JPH0890726A - Antibacterial laminate - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a laminate having excellent antibacterial properties that inhibits the growth of microorganisms on the surface located outside when used in a container. An antibacterial laminate for use in a container, comprising a polymer laminate comprising at least two layers, wherein an antibacterial agent is added to at least a resin layer forming an outermost layer of the container.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer laminate used in plastic containers prepared by various molding methods. More specifically, the present invention relates to an antibacterial laminate used in a container in which an antibacterial agent or the like is added to the surface of the container for the purpose of preventing the growth of mold, bacteria and the like.

[0002]

2. Description of the Related Art Plastic products (containers such as shampoo and conditioner) that are placed under high temperature and high humidity conditions in bathrooms are used for several months. Are known. Therefore, not only the appearance is impaired, but also the mold spores are considered as one of the causes of symptoms such as allergy. Further, it is considered that the slippage on the container surface is due to the growth of bacteria and yeast.

A container having an antimicrobial agent added to the inner surface of the container in order to prevent the growth of microorganisms and to prevent the deterioration of the contents of the container such as cosmetics and pharmaceuticals (for example, Japanese Utility Model Publication 58-2783).
No.), a container in which an inorganic antibacterial substance is added to the innermost layer of a multi-layer container (for example, JP-A-3-150122) is proposed, but these are all for preventing alteration of the contents. There has been a demand for a container that prevents the growth of microorganisms on the container surface and does not cause slippage.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer laminate which inhibits the growth of microorganisms on the surface of a container as described above.

[0005]

DISCLOSURE OF THE INVENTION The present invention was conceived to solve the above problems. First, a resin used for a container is composed of at least two layers and forms at least the outermost layer of the container. An antibacterial laminate in which an antibacterial agent is added to a layer. Secondly, in a polymer laminate comprising at least two layers used in a container, a resin layer forming an outer surface of the container and a resin layer forming an inner surface of the container The antibacterial laminate is characterized by adding an antibacterial agent to each of the above. Third, the antibacterial agent added to the resin layer forming the outer surface of the container is an organic antibacterial agent, and the resin layer forming the inner surface is An antibacterial laminate, wherein the antibacterial agent added is an antibacterial agent containing a metal or a metal ion as an antibacterial component.

The present invention will be described in more detail below.

Organic antibacterial agents are preferable as antibacterial agents to be added to at least the outermost resin layer of the polymer laminate of the present invention, and 1,2-benzisothiazolin-3-one (trade name: Proxel CRL), N-fluorodichloromethylthiophthalimide (trade name: fluorophorpet), 2,3,5,6-tetrachloroisophthalonitrile (generic name: TPN, trade name: daconyl,
Nopsite N-96), 2- (4-thiazoyl) benzimidazole (generic name: benzimidazole, TB
Z), methyl benzimidazole carbamate 10,
10'-oxybisphenoxane acyl (trade name: Vinadine), 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine (trade name: Dausyl-S-1)
3), 2-pyridinethiol-1-oxide zinc, N,
N-dimethyl-N '-(fluorodichloromethylthio)
-N'-phenylsulfamide and the like can be used and can be arbitrarily selected in consideration of various properties such as heat resistance and antibacterial property.

The amount of the antibacterial agent added can be arbitrarily set in consideration of the desired antibacterial effect, the effect of coloring of the added resin, the price, and the like.

In many cases, the microorganisms grow on the plastic surface because the stains of the organic matter adhere to the plastic surface and the microorganisms that utilize the organic matter grow. It is considered that these antibacterial agents diffuse into the organic substance from the plastic surface and inhibit the growth of microorganisms.

Recently, many antibacterial agents have been developed in which silver is supported on an inorganic mineral such as zeolite. These antibacterial agents are effective when the bacterial cells and the antibacterial agent are in direct contact with each other, but the antibacterial effect is weak when the organic adhering substances intended by the present invention are present. Cannot be used on the body.

As a means for adding these antibacterial agents of the present invention and forming a resin layer forming the outermost layer of a container, these antibacterial agents are melted and mixed with a resin, and the resin layer is mixed with other resin layers from a die. It can be formed by using a known technique such as an extrusion method, a method of mixing with a resin dissolved in a solvent, applying on a substrate, and then drying to form.

As the resin constituting the antibacterial laminate of the present invention, it is possible to use any resin which is usually used for containers. However, considering the antibacterial effect, the resin used for the outermost layer is polyolefin. , Polystyrene is good. This is because these resins easily pass through the antibacterial agent, and the antibacterial agent added to the resin is easily diffused in the organic deposit. Other resins may be mixed with these resins for the purpose of controlling the diffusion amount of the antibacterial agent and modifying the surface condition.

