JPH03176390A - Barrier pack in double wall aerosol container - Google Patents

Abstract

PURPOSE:To provide an antibacterial double wall aerosol container with a barrier pack as its inner container by forming an antibacterial zeolite-containing coating layer on at least the inner surface of the barrier pack. CONSTITUTION:A coating layer for use on a barrier pack in a double wall aerosol container is of an organic high-molecular compound containing an antibacterial zeolite and it can be used without any restriction, if the antibacterial zeolite is uniformly dispersed. By way of example, the organic high-molecular compound may be polyethylene and polypropylene. The method of forming an antibacterial zeolite-containing coating layer 1 on the barrier pack 2 in the double wall aersol container is not specifically designated and a multiple resin layer 6 is built up on the barrier pack 2 by the conventional method such as simultaneous extrusion multilayer blow molding. In the case of the barrier pack 2 consisting of a single aluminum layer 5 or a laminate layer 7 having an aluminum foil 9 in its interior, a coating layer 1 may be formed previously on the blank material.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a barrier pack for dual aerosol containers.

More specifically, the present invention relates to a barrier pack for a double aerosol container that has antibacterial properties at least on the inner surface of the barrier pack.

[Prior Art] Conventionally, double aerosol containers have been used in which the contents ejected from the aerosol container and a propellant for pressurizing the contents are separated and sealed. Such double aerosol containers usually have a pressure-resistant outer container made of metal such as aluminum or steel, and a synthetic resin container that is suspended within the outer container and is crushed by the pressing force of the propellant. Or the bottom is grooved with a double traverse of IJ 7 bags made of aluminum. Such double aerosol containers are used for various purposes such as cosmetics and food, but when storing food etc. inside the barrier bag, it is important that bacteria and mold do not grow inside the barrier bag. This is desirable.

However, the barrier bag of double aerosol containers, which can prevent the growth of bacteria and mold even when food etc. is stored for a long time inside the barrier bag of double aerosol containers, has not been completely eliminated. be.

[Problems to be Solved by the Invention] Therefore, as a result of extensive research in view of the above-mentioned prior art, the present inventors found that a coating layer (1) containing antibacterial zeolite is provided on the inner surface. Surprisingly, they discovered that even when food and the like are stored in a barrier bag for a long time, the growth of bacteria and mold can be prevented, and the present invention was completed.

[Means for Solving the Problems] That is, the present invention includes an antibacterial zeolite as an antibacterial agent.
This is a barrier bag for a double aerosol container provided in 3).

[Made by JIJ and Fire Example] In the present invention, there is no particular limitation on the type and size of the double container barrier bag provided with the dust layer (1).
Barrier pack consisting of Ji4, or Kamoki 11)
It can be provided in a commonly used barrier bag such as a barrier pack made of eR4.

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

As for the ion exchangeable ions in the zeolite,
Examples include sodium ions, calcium ions, potassium ions, magnesium ions, and iron ions.

Specific examples of the antibacterial metal ions include silver,
Examples include metal ions such as 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 (1) containing antibacterial zeolite containing ammonium ions 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 antibacterial zeolite is 0.1 = 159
6 (wt%, the same applies hereinafter), preferably <0.1 to 5%. In addition, when copper ions or zinc ions are used as anti-abandonant ions, the content of copper ions or zinc ions in the antibacterial zeolite is 0.1 to 0.1.
It is preferably 8%. If the content of the anti-cleavage metal ion is lower than the above range, the antibacterial activity tends to be too small, and if it exceeds the above range, the antibacterial effect remains the same but it is economically disadvantageous. There is a tendency to

In addition, when ammonium ions are added to antibacterial zeolite, the content of ammonium ions in antibacterial zeolite is 0.5 to 5 to 6, preferably 0.5.
It is appropriate to set the content to 2% because it effectively prevents the antibacterial zeolite from discoloring.

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

The zeolite generally has three-dimensional bone Fb 4m m a
It is an aluminosilicate with the general formula: % formula % (wherein H represents an ion exchangeable ion,
is a monovalent or divalent metal ion, n is the metal ion source f
This is a compound represented by the following formula: valence, X and Y respectively indicate the molar ratio of metal oxide and phosphoric acid, and 2 indicates the number of water of crystallization. Specific examples of such zeolites include synthetic zeolites such as A-type zeolite, X-type zeolite, and Y-type zeolite; and natural zeolites such as mordenite, clinoptilolite, chabasite, and erionite.

