content of 0.5 to 5% and a silver ion content of 0.1 to 5%. Further, when the zeolite contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 to 0.85 mol/L, and the zinc ion concentration is 0.15 to 1.2 mol/L. By doing so, it is possible to obtain zeolite having a copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8%.

In the present invention, in addition to the above-mentioned mixed aqueous solution, ion exchange can also be carried out by using an aqueous solution containing ions of each antibacterial metal individually and bringing each aqueous solution into contact with zeolite one after another. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution. Antibacterial zeolite can be obtained by thoroughly washing the ion-exchanged zeolite with water or hot water and then drying it. Such drying is carried out at 105-115°C under normal pressure or at reduced pressure (1-115°C).
It is preferable to carry out at 70-90 degreeC under 30 torr).

The coating layer used in the laminate tube container of the present invention can be used without any limitation as long as it is made by uniformly dispersing antibacterial zeolite in various organic polymer compounds. Examples of organic polymer compounds that can be used include polyethylene, polypropylene, polyamide, polyurethane, polycarbonate, polystyrene, polyacrylate, vinyl chloride resin, vinylidene chloride resin, and the like.

[0031] There are no particular limitations on the method of providing the coating layer containing antibacterial zeolite on the inner surface 2 and/or outer surface 3 of the laminated tube container, and methods such as co-extrusion processing and bonding processing may be used. be exposed.

[0032] The content of antibacterial zeolite in the coating layer provided on the inner surface 2 and/or outer surface 3 of the laminate tube container 1 of the present invention is determined by the use of the laminate tube container and the content of antibacterial zeolite that is originally present on the surface of the laminate tube container. The antibacterial properties required vary depending on the number of bacteria present, so it cannot be determined unconditionally. However, according to test results, 1 to 5% of If a polymer compound containing 50% antibacterial zeolite is mixed with a synthetic resin such as polyethylene resin, and the coating layer 5 has a thickness of 5 to 50 μm, the desired antibacterial effect can be achieved. I got it. That is, preferably the thickness of the coating layer 5 is 5 to 5.
If it is 0 μm, the zeolite particles will be exposed on the surface of the coating layer 5 formed on the inner surface 2 and/or outer surface 3 of the laminate tube container, so that a sufficient antibacterial effect can be obtained.

The antibacterial zeolite contained in such a coating layer 1 is preferably 1 to 5%, and the number of antibacterial zeolite particles dispersed per 100 μm x 100 μm of the coating layer 1 (hereinafter referred to as dispersed (referred to as the number of pieces) is
1 to 11,000, preferably 12 to 9,500
It is preferable to adjust it individually. The number of antibacterial zeolite particles contained in the coating layer per 10,000 μm 2 was determined by scanning electron microscopy analysis. If the number of dispersed particles is less than the above range, antibacterial properties are not imparted, and if it exceeds the above range, antibacterial properties are improved, but this tends to be economically disadvantageous.

Furthermore, if the thickness of the coating layer 1 is less than 1 μm, it tends to be difficult to form a uniform film during molding.
It has also been found that when the thickness exceeds 200 μm, the antibacterial zeolite is often completely buried in the coating layer 1, and the desired antibacterial properties cannot be obtained.

Next, the antibacterial effect of the laminate tube container of the present invention will be explained based on Examples and Comparative Examples.

■Test Sample Example 1 As shown in FIG.
An antibacterial sheet was obtained by laminating the antibacterial sheet with the coating layer 5 containing O2). Next, an inner resin layer 7 made of low-density polyethylene with a thickness of 20 μm, a paper 11, and a first layer made of EAA are prepared.
A laminate sheet 4 was produced by laminating in this order an adhesive layer 10, an aluminum foil 6 with a thickness of 15 μm, a second adhesive layer 9 made of EAA, and an outer resin layer 8 made of low density polyethylene with a thickness of 45 μm. Further, the antibacterial sheet and the laminate sheet 4 were bonded together to produce an original fabric having a total thickness of 325 μm. Further, the original fabric was formed into a tube container having an outer diameter of 27 mm and a length of 140 mm to obtain the laminate tube of Example 1.

