JP2000153883A - Antibacterial resin multi-layered molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep good antibacterial properties to microorganisms for a long term even under bad conditions where water is frequency used by including at least an antibacterial outer layer, an antibacterial intermediate layer and further an inner layer. SOLUTION: This antibacterial resin multi-layered molding comprises an antibacterial outer layer 11, an antibacterial intermediate layer 12 and an inner layer 13. An antibacterial agent which is difficult to migrate is added to the antibacterial outer layer 11. In addition, an antibacterial agent which is likely to migrate is added to the antibacterial intermediate layer 12. The antibacterial resin multi-layered molding thus constituted prevents both blackening caused by growth of mold and slime caused by growth of bacteria by adding the antibacterial agent which is hard to migrate or substantially does not migrate in a resin and the antibacterial agent which is apt to migrate in the resin, while their effects can be kept for a long time even under bad conditions where water is frequency used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layered antibacterial resin product which prevents the occurrence of darkening, slimming and the like on the surface of a resin product caused by microorganisms such as mold, yeast and bacteria. More specifically, the present invention relates to a resin multilayer molded product used for soap containers used in bathrooms, kitchens, lavatories, etc., water-related products such as chairs, baskets, drainage baskets, containers such as shampoos, washing tubs of washing machines, and the like. Things.

[0002]

2. Description of the Related Art At present, an antibacterial agent which can be added to a resin has been developed and has been widely used. Antibacterial agents are roughly classified into two types: inorganic antibacterial agents in which silver, zinc or the like is supported on zeolite or the like, and organic antibacterial agents comprising an organic substance having antibacterial properties. Silver is mainly used as the inorganic antibacterial agent, and zinc is used when discoloration due to light poses a problem. These antibacterial agents have already been used in cooking utensils such as cutting boards and bowls, water-related products such as bathroom chairs and washbasins, filters and water tanks in washing tubs and humidifiers, and stationery such as ballpoint pens. It is widely used. As organic antibacterial agents, imidazole antibacterial agents and thiazoline antibacterial agents are used in washing tubs of washing machines. Each of these antibacterial agents is added directly to the resin at the time of molding or as a high-concentration masterbatch and molded. In recent years, antibacterial agents in which two or more kinds of components are mixed have been developed, and in some cases, a plurality of antibacterial agents are used in combination.

[0003]

A wide variety of antibacterial agents have been put on the market, but these antibacterial agents may not show any effect depending on the target microorganisms. Careful selection must be made with careful consideration as to whether or not the target is a microorganism. In addition, although it has an antibacterial effect, it does not always suit the use form of the product due to problems such as solubility and heat resistance. Inorganic antibacterial agents are said to have high safety to the human body and have high heat resistance, so that they do not impose restrictions on moldability when added to resins, and are excellent antibacterial agents. However, the antibacterial effect of silver on mold is small, and a large amount of addition is required to prevent darkening due to mold. Further, there is a problem that discoloration occurs when receiving light. Further, the antibacterial effect of zinc is extremely smaller than that of silver, and it is difficult to obtain an antibacterial effect by using a zinc-based antibacterial agent alone. In the case of organic antibacterial agents, few have antibacterial properties against both mold and bacteria. For example,
According to the study of the inventors, when an agent having an antibacterial component of benzalkonium salt, which is a mixture of alkyldimethylbenzylammonium salts having different alkyl chain lengths, which is an example of quaternary ammonium, is added to polyethylene, While the addition of 0.02-2.5% by weight or more of ruconium ions has an antibacterial effect against general bacteria, it is necessary to add 10 times or more of this to fungi. Also,
2-n-octyl-4-isothiazolin-3-one, which is a thiazoline compound, exhibits an antibacterial effect against fungi at an addition amount of 0.005 to 0.5% by weight, whereas Pseudomonas, a gram-negative bacterium, No antibacterial effect was observed.