The ion exchange capacity of these exemplified zeolites is AW
Zeolite is 7 mm/ffl/g, X-type zeolite is 6.4 mm/u/g, Y-type zeolite is 5 mm/mu
gs mordenite is 2.6 mm/g.

Clinoptilolite has 2.6 mm/W/g, chabasite has 5 mm/W/g, and erionite has 3.8 mm/W/g, all of which are ion-exchanged with ammonium ions and antibacterial metal ions. It has sufficient capacity to

Of these, zeolite has a pore volume of 0.000, from the viewpoint of good compatibility with the resin in the coating layer, high contact with antibacterial metals, and stable antibacterial activity. Zeolites having a lcj/g or higher are preferred, but are not limited thereto. Pore volume 0. I cj/g or less] As the second zeolite, synthetic zeolite has a particle size of 50 μm in terms of length.
Examples include the following A-type zeolite, X-type zeolite, Y-type zeolite, mordenite, and erionite having a crystallinity of 85% or more. Examples of natural zeolites include clinoptilolite, mordenite, chabasite, etc., which have an apical particle size of 10 am or less and a crystallinity of 60% or more.

In this specification, the pore volume refers to the volume of pores in the zeolite, and is based on the B, F, Roberts method (J, Co
11 &In1cr['ace 5science 2
Volume 3, page 266).

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

An aqueous solution of salts containing antibacterial metal ions is prepared in advance, and zeolite is brought into contact with a mixed aqueous solution containing antibacterial metal ions (silver ions, copper ions, zinc ions) and, if necessary, ammonium ions. The ion-exchangeable ions in the zeolite are replaced with the antibacterial metal ions. The conditions for contact are a temperature of 10 to 7
0°C, preferably 40-60°C, time 3-24[1,
The process is batchwise or continuous (e.g. column process). In addition, the pH of the mixed aqueous solution is 3 to 10, in order to prevent silver oxide etc. from precipitating on the zeolite surface or into the pores.
Preferably 5 to 7, M is avoided. 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 nitrate (It) and zinc sulfate; ammonium ions include ammonium nitrate, ammonium sulfate, etc.
Each is supplied in the form of a salt such as ammonium acetate.

The content of antibacterial metal ions and ammonium ions in the zeolite is determined by each ion (salt) in the mixed aqueous solution.
It can be appropriately controlled by adjusting the a degree. For example, when zeolite contains silver ions and ammonium ions, the ammonium ion concentration in the mixed aqueous solution is set to 0.85 to 3.1 mol/R,
By setting the silver ion L1 degree to 0.002 to O, 15 mol/R, the target ammonium ion content is 0.5 to 5%, and the silver ion content is 0.1 to 5%. You can explore zeolite. In addition, when zeolite contains copper ions and zinc ions,
The copper ion concentration in the mixed aqueous solution is 0.1 to 0.85 m
ol#! , zinc ion concentration is 0.15~], 2 mo
By setting l/j7, the copper ion content is 0.1
8%, with a zinc ion content of 0.1 to 8%.

In the present invention, in addition to the above mixed aqueous solution, an aqueous solution containing each antibacterial metal ion alone can be used, and ion exchange can be carried out by sequentially bringing each aqueous solution into contact with zeolite. The concentration of each ion in the aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution. After ion exchange has been completed, the zeolite is thoroughly washed with water or hot water and then dried to convert it into an antibacterial zeolite.

Such drying is preferably carried out at 105 to 115° C. under normal pressure or at 70 to 90° C. under reduced pressure (1 to 30 torr).

The coating layer used in the barrier pack of the double aerosol container of the present invention is an organic polymer compound containing the above-mentioned antibacterial zeolite, and can be used without any restriction as long as the antibacterial zeolite is uniformly dispersed therein. Examples of usable polymeric compounds include polyolefins such as polyethylene, polypropylene, and polybutene, polyamides, polyurethanes, polystyrene, polycarbonates, polyacrylates, vinyl chloride resins, and vinylidene chloride resins.