As the material for forming the antibacterial laminate of the present invention, a material other than resin such as paper or metal may be used in addition to the resin layer forming the outermost layer of the container, and the outermost layer of the container is formed. When a so-called burr is added to a layer other than the resin layer, for example, the intermediate layer of the multilayer container, the antibacterial agent is eventually added. Thus, the antibacterial agent may be added to the layers other than the resin layer forming the outermost layer of the container.

[0014]

The polymer laminate of the present invention has an excellent function of inhibiting the growth of microorganisms on the outer surface of the container because an antibacterial agent, particularly an organic antibacterial agent is added to the resin layer forming the outermost layer of the container. It is possible to prevent the generation of mold and slippage.

Examples of the present invention will be described below.

[0016]

【Example】

<Example 1> A sheet having an antibacterial agent-added polypropylene layer (1) 100 µm / polypropylene layer (2) 400 µm was formed by a normal extrusion method (Fig. 1). As the antibacterial agent, 2% by weight of benzalkonium chloride was added.

Example 2 A sheet composed of an antibacterial agent-added polypropylene layer (3) 100 μm / polypropylene layer (4) 400 μm / antibacterial agent-added polypropylene (5) 100 μm was formed by a conventional extrusion molding method ( (Fig. 2).
Antibacterial agent (3) layer is 2% by weight of benzalkonium chloride
The layer of (5) was added and the silver-substituted zeolite (silver content 2.
5% by weight) was added.

<Comparative Example 1> A sheet consisting of 100 μm of polypropylene layer (7) / 400 μm of polypropylene layer (6) was molded by a conventional extrusion molding method (FIG. 3). Antibacterial agent is silver-substituted zeolite (silver content 2.5
5% by weight) was added.

Comparative Example 2 A polypropylene single layer sheet (8) of 500 μm was produced by a usual extrusion molding method (FIG. 4). The following experiments were conducted using the above four types of sheets.

After coating black mold spores on a plate of potato dextrose agar, the above sheet was punched into a circle having a diameter of 28 mm, and an antibacterial agent was added (Example 1).
In Comparative Example 1), the antibacterial agent-added layer was brought into close contact with the medium so that the layers were brought into close contact with each other, followed by culturing at 25 ° C. and observing the mold growth condition. As a result, in the case of Examples 1 and 2, an inhibition circle (9) (portion where no growth of microorganisms was observed) could be observed around the sheet (FIG. 5), while Comparative Examples 1, 2 Neither blocking circle was observed (Fig. 6).

<Example 3> By the usual blow molding method,
A container having an antimicrobial agent-added polyethylene layer (14) / polyethylene + burr (15) / polyethylene (16) with an internal capacity of 800 ml was molded in order from the outside (FIG. 7). The basis weight is 55 g. The composition ratio is a thickness ratio of 1: 7: 2. 1 antibacterial agent
0.2% of 0,10'-oxybisphenoxane acyl was added. The amount of burr added to the intermediate layer was 50% by weight, which means that about 0.01% by weight of 10,10′-oxybisphenoxane acyl was added to the intermediate layer in calculation.

<Comparative Example 3> By a usual blow molding method,
From the outside, polyethylene layer / polyethylene + burr /
A container having a polyethylene content of 800 ml was molded.
The basis weight is 55 g. The composition ratio is a thickness ratio of 1: 7: 2.

The above container was left in a bathroom of a general household at a position where the body was washed with hot water and the like, and after 3 months, the condition of the container surface was observed. As a result, mold was generated in the container of Comparative Example 3, and the substance on the red color was attached to the vicinity of the portion in contact with the floor of the container to cause slippage, whereas in Example 3
No particular change was observed on the surface of the container.

Example 1 is an example in which the polymer laminate according to the present invention exhibits superior antibacterial properties to those obtained by adding an antibacterial agent containing silver as an antibacterial component. Example 2 is an example showing excellent antibacterial properties and surface protection properties under general use conditions when the polymer laminate according to the present invention is used in a container.

<Example 4> By a usual blow molding method,
Content of the antibacterial agent-added polyethylene layer / polyethylene layer / antibacterial agent-added polyethylene layer is 800 from the outside.
A ml container was molded. The basis weight is 55 g, and the thickness ratio of each layer is 1: 8: 1. As the antibacterial agent, 0.2% by weight of 10,10-oxybisphenoxane acyl was added.

<Example 5> By a usual blow molding method,
Content of the antibacterial agent-added polyethylene layer / polyethylene layer / antibacterial agent-added polyethylene layer is 800 from the outside.
A ml container was molded. The basis weight is 55 g, and the thickness ratio of each layer is 1: 8: 1. As an antibacterial agent, 0.2% by weight of 10,10-oxybisphenoxane acyl was added to the resin layer forming the outermost layer of the container, and a silver-substituted zeolite (silver content ratio of 2. 5% by weight) was added.

