JP3433665B2 - Antibacterial multilayer resin structure - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer resin structure having antibacterial properties to prevent darkening, slimyness and the like on the surface of resin products caused by microorganisms such as mold, yeast and bacteria. Is. More specifically, the bathroom,
Suitable for use in detergents, shampoos, rinses, liquid or powder soaps, etc. used in kitchens, washrooms, etc. where microorganisms are likely to grow and in hospitals, etc. where hygiene is required. And a multi-layer structure.

[0002]

2. Description of the Related Art Antibacterial agents that can be added to resins have been developed and are already widely used. Such antibacterial agents are roughly classified into inorganic antibacterial agents in which silver, zinc, etc. are supported on zeolite or the like. , Two types of organic antibacterial agents consisting of organic substances having antibacterial properties.

Silver is widely used as the inorganic antibacterial agent, and zinc is used when discoloration due to light is a problem. Resins containing this inorganic antibacterial agent are used in cooking utensils such as cutting boards and balls, bathroom chairs, bath products such as washbasins, washing tubs for washing machines, filters and water tanks for humidifiers, etc. Widely used in stationery such as ballpoint pens.

As a resin containing an organic antibacterial agent, an imidazole antibacterial agent or a thiazoline antibacterial agent is used in a washing tub of a washing machine. Resins to which any of these inorganic antibacterial agents and organic antibacterial agents have been added are either added directly to the resin at the time of molding or as a high-concentration masterbatch and molded into various products.

[0005]

Inorganic antibacterial agents are said to be highly safe for the human body, and because they have high heat resistance, they are not very restricted when added to resins and are extremely useful. It is an antibacterial agent. However, silver
Since the antibacterial effect against fungi such as mold and yeast is small,
For example, a large amount of addition is necessary in order to prevent mold crazing. Further, silver has a problem that it causes discoloration due to light. On the other hand, zinc is not discolored by light, but its antibacterial effect is extremely smaller than that of silver, so it is impossible to obtain the antibacterial effect by itself.

In the case of organic antibacterial agents, few have antibacterial properties against both mold and bacteria. For example, according to the research results of the inventors, a drug containing a benzalkonium salt, which is a mixture of alkyldimethylbenzylammonium salts having different alkyl chain lengths, which is an example of a quaternary ammonium salt, as an antibacterial component was added to polyethylene. In this case, addition of 0.02% by weight or more as benzalkonium ion shows an antibacterial effect against general bacteria. However, no antibacterial effect was observed against mold.

In addition, 2 which is an example of a thiazoline compound
-When an agent containing octyl-4-isothiazolin-3-one as an antibacterial component is added to polyethylene, 0.005- is obtained as 2-octyl-4-isothiazolin-3-one.
0.5% by weight is effective against mold. However, no effect was observed against Pseudomonas bacteria which are gram-negative bacteria. Further, when a thiazoline compound is added to the resin, in a molding product processing method such as extrusion molding or direct blow molding, the thiazoline compound that comes into contact with the metal part of the molding machine in the resin molten state during molding of the resin composition is the metal of the molding machine. There is a problem that the surface of the resin composition is roughened by being adhered to a portion, the surface of the resin composition becomes sticky, and the ink adhesion during printing is impaired.

In the case of a thiazoline compound, although it has an antibacterial effect against mold immediately after molding, it decomposes by receiving light over time, loses its effect, or is decomposed by heat during molding. A decrease in antibacterial activity occurs, usually
There is a problem that the antibacterial property cannot be maintained for a long period of time under the environment where the resin product is used.

The present invention solves the problems and retains good antibacterial properties against microorganisms (molds, bacteria, etc.) for a long period of time, does not cause discoloration or deterioration of strength of the resin, and has good moldability. It is an object of the present invention to provide a flexible multilayer resin structure.

[0010]

According to a first aspect of the present invention, there is provided an outer layer on the outer surface side of a container made of a resin to which at least a quaternary ammonium salt chemical is added, and an inner layer of the outer layer.
An adjacent layer made of a resin to which a chemical agent selected from a thiazoline compound is added, and an inner surface side of the container of the adjacent layer.
A container inner layer made of a resin that does not contain misaligned chemicals
It is an antibacterial multilayer resin structure characterized by having .
The invention described in claim 2 is the same as the invention described in claim 1.
A recovery layer is provided between the adjacent layer and the inner layer.
Is an antibacterial multilayer resin structure. The invention according to claim 3
Is the adjacent layer in the invention according to claim 1 or 2.
The antibacterial multilayer resin structure is characterized in that a gas barrier resin layer is provided on the inner surface side of the container .