There is no particular limitation on the method of providing the coating layer (1) containing antibacterial zeolite on the barrier pack (2) of the double aerosol container. It is processed by a commonly used molding method such as extrusion multilayer blow molding, and is also applied to a barrier pack (2) consisting of a single aluminum layer (5) or a laminate layer (7) with aluminum foil (9) inside. Well,
This is done by a method such as sinking the coating layer (1) into the original fabric.

Barrier pack for double aerosol container according to the present invention (
coating layer (1) provided on at least the inner surface (3) of
) The content of antibacterial zeolite in Barrier Pack (2
) The required antibacterial properties differ depending on the intended use or the number of bacteria originally existing on the surface, so it cannot be determined in part. However, test results show that 1 to 5% of a polymeric compound containing antibacterial Viola 4150% is mixed with, for example, polyethylene resin, and this coating layer (
1) with a thickness of 1 to 200-, for example, 10
0-300 printing aluminum single layer (5), 200-50
When provided on the inner surface (3) of a barrier pack (2) consisting of a 0 μm multilayer resin layer (6) or laminate layer (7), the desired antibacterial effect was achieved. Further, preferably, if the thickness of the coating layer (1) is 5 to 50, the surface of the coating layer (1) formed on the inner surface (3) of the barrier pack ('2J) of the double aerosol container is It is thought that a sufficient antibacterial effect can be obtained due to the exposure of zeolite particles.

The antibacterial zeolite contained in such a coating layer (1) is preferably 0.5 to 50%;
) The number of antibacterial zeolite particles dispersed per 100 prints (hereinafter referred to as the number of dispersed particles) is:
It is desirable to reduce the number to 1-11,000, preferably 12-9,500. The number of antibacterial zeolite particles per 10,000-2 particles contained in the coating layer 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 there is a tendency to be economically disadvantageous. Furthermore, if the thickness of the coating layer (1) is less than one printing, it tends to be difficult to form a uniform film, and if it exceeds 200 mm, the antibacterial zeolite may not be present in the coating layer (1). In many cases, the antibacterial properties were completely leaked, and it was found that the antibacterial properties could not be changed.

Next, a barrier pack for a double aerosol container according to the present invention will be described based on an embodiment shown in the attached drawings.

Fig. 1 is a partially cutaway front view showing a barrier pack of a double aerosol container according to the present invention, and Fig. 2 is a (a) of Fig. 1.
3 is a partially enlarged sectional view of a barrier pack (2) having a multilayer resin layer (6) provided with a coating layer (1) containing antibacterial zeolite on the inner surface (3). , resin layers (6a) and (6b) made of polyolefin resin are laminated on both sides of the gas barrier resin (8). Figure 4 shows a double aerosol container barrier pack ('2J) consisting of a laminate layer (71) with aluminum foil (9) inside.
A coating layer (3) containing antibacterial zeolite is coated on the inner surface (3) of the
This is a partially enlarged sectional view of the barrier pack (2) provided with the barrier pack (1), in which resin layers (7a>, (7b) such as polyolefin resin layers are laminated on both sides of the aluminum foil (9). In the embodiments shown in FIGS. 1 to 4, the coating layer (1) containing antibacterial zeolite may be provided not only on the inner surface (3) but also on the outer surface (4), and the barrier pack (2) can be changed as appropriate depending on the situation in which it is used.Furthermore, in the embodiments shown in Figs. 2 and 3, it is also possible to provide an adhesive layer between each layer. In the embodiments shown in FIGS. 3 and 4, a polyamide resin or a polyester resin may be used instead of the polyolefin resin, or a mixture of these resins may be used.

Next, the antibacterial test results of the barrier pack of the double aerosol container according to the present invention are shown below.

■Sample Sample A; Barrier pack sample B not treated with antibacterial zeolite; Inner surface of barrier pack treated with antibacterial zeolite: Antibacterial zeolite (Y-type zeolite containing 2.5% silver, 8% zinc, and 1% ammonia; particle size 1) .1 Misaki, pore body taO, 9cm' 7g) 85 parts of 2096-containing low-density polyethylene...2oJ! m Middle IA: Low density polyethylene...320 am Outer surface: Same as inner surface.
...20 Number of antibacterial zeolite particles in the shell coating layer: 7,000 pieces Ha0,000 Misaki 2 ■Test conditions Sample (50 ga +
ml )1 ml was added dropwise, and after culturing at 37°C for 4 hours, the bacterial solution was washed out with sterilized raw raccoon saline. 12 about the spilled liquid! The number of songs was measured using i-wipe paper (for general use and for large intestine 1'a).