The present inventors have invented an antimicrobial resin composition which solves these problems by using two or more organic antimicrobial agents in Japanese Patent Application No. 7-121792. However, when the product is used under adverse conditions such as in a bathroom or a kitchen where water or hot water is frequently applied, sustainability of the antibacterial effect is further required. It is considered that an antibacterial agent having a small molecular weight and an antibacterial agent having an affinity for water and contents are easily eluted. Even if two or more antibacterial agents are used in combination, if one of them is eluted, the effect is reduced by half. Further, when the antimicrobial agent-added layer is thickened, an antimicrobial agent having a property that is difficult to migrate is excessively added, which is not economical. In recent years, reuse of containers has been promoted due to increasing environmental awareness, and it is expected that how to increase the sustainability of the effect will lead to an extension of the reuse period in the future. The present invention provides a multi-layered antimicrobial resin article, which comprises adding an antimicrobial agent that hardly migrates in the resin or an antimicrobial agent that hardly migrates in the resin and an antimicrobial agent that easily migrates in the resin, so that the antimicrobial agent can be extended under adverse conditions such as around water. It is an object of the present invention to provide an antibacterial resin multilayer molded article which retains good antibacterial properties against microorganisms (molds, bacteria, etc.) over a period of time and does not cause discoloration of the resin or a decrease in strength.

[0005]

The present invention relates to an antimicrobial resin multilayer molded article (1) comprising at least an antimicrobial outer layer (11), an antimicrobial intermediate layer (12) and an inner layer (13). is there.

In the present invention, the antibacterial agent shielding layer (1) is provided between the antibacterial intermediate layer (12) and the inner layer (13).
The antibacterial resin multilayer molded article (1) provided with 4).

Further, the present invention is the multi-layered antimicrobial resin product (1) according to the above invention, wherein a recovery layer (15) is provided between the antimicrobial intermediate layer (12) and the inner layer (13).

In the present invention, the antibacterial agent shielding layer (1) is provided between the antibacterial intermediate layer (12) and the inner layer (13).
4) and an antibacterial resin multilayer molded article (1) provided with a recovery layer (15).

Further, the present invention is the antibacterial resin multilayer molded article (1) according to the above invention, wherein the recovery layer (15) has an antibacterial agent shielding function.

In the present invention, the antibacterial outer layer (11) contains an antibacterial agent which hardly migrates in the resin, and the antibacterial intermediate layer (12) is in the resin and the antibacterial outer layer (11). It is an antibacterial resin multilayer molded article (1) containing an antibacterial agent capable of migrating the compound.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. FIG. 1 is a schematic perspective view of one embodiment of the multilayered antibacterial resin product of the present invention. FIG. 2 is a schematic cross-sectional view of one embodiment of the multilayered antibacterial resin product of the present invention. FIG. 3 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention. FIG. 4 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention.
FIG. 5 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention. FIG. 6 is a schematic diagram showing a halo in a halo (inhibition circle) method, which is one of the antibacterial assay methods. 1 to 6, reference numeral 1 denotes an antibacterial resin multilayer molded product, 11 denotes an antibacterial outer layer, 12 denotes an antibacterial intermediate layer, 13 denotes an inner layer, 14 denotes an antibacterial agent shielding layer, 15 denotes a collecting layer, 2 denotes a petri dish, and 21 denotes a petri dish. The growth area of the fungus, 22 is a halo (inhibition circle), and 3 is a test piece.

As the hard-to-migrate antibacterial agent to be added to the antibacterial outer layer (11), alkyldimethylammonium chloride (n = 1 to 17) classified as a quaternary ammonium (also known as benzalkonium chloride) And pyridinium chloride (n = 6-1)
6) Those obtained by binding (for example, cetylpyridinium chloride with n = 14 most frequently) to a phosphate such as zirconium phosphate or titanium phosphate by ion exchange can be suitably used. The content of the quaternary ammonium ion in the support is determined by the ion exchange capacity when the quaternary ammonium ion is retained by, for example, ion exchange, but is generally 5 to 30% by weight. The content of the antibacterial component is such that the quaternary ammonium salt is 0.0
2 to 2.5% by weight is suitable. In addition, a thiazole compound such as 2-n-octyl-4-isothiazolin-3-one described in JP-A-5-213609 is used as an antimicrobial agent that is difficult to transfer, between the layers of the layered phosphate. A supported antibacterial agent or the like can be used, and as an antibacterial agent that hardly migrates, an antibacterial agent having silver ions, zinc ions, and copper ions supported on an inorganic substance such as zeolite can be used, although there is a problem such as discoloration.