The invention according to claim 4 is the invention according to claims 1 to 3.
The antibacterial multilayer resin structure according to any one of claim 3
Oite, the quaternary ammonium salt-based agents, selected from alkyl dimethyl benzyl ammonium salt (alkyl carbon number of groups C ₈ -C ₁₈₎ and alkylpyridinium salts (number of carbon atoms in the alkyl group C ₈ -C ₁₈₎ It is an antibacterial multilayer resin structure characterized by comprising a single substance or a plurality of substances. The invention according to claim 5 is the antibacterial property according to claim 4.
In the multilayer resin structure, the content concentration of the quaternary ammonium salt-based drug is 0.02 to 2.5% by weight as quaternary ammonium ion, which is an antibacterial multilayer resin structure. The invention according to claim 6 is a claim
Item 1. The antibacterial multi-layer tree according to any one of items 1 to 5.
In fat structure, said thiazoline compound is 2-octyl-4-isothiazolin-3-one Japanese
It is an antibacterial multi-layered resin structure as a characteristic. Claim 7
The present invention provides an antibacterial multilayer resin structure according to claim 6.
The content concentration of the thiazoline compound is 0.00
The antibacterial multilayer resin structure is characterized by being 5 to 0.5% by weight.

[0012] The invention according to claim 8 is from claim 1 to contract.
The antibacterial multilayer resin structure according to any one of claim 7
In at least the adjacent layer, an antibacterial multilayer resin structure is characterized in that it comprises a resin to which an ultraviolet absorber and / or a light / heat stabilizer is added. In claim 9
The described invention is the antibacterial multilayer resin structure according to claim 8.
2. In the antibacterial multilayer resin structure , the ultraviolet absorber is a benzotriazole-based compound. The invention described in claim 10 is claim 8 or claim.
9. The antibacterial multilayer resin structure according to item 9,
The stabilizer is an antibacterial multilayer resin structure characterized in that it is a hindered amine compound. Claim 11
The present invention provides an antibacterial multilayer resin structure according to claim 9.
The benzotriazole compound is 2- (3-
t-butyl-5-methyl-2-hydroxyphenyl)-
5-chlorobenzotriazole, the content concentration of which is 0.
It is an antibacterial multilayer resin structure characterized by being 005 to 1.0% by weight. The invention according to claim 12 is a claim
Item 10. The antibacterial multilayer resin structure according to Item 10,
The dad amine compounds are dimethyl succinate 1-
(2-hydroxyethyl) -4-hydroxy-2,2
An antibacterial multilayer resin structure, which is a polycondensation product of 6,6-tetramethylpiperidine and has a content concentration of 0.005 to 1.0% by weight.

The invention according to claim 13 is the first to the third aspects.
The antibacterial multilayer resin structure according to claim 12.
In the body, the structure of the antibacterial multilayer resin structure is
-Antibacterial multi-layer resin structure characterized by being a molded product
Is.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be specifically described. FIG. 1 is a cross-sectional view showing an example of the multilayer resin structure of the present invention. An outer layer 11 made of a resin to which a quaternary ammonium salt-based agent is added, and a drug selected from a thiazoline-based compound inside the outer layer 11 are shown. An antibacterial multilayer resin structure having a multilayer structure having an adjacent layer 12 made of added resin. FIG. 2 is a cross-sectional view showing another example of the multilayer resin structure of the present invention, in which an inner layer 13 made of a resin containing neither drug is provided inside the adjacent layer 12 of FIG. It is a structure. FIG. 3 is a cross-sectional view showing another example of the multilayer resin structure of the present invention, which is an antibacterial multilayer resin structure in which a recovery layer 14 is provided between the adjacent layer 12 and the inner layer 13 of FIG. FIG. 4 is a cross-sectional view showing another example of the multilayer resin structure of the present invention, which is an antibacterial multilayer resin structure in which the gas barrier resin layer 15 is provided inside the adjacent layer 12 of FIG.

Here, the quaternary ammonium to be added to the outer layer 11 is represented by the general formula [C ₆ H ₅ .CH ₂ .N + (CH
₃ ) ₂ R] Cl- (where R is a mixture of C ₈ H ₁₇ to C ₁₈ H ₃₇ ) and benzalkonium chloride, as shown in the general formula [C ₂₁ H ₃₈ ClN.H ₂ O]. The above cetylpyridinium chloride is bound to a phosphate such as zirconium phosphate or titanium phosphate by ion exchange. In other words, those supported on an inorganic carrier, such as those in the form of a salt of quaternary ammonium and phosphoric acid, can be suitably used. The content of quaternary ammonium in this support is determined by the ion exchange capacity when it is retained by ion exchange, for example, but it is generally 5% by weight.
To 30% by weight.