The coating layer is made of Zeolite, which is an antibacterial zeolite.
Contains 1.39% O and has a diameter of 10,000 μm2
The number of ZeO particles per sample was about 80.

[0038] The content of ZeO was determined by weighing the sample and
Ashing was carried out at 0°C for 1 hour, the ash content was transferred to a platinum dish, nitric acid-hydrofluoric acid was added and evaporated to dryness, then nitric acid was added to dissolve it, the volume was made up to 100 ml and measured using an atomic absorption spectrophotometer. .

Comparative Example 1 A laminate tube of Comparative Example 1 having the same shape as Example 1 was obtained using only the laminate sheet 4.

■Test conditions A part of the laminate tube was cut out to a size of 50 mm x 50 mm, and a bacterial solution (105 cells/m2) was placed on the inner surface.
Immediately after, 1 ml of 1) was added dropwise, and the bacterial solution was washed out with sterilized physiological saline after 1 and 18 hours of maintaining the temperature at 36°C. The number of bacteria in the drained liquid was measured using bacteria test paper (for general bacteria and for Escherichia coli).

■Test results The above results are shown in Table 1.

[0042]

[Table 1]

As is clear from the results in Table 1, Comparative Example 1
It can be seen that in the laminate tube of Example 1, both general bacteria and E. coli increased after a certain period of time, whereas in the laminate tube of Example 1, 100% were killed.

Next, the laminate tubes of Example 1 and Comparative Example 1 were each cut into a size of 50 mm x 50 mm, and Aspergillus niger was injected onto the inner surface (surface treated with antibacterial zeolite).
) 1 ml of bacterial solution (10 5 cells/ml) was sprayed, and immediately thereafter, the mixture was maintained at 20° C. After 18 hours, the bacterial solution was washed out with sterilized physiological saline. Furthermore, the washed solution was smeared on an ordinary agar medium to measure the number of viable bacteria. The results are shown in Table 2. As a control, a test using only the bacterial solution was also conducted.

[0045]

[Table 2]

According to Table 2, the number of bacteria in the tube of Comparative Example 1 and the bacterial solution alone was the same as the original number, or even increased, whereas in the laminate tube of Example 1, Aspergillus niger was killed. I understand that.

[0047]

Effects of the Invention The laminate tube container of the present invention can prevent the growth of bacteria, mold, etc. even if food etc. are stored in the container for a long time.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway side view showing an embodiment of the laminate tube container of the present invention.

FIG. 2 is an enlarged sectional view of section a of the container in FIG. 1;

FIG. 3 is an enlarged cross-sectional view of essential parts showing another embodiment of the laminate tube container of the present invention.

[Explanation of symbols]

1 Laminated tube container 2 Inner surface 3 Outer surface 5 Coating layer

Claims (6)

[Claims] 1. A laminate tube container comprising a barrier layer of aluminum foil and a coating layer containing antibacterial zeolite as an antibacterial agent on its inner and/or outer surfaces. 2. The laminate tube container according to claim 1, wherein the coating layer is a synthetic resin layer containing 1 to 5% by weight of antibacterial zeolite. [Claim 3] Antibacterial zeolite SiO2/A
The laminate tube container according to claim 1, wherein the l2O3 molar ratio is 4.5 or less. [Claim 4] The coating layer contains antibacterial zeolite particles.
The laminate tube container according to claim 1, containing 1 to 11,000 particles per 0,000 μm2. [Claim 5] The antibacterial zeolite has an average particle size of 0.5.
The laminate tube container according to claim 1, which is a synthetic zeolite of ~10 μm. 6. The laminate tube container according to claim 1, wherein the coating layer has a thickness of 1 to 200 μm.