[0013]

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[0014]

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The antimicrobial outer layer (11) and the antimicrobial intermediate layer (1)
Examples of the antimicrobial agent which is easily added to 2) include 2-n-octyl-4-isothiazolin-3-one, which is a thiazoline compound represented by [Chemical Formula 3] or [Chemical Formula 4].
A material in which 5-chloro-2-methyl-4-isothiazolin-3-one or the like is retained by adsorption on an inorganic substance such as silicon oxide or zinc oxide can be suitably used. The content of the thiazoline compound in the support is suitably in the range of 25 to 70% by weight. The amount of the antimicrobial component added to the antimicrobial outer layer (11) and the antimicrobial intermediate layer (12) is 0.005 to 0.005.
0.5% by weight is suitable. Other antimicrobial agents that can be easily transferred include triclosan, thiabedazole, zinc pyrithione, orthophenylphenol, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate,
Those obtained by holding benzoic acid esters such as propyl hydroxybenzoate, butyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, and isobutyl 4-hydroxybenzoate in an inorganic substance or the like can be used. It is also possible to add an antimicrobial agent that easily migrates to the recovery layer (15) or the inner layer (13). For quaternary ammonium, which is an antibacterial agent that is difficult to migrate, bound to phosphate,
Examinations by the inventors have revealed that a layer thickness exceeding a certain value does not affect the efficacy.

[0016]

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[0017]

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The resin used in the antibacterial resin multilayer molded product of the present invention includes thermoplastic resins such as polyethylene, polyvinyl chloride, and polypropylene; thermosetting resins such as phenolic resin and melamine resin; It is appropriately selected from those containing natural resins such as Celax, mainly in consideration of the degree of migration of the antibacterial agent and the like. Furthermore, an antioxidant for the antibacterial resin multilayer molded article of the present invention,
Substances usually added to the resin, such as an ultraviolet absorber, a colorant, an antistatic agent, and a plasticizer, are not limited. However, care must be taken when using an anionic additive because it reduces the effect of the quaternary ammonium antibacterial agent. By adding an antimicrobial agent that hardly migrates in the resin or an antimicrobial agent that hardly migrates and an antimicrobial agent that easily migrates in the resin, it has an antimicrobial effect, and it is effective for a long time even under adverse conditions such as bathtubs and kitchens It has become possible to obtain a long-lasting antibacterial resin multilayer molded article.

[0019]

Embodiments of the present invention will be specifically described below.

<Example 1> A multi-layer polyethylene bottle composed of four layers (average body thickness about 1000 μm, layer ratio: 10%: 15%: 6 from the outside) by a general multilayer blow molding method.
5%: 10%). Benzalkonium chloride, which is a quaternary ammonium salt, is used as a benzalkonium ion as an antibacterial agent that hardly migrates to the antibacterial outer layer (11).
5% by weight of a thiazoline-based compound, 2-n-octyl-4-isothiazoline-3-
0.02% by weight of ON and the antibacterial outer layer (11)
0.02% by weight of a thiazoline-based compound, 2-n-octyl-4-isothiazolin-3-one, was added to the inner antibacterial intermediate layer (12) that was in contact with. Inside the antibacterial intermediate layer (12), burrs generated at the time of bottle molding, that is, a burr-added layer which is a collection layer (15) to which crushed parison is added, and further, this collection layer (1)
The inside of 5) is the innermost layer to which no antimicrobial agent, burrs or the like are added. The benzalkonium salt was formed by supporting benzalkonium chloride on aluminum tripolyphosphate by ion exchange, and the 2-n-octyl-4-isothiazolin-3-one was supported on zinc oxide by adsorption. Sometimes added.

<Example 2> In the same manner as in Example 1, as an antibacterial agent which hardly migrates to the antibacterial outer layer (11), benzalkonium chloride, which is a quaternary ammonium salt, is used in an amount of 0.5 as benzalkonium ion. % By weight of the antimicrobial outer layer (1
The antibacterial agent, 2-n-, which is a thiazoline-based compound, is easily transferred to the inner antibacterial intermediate layer (12) in contact with 1).
A multilayer polyethylene bottle containing 0.02% by weight of octyl-4-isothiazolin-3-one and having an average body thickness of about 1000 μm was prepared.