Examples of the thiazoline compound added to the adjacent layer 12 provided inside the outer layer 11 include 2-octyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4.
Examples thereof include -isothiazolin-3-one, and 2-octyl-4-isothiazolin-3-one retained by adsorption on an inorganic substance such as silicon oxide can be preferably used. The content of the thiazoline compound in this support is appropriately in the range of 25% by weight to 70% by weight. And, in the resin of the resin structure according to the present invention, the content of the antibacterial component of the outer layer 11 is such that the quaternary ammonium salt is 0.02 wt% to 2.5 wt% as quaternary ammonium ion,
0.005% to 0.5% by weight of thiazoline compound
Is appropriate. As the organic antibacterial agent added to the adjacent layer 12, in addition to the thiazoline compound, a nitrile compound,
Anilide type, ester type, phenol type, ether type,
Surfactant-based, pyridine-based, triazone-based compounds and the like can be used. A thiazoline compound is added to the outer layer 11, that is, a resin layer containing a quaternary ammonium salt-based antibacterial agent, and a quaternary ammonium salt-based antibacterial agent is added to the adjacent layer 12 provided inside the outer layer 11 to assist the antibacterial property. It is also possible to add a small amount of each agent. The adjacent layer 12 may have a structure not only in direct contact with the outer layer 11 but also with a thin resin layer interposed therebetween.

The benzotriazole-based compound used as the ultraviolet absorber is 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, the concentration of which is 0.005-1. 0.0% by weight is suitable. Further, it is a hindered amine-based dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate used as a light / heat stabilizer, and its content concentration is 0. .005
~ 1.0 wt% is suitable. Further, a benzoate compound or the like can be used as the light / heat stabilizer.

Added to the multilayer resin structure according to the invention,
The action of the ultraviolet absorber and the light / heat stabilizer is that the ultraviolet absorber and the light / heat stabilizer convert light energy into heat energy and further absorb the heat energy, that is, the antibacterial agent, that is, thiazoline in the adjacent layer 12. It prevents the compounds from being affected by ultraviolet rays, light, or heat, or blocks light, stabilizes molecules activated by light or heat, and prevents deterioration of antibacterial performance. Further, the antibacterial property is stably maintained for a long period of time. Further, the content concentration of the ultraviolet absorber and the light / heat stabilizer is set in the range of 0.005 to 1.0% by weight because the content of the thiazoline compound is less than 0.005% by weight. The sustainability is not sufficiently exerted, and when the content of each of the ultraviolet absorber and the light / heat stabilizer exceeds 1.0% by weight, the sustainability of the antibacterial effect becomes constant, which is not economical. The concentration of each of the antibacterial agent, the ultraviolet absorber and the light / heat stabilizer is the concentration for each layer.

As a method of adding an ultraviolet absorber and a stabilizer to the resin, the outer layer 11 and the adjacent layer 12 have a light resistance imparting agent, a light / heat stabilizer and an antibacterial agent dispersed on or near the surface of the final product. As long as it is a method that can be arranged well,
For example, prepare a high-concentration antibacterial agent masterbatch, a high-concentration lightfastness-imparting agent, and a light / heat stabilizer masterbatch separately, and mix them with the virgin resin at the same time to achieve the desired concentration when molding the product. , A method of molding, a method of adding an antibacterial agent, a light resistance-imparting agent, and a heat / light stabilizer to the same masterbatch in advance and mixing with a virgin resin at the time of molding of the product, and the like. At this time, the masterbatch is designed to be added in an amount of 5% or more with respect to the virgin resin,
Molding improves the dispersibility of the drug.

The outer layer 11 and the adjacent layer 12 which are made of a resin to which an antibacterial agent, an ultraviolet absorber and a light / heat stabilizer are added in the present invention are specifically exemplified by polyethylene resin and polypropylene resin. Thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyester resins, acrylic resins, nitrile resins, and styrene resins, and modified products of these resins, natural resins such as gum arabic, cerax, nitrified cotton, and phenolic resins. A thermosetting resin such as melamine resin or an isocyanate resin can be used, and if they have a laminated structure, they may be a simple substance or a composite of these resins. Also, melt the resin in a solvent,
After coating, it is an article containing ink, varnish, etc. that forms a resin layer by vaporizing a solvent, curing with ultraviolet rays, and curing with heat.
Further, substances that are usually added to the resin composition such as an antioxidant, an ultraviolet absorber, a colorant, an antistatic agent and a plasticizer with respect to the resin composition of the present invention are not limited.