<Comparative Example 4> By a usual blow molding method,
Content of the antibacterial agent-added polyethylene layer / polyethylene layer / antibacterial agent-added polyethylene layer is 800 from the outside.
A ml container was molded. The basis weight is 55 g, and the thickness ratio of each layer is 1: 8: 1. 5% by weight of silver-substituted zeolite (silver content 2.5% by weight) as the antibacterial agent for both the inner and outer layers
Was added.

<Comparative Example 5> By a usual blow molding method,
A container having an internal capacity of 800 ml having a constitution of an antibacterial agent-added polyethylene layer / polyethylene layer was formed in order from the outside. The basis weight is 55 g, and the thickness ratio of each layer is 1: 9. As the antibacterial agent, 10,10-oxybisphenoxane acyl was added to 0.1.
2% by volume was added.

<Comparative Example 6> By a usual blow molding method,
A container having an internal volume of 800 ml having a constitution of polyethylene layer / polyethylene layer containing antibacterial agent was molded in order from the outside. The basis weight is 55 g, and the thickness ratio of each layer is 9: 1. As the antibacterial agent, 10,10-oxybisphenoxane acyl was added to 0.1.
2% by volume was added.

<Comparative Example 7> By a usual blow molding method,
A container having a polyethylene single layer structure and an internal volume of 800 ml was molded. The basis weight is 55 g.

The following experiments were carried out using the containers having the constructions described in each of the above Examples and Comparative Examples.

Escherichia coli was added to a sterilized 0.1% polypeptone aqueous solution at a concentration of about 1000 cells / ml,
Each container was filled with 800 ml, sealed tightly, left in a bathroom of a general household, and after 2 months, the number of surviving bacteria in the aqueous solution of polypeptone, the slip on the outer surface of the container, and the occurrence of mold were observed. The results are shown in Table 1.

[0033]

[Table 1]

Example 4 is an example in which an organic antibacterial agent is added to both surfaces of the polymer laminate, and the growth of microorganisms in the contents of the container using the polymer laminate and the mold on the outer surface, The occurrence of slippage can be prevented.

In Example 2, an organic antibacterial agent was added to the layer forming the outer surface of the container, and a silver antibacterial agent was added to the layer forming the inner surface of the container. It is possible to prevent the growth of microorganisms and the generation of mold and slip on the outer surface.

In Comparative Example 4, a silver antibacterial agent was added to the layers constituting both surfaces of the polymer laminate, and in Comparative Example 6, an organic antibacterial agent was added only to the layers constituting the inner surface of the container. It is added, and in any case, it is possible to inhibit the growth of microorganisms in the contents, but it is not possible to inhibit the occurrence of slippage and mold on the outer surface.

Further, in Comparative Example 5, the organic antibacterial agent was added only to the layer constituting the outer surface of the container, but slippage of the outer surface of the container and generation of mold could be inhibited, but It was not possible to inhibit the growth of the microorganisms. Further, as in Comparative Example 7, when no antibacterial agent was added at all, no antibacterial effect was exhibited on both the inner and outer surfaces of the container.

[0038]

INDUSTRIAL APPLICABILITY As described above, by using the polymer laminate of the present invention in a container, it is possible to prevent the occurrence of mold and slip on the surface of the container. By providing it on the outer surface, the function of preventing the generation of mold and slipping becomes reliable.

Further, by using different kinds of antibacterial agents for the outer surface and the inner surface of the container, the effect of preventing alteration of the contents can be obtained.

[0040]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a laminated body of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of the laminated body of the present invention.

FIG. 3 is a cross-sectional view showing a comparative example of the laminated body of the present invention.

FIG. 4 is a cross-sectional view showing another comparative example of the laminated body of the invention.

FIG. 5 is an explanatory diagram showing a situation of generation of a blocking circle according to an experiment of the present invention.

FIG. 6 is an explanatory diagram showing an experimental result of a comparative example of the present invention.

FIG. 7 is an explanatory diagram showing an example in which the laminate of the present invention is applied to a container.

[Explanation of symbols]

1, 3: Benzalkonium chloride-added polypropylene layer 2: Polypropylene layer 4: Polypropylene layer 5: Silver zeolite-added polypropylene layer 9: Blocking circle 14:10, 10'-oxybisphenoxane acyl-added polyethylene layer 15: Burr-added polyethylene Layer 16: Polyethylene layer

Claims (3)

[Claims] 1. An antibacterial laminate for use in a container, comprising a polymer laminate comprising at least two layers, wherein an antibacterial agent is added to at least a resin layer forming an outermost layer of the container. 2. A polymer laminate comprising at least two layers for use in a container, wherein an antibacterial agent is added to each of a resin layer forming an outer surface of the container and a resin layer forming an inner surface of the container. Antibacterial laminate. 3. The antibacterial agent added to the resin layer forming the outer surface of the container is an organic antibacterial agent, and the antibacterial agent added to the resin layer forming the inner surface is an antibacterial agent containing a metal or a metal ion as an antibacterial component. The antibacterial laminate according to claim 1 or 2, wherein