<Comparative Example 1> Average body thickness about 1000 μm
Was produced.

<Comparative Example 2> In the same manner as in Example 1, as an antibacterial agent which hardly migrates to the antibacterial outer layer (11), benzalkonium chloride, which is a quaternary ammonium salt, is used in an amount of 0.5 as benzalkonium ion. A multilayer polyethylene bottle having a body average thickness of about 1000 μm containing weight% was prepared.

<Comparative Example 3> In the same manner as in Example 1, thiazoline as an antibacterial agent which is easily transferred to the antibacterial outer layer (11) and the inner antibacterial intermediate layer (12) in contact with the antibacterial outer layer (11). A multilayer polyethylene bottle containing 0.02% by weight of 2-n-octyl-4-isothiazolin-3-one as a system compound and having an average body thickness of about 1000 μm was prepared.

[Experiment 1] Penici was used as a mold indicator fungus.
lium citrinum IFO 6352 spores was used as a bacterial indicator bacterium for Methylobacterium e isolated from red slime generated on the bathroom floor.
xtorquens (Furuhata et al .: Fungicide and fungicide, 18,407)
-410 (1990))
Bacterium extorquens IFO
3708 cells were smeared on an agar medium, and the samples of Examples and Comparative Examples were punched into a circular shape having a diameter of 10 mm.
The cells were brought into close contact with the medium and cultured. Potato dextrose agar was used for mold, and standard agar was used for bacteria.
The mold culture temperature was 25 ° C, and the bacterial culture temperature was 30 ° C. After culturing for one week, the presence or absence of a halo (inhibition circle, see FIG. 5) was observed and the size was measured. The results are as shown in [Table 1]. If it has antibacterial properties, it forms a halo (inhibition circle). The size of the halo was an average of the maximum diameter and the minimum diameter.

[0026]

[Table 1]

[Experiment 2] The bottles of Examples and Comparative Examples were left in a bathroom of a general household to observe the occurrence of darkening and slimming. The results are as shown in [Table 2].

[0028]

[Table 2]

[Experiment 3] The presence or absence of a halo (blocking circle, see FIG. 5) was observed in the same manner as in Experiment 1 for the samples of Examples and Comparative Examples subjected to Experiment 2. The results are as shown in [Table 3] and [Table 4].

[0030]

[Table 3]

[0031]

[Table 4]

That is, according to the results of Experiment 1, by adding simultaneously an antibacterial agent effective against bacteria and an antibacterial agent effective against mold, including the resin laminate according to the present invention, both bacteria and mold can be prevented. It was shown that it is possible to obtain a resin laminate having an antibacterial action. In this experiment,
Antibacterial agents effective against bacteria are quaternary ammonium salt antibacterial agents,
Antibacterial agents effective against mold are thiazoline antibacterial agents. In addition, a synergistic effect was observed by adding the two kinds of drugs, and the polyethylene bottle provided higher antibacterial properties. In Experiments 2 and 3, the persistence of the effect was confirmed in Example 2. However, as shown in Example 1, as a result of adding an antimicrobial agent which easily migrates over two layers, the persistence of the antibacterial effect was further improved. Heightened. By increasing the layer ratio of the antibacterial outer layer (11), it is expected that the amount of the antibacterial agent will increase and the sustainability of the antibacterial activity will increase. The amount is large and it is not economical. The antibacterial resin laminate developed according to the present invention is economical and extremely excellent in that the amount of the antibacterial agent to be added is minimized and the effect is maximized. In addition, it was confirmed that it was effective for maintaining the effect on both mold and bacteria.

From the results of Experiment 2, it was found that even when the resin laminate according to the present invention was actually applied and used, the effect of preventing slime and darkening was exhibited over a long period of time. In recent years, the use of refill containers has been increasing due to environmental considerations. The issues here are durability and how to keep it clean. By using the antibacterial resin laminate according to the present invention, it is possible to suppress the occurrence of slimming and darkening over a long period of time, and to produce an antibacterial resin multilayer molded article that can respond to the consumer's desire for cleanliness. is there.