Further, the inner layer 13 is made of the resin described above, and is made of a resin to which an antibacterial agent, an ultraviolet absorber and a light / heat stabilizer are not added, and the recovery layer 14 is formed when the resin is molded. , Made of a resin mixed with unnecessary parts. It may be appropriately selected from the gas barrier resin layer 15 and resins such as ethylene-vinyl alcohol copolymer, nylon and polyester.

The antibacterial multilayer resin structure of the present invention may be molded by any method capable of forming a multilayer structure, such as direct blow molding, injection blow molding, blow molding such as stretch blow molding, coat hanger and the like. Sheet extrusion using a die, and sheet forming such as vacuum, compressed air, press, and plug assist molding.

In the antibacterial multilayer resin structure according to the present invention, the resin of the outer layer 11 contains a quaternary ammonium salt, the adjacent layer 12 inside thereof contains a thiazoline compound, and further an ultraviolet absorber and a light / heat stabilizer are added. By doing so, during processing of the molded product such as extrusion molding and direct blow molding, the thiazoline compound comes into contact with the metal part and adheres to the metal part of the molding machine to cause roughening of the surface of the resin composition or the surface of the resin composition. It is not sticky or inhibits ink adhesion during printing, has an excellent antibacterial action against mold and bacteria, and is free from discoloration due to light and deterioration of antibacterial property.

[0024]

<Example 1> 0.5% by weight of benzalkonium salt as a quaternary ammonium salt as a benzalkonium ion in the outer layer, and 2-octyl as a thiazoline-based substance in an inner adjacent layer in contact with the outer layer. 0.04% by weight of 4-isothiazolin-3-one and 2 as an ultraviolet absorber
0.05% by weight of-(3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and dimethyl succinate 1- (2- as a light / heat stabilizer.
Hydroxyethyl) -4-hydroxy-2,2,6,6
0.04% by weight of tetramethylpiperidine polycondensate,
A four-layer multi-layer high-density polyethylene consisting of a recovery layer containing burrs generated during bottle molding, that is, a ground parison crushed product inside the adjacent layer, and an inner layer containing no antibacterial agent or burrs inside the recovery layer. Bottle (average body thickness of about 1000 μm, layer ratio 10%: 15%: 65%: 10
%) Was prepared. The benzalkonium salt is benzalkonium chloride supported on aluminum tripolyphosphate by ion exchange, and 2-octyl-4-isothiazolin-3-one is supported on silica gel by adsorption. The parison was added during extrusion to achieve the desired drug concentration.

<Comparative Example 1> The average thickness of the body is about 1000μ.
m high density polyethylene bottle was prepared.

<Comparative Example 2> In the same manner as in Example 1, benzalkonium salt as a quaternary ammonium salt was added to the outer layer in an amount of 0.5% by weight as a benzalkonium ion, and 2-octyl-4- as a thiazoline-based substance. Isothiazoline-3-
0.02% by weight of on and 2- (3-
t-butyl-5-methyl-2-hydroxyphenyl)-
0.05% by weight of 5-chlorobenzotriazole and light /
0.06% by weight of dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate as a heat stabilizer, and the burrs formed inside during bottle molding That is, a multi-layered high-density polyethylene bottle with a recovery layer containing crushed top and bottom parison and an inner layer containing no antibacterial agent and burrs (average body thickness of about 1000 μm, layer ratio 10%: 80%: 10
%) Was prepared. The benzalkonium salt is benzalkonium chloride supported on aluminum tripolyphosphate by ion exchange, and 2-octyl-4-isothiazolin-3-one is supported on silica gel by adsorption. The parison was added during extrusion to achieve the desired drug concentration. The following experiments were carried out using the above three samples.

<Experiment 1> The surface of each molded bottle was visually observed. The results of that state are shown in Table 1.

[0028]

[Table 1] As described above, good moldability was obtained in Example 1 and Comparative Example 1, but in Comparative Example 2, vertical streaks were generated on the bottle surface, and good moldability could not be obtained.