■Test Summary From the comparison results of Samples A and H above, the barrier pack of the double aerosol container of the present invention, which has a coating layer (1) containing antibacterial zeolite on the inner surface (3), It was found that the surface (3) exhibited excellent antibacterial properties. In the antibacterial test, polyethylene was used as the 1ul1 layer (1), but the material is not limited thereto.

In addition, a retention 7f test and an odor control test were conducted on the samples prepared in the examples.

[Wiping Test Example 1] Each barrier bag of Samples A and B prepared in the storage test example was filled with custard cream prepared with sugar, soft flour, and milk. This was left for 3 weeks at a temperature of 20-22°C. After being left standing, it was taken out from the container and changes in morphology were visually observed.

Result: Some oil and water separated from the cream added to Sample A, and there was a slight putrid odor. On the other hand, sample B had no change from before filling.

[Test Example 2] Each of the sample A and B barrier packs prepared in the deodorizing wiping test example was filled with a lotion having the following formulation. This was left for 3 weeks at a temperature of 20-22°C. After leaving it for a while, take an aliquot from the container and add 5
The mixture was heated to 0~GO°C, and the components that evaporated were compared with those before being left to stand by gas chromatography.

Results: Components (glycol decomposition products, microbial secretions) other than those before standing were detected in the lotion added to Sample A. On the other hand, sample B showed no change from before being left.

(Composition) Ethanol e, o parts dl-
Camphor 0.2 parts Jo Seisui
85.3 parts bentonite 0.3
Part 1.3-butylene glycol 8.0 parts Talc
2.0 copies fee
0.2 part [Effect of the invention] As explained above, the barrier pack of the double aerosol container of the present invention has antibacterial properties on its inner surface (3) using an antibacterial agent that is safe for the human body. , which has the effect of preventing bacteria, mold, etc. from growing on its inner surface for a long period of time. It also has excellent preservability and odor resistance for cosmetics, foods, etc. Therefore, the barrier pack of the double niazole container of the present invention is suitable for applications such as single layer aluminum for pharmaceuticals, food products, etc. where antibacterial properties are required*.
It is suitable for use as a multilayer or laminate barrier pack.

[Brief explanation of drawings]

The first image is a cross-sectional view of a single-layer aluminum barrier pack with a wave membrane layer containing antibacterial zeolite on its inner surface, and the aerosol container that houses it.
Large-scale cross-sectional view of the area; Figure 3 is a partially enlarged cross-sectional view of a multilayer resin barrier pack with a coating layer containing antibacterial zeolite on the inner surface; Figure 4 is a partially enlarged cross-sectional view of the barrier pack containing antibacterial zeolite on the inner surface. FIG. 2 is a partially enlarged sectional view of a barrier pack of a laminate layer provided with a corrugated film layer. (Main symbols in the drawings) (1): Wave film layer (2J: Barrier pack (3): Inner surface (4): Outer surface (5) Nial Minilam 11 layer (6): Multilayer resin layer (71 = Laminate If4 (8) ): Gas barrier resin (9) Ni-aluminum foil patent applicant Shikinai Breath Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. A barrier pack for a double aerosol container, which is provided with a coating layer containing antibacterial zeolite as an antibacterial agent on at least its inner surface. 2. The barrier pack for a double aerosol container according to claim 1, wherein the antibacterial zeolite has a pore volume of 0.1 cm^3/g or more. 3. The barrier pack for a double aerosol container according to claim 1, wherein the coating layer has a thickness of 1 to 200 μm. 4. The barrier pack for a double aerosol container according to claim 1, wherein the barrier pack is composed of a single layer of aluminum. 5. The barrier pack for a double aerosol container according to claim 1, wherein the barrier pack is composed of multilayer resin layers. 6. The barrier pack for a double aerosol container according to claim 1, wherein the barrier pack is composed of a laminate layer having aluminum foil.