[0034]

According to the antibacterial resin multilayer molded article of the present invention, the growth of mold can be achieved by adding an antibacterial agent which hardly migrates in the resin or an antibacterial agent which hardly migrates and an antibacterial agent which easily migrates in the resin. It has become possible to provide an antibacterial resin multilayer molded article that prevents both darkening caused by bleeding and slimming caused by the growth of bacteria, and maintains its effects for a long period of time even under adverse conditions such as around water. is there.

Specifically, by simultaneously adding an antibacterial agent effective against bacteria and an antibacterial agent effective against mold, including the resin laminate according to the present invention, both bacteria and mold can be prevented. Thus, it was shown that it was possible to obtain a resin laminate having an antibacterial action. In this experiment,
Antibacterial agents effective against bacteria are quaternary ammonium salt antibacterial agents,
Antibacterial agents effective against mold are thiazoline antibacterial agents. In addition, a synergistic effect was observed by adding the two kinds of drugs, and the polyethylene bottle provided higher antibacterial properties. In Experiments 2 and 3, the persistence of the effect was confirmed in Example 2. However, as shown in Example 1, as a result of adding an antimicrobial agent which easily migrates over two layers, the persistence of the antibacterial effect was further improved. Heightened. By increasing the layer ratio of the antibacterial outer layer (11), it is expected that the amount of the antibacterial agent will increase and the sustainability of the antibacterial activity will increase. The amount is large and it is not economical. The antibacterial resin laminate developed according to the present invention is economical and extremely excellent in that the amount of the antibacterial agent to be added is minimized and the effect is maximized. In addition, it was confirmed that it was effective for maintaining the effect on both mold and bacteria.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of an embodiment of an antibacterial resin multilayer molded product according to the present invention.

FIG. 2 is a schematic cross-sectional view of one embodiment of the multilayered antibacterial resin product of the present invention.

FIG. 3 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention.

FIG. 4 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention.

FIG. 5 is a schematic cross-sectional view of another embodiment of the multilayered antibacterial resin product of the present invention.

FIG. 6 is a schematic diagram showing a halo in a halo (inhibition circle) method, which is one of the antibacterial assay methods.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Antibacterial resin multilayer molded article 11 ... Antibacterial outer layer 12 ... Antibacterial intermediate layer 13 ... Inner layer 14 ... Antibacterial agent shielding layer 15 ... Recovery layer 2 ... Petri dish 21 ... Bacteria growth area 22 ... Halo (blocking circle) 3 ... Test pieces

Continued on front page F-term (reference) 3E067 AA03 AB83 BA02A BB14A BB25A EE32 EE33 GC05 4F100 AK01A AK01B AK04A AK04B AK04C AK04D BA03 BA04 BA07 BA10A BA10C CA12A CA12B CA12D GB08 J16 GB56J01J00 J00 GB00J01J00

Claims (6)

[Claims] An antibacterial resin multilayer molded product (1) comprising at least an antibacterial outer layer (11), an antibacterial intermediate layer (12) and an inner layer (13). 2. The antimicrobial resin multilayer molded article (1) according to claim 1, wherein an antimicrobial agent shielding layer (14) is provided between the antimicrobial intermediate layer (12) and the inner layer (13). 3. The antibacterial resin multilayer molded article (1) according to claim 1, wherein a collecting layer (15) is provided between the antibacterial intermediate layer (12) and the inner layer (13). 4. The antibacterial resin multilayer molded article according to claim 1, wherein an antibacterial agent shielding layer (14) and a collecting layer (15) are provided between the antibacterial intermediate layer (12) and the inner layer (13). 1). 5. The antibacterial resin multilayer molded article (1) according to claim 3, wherein the collecting layer (15) has an antibacterial agent shielding function. 6. The antibacterial outer layer (11) contains an antibacterial agent which hardly migrates in the resin, and the antibacterial intermediate layer (12) contains an antibacterial agent which can migrate in the resin and the antibacterial outer layer (11). The antibacterial resin multilayer molded article (1) according to any one of claims 1 to 5, which contains the antibacterial resin multilayer molded article (1).