<Experiment 2> In order to evaluate the printability, the surface of each molded bottle was subjected to a flame treatment at 62 dyne / cm ² and then subjected to a silk screen printing treatment with a polyester-based ultraviolet curable ink. After that, the printed part was immersed in warm water of 40 ° C. for 24 hours, and then a peeling test was performed using a commercially available cellophane tape to evaluate the ink / bottle adhesion. The results are shown in Table 2.

[0030]

[Table 2] As described above, in Example 1 and Comparative Example 1, good printability was obtained, but in Comparative Example 2, peeling of the printing ink occurred, and good printability could not be obtained.

<Experiment 3> Methylobacterium e isolated from red slime that grows on the bathroom floor as a bacterial indicator bacterium
xtorquens (Furuhata et al .: Antibacterial and antifungal, 18, 407-410, (199
0)), the same species as Methylobacterium extorquens IFO
The 3708 bacterial cells were added to a standard agar medium cooled to 48 ° C. after autoclaving at about 10 ⁶ (cells / ml). Bottle piece 1 sterilized with ethanol for disinfection
As shown in FIG. 5, 1 ml of agar medium 2 was dropped into each (sterilized petri dish), and culture was carried out at 30 ° C. for 48 hours so as not to dry, and then observed.

As shown in FIG. 6, in both Example 1 and Comparative Example 2, a portion (inhibition zone) for inhibiting the growth of M. extorquens IFO 3708 was formed in the portion of the dropped medium 2 in contact with the bottle surface. , M. extorquens IFO 3708 was confirmed, but in Comparative Example 1, no inhibition zone was formed and no antibacterial property was confirmed.

<Experiment 4> Penicillum c as a fungus indicator bacterium
itrinum IFO the 6352 spores, pressurized steam sterilized after the potato dextrose agar medium about 10 ⁶ during cooling to 48 ℃ (number /
(ml) was added. Bottle piece 1 (in a sterilized petri dish) sterilized with ethanol for disinfection
As shown in FIG. 7, 1 ml of agar medium 2 was added dropwise to each of them, and the mixture was incubated at 25 ° C. for 72 hours so as not to dry, and observed.

As shown in FIG. 8, in both Example 1 and Comparative Example 2, a portion of the dropped medium was contacted with the bottle surface.
Part that inhibits growth of P. citrinum IFO 6352 (zone of inhibition)
Was observed and antibacterial activity against P. citrinum IFO 6352 was confirmed, but in Comparative Example 1, no inhibition zone was formed and antibacterial activity was not confirmed.

[0035]

According to the present invention, the resin of the outer layer contains a quaternary ammonium salt, the resin layer of the inner layer contains a thiazoline compound, and an ultraviolet absorber and a light / heat stabilizer are added to the resin for extrusion. During molding and processing of molded products such as direct blow molding, the thiazoline compound comes into contact with the metal part and adheres to the metal part of the molding machine, causing the surface of the resin layer to become rough, and the surface of the resin layer due to the thiazoline compound becomes sticky and printing. It is possible to obtain an antibacterial multilayer resin composition that does not impair ink adhesion at the time, has an excellent antibacterial action against mold and bacteria, and does not have discoloration due to light and deterioration of antibacterial property. .

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view showing another example of the resin structure of the present invention.

FIG. 3 is a cross-sectional view showing another example of the resin structure of the present invention.

FIG. 4 is a cross-sectional view showing another example of the resin structure of the present invention.

FIG. 5 is an explanatory diagram showing a state of Experimental Example 3;

FIG. 6 is an explanatory diagram showing the results of Experimental Example 3.

FIG. 7 is an explanatory diagram showing a state of Experimental Example 4;

FIG. 8 is an explanatory diagram showing the results of Experimental Example 4.

[Explanation of symbols]

1 ... Bottle section 2 ... Agar medium 11 ... Outer layer 12 ... Adjacent layer 13 ... inner layer 14 ... Collection layer 15 ... Gas barrier resin layer

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-90726 (JP, A) JP-A-8-310903 (JP, A) JP-A-1-164722 (JP, A) JP-A-3- 181538 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B65D 1/00-1/48 A01N 25/00-25/34 A01N 43/80

Claims (13)

(57) [Claims] 1. An outer layer on the outer surface side of a container, which is made of a resin to which at least a quaternary ammonium salt chemical is added, and the outer layer.
On the inner surface side of the container, an adjacent layer made of a resin to which a drug selected from a thiazoline compound is added, and the inner surface of the container of the adjacent layer
On the inner side of the container made of resin that does not contain any chemicals.
Antibacterial multi-functionality characterized by having an inner layer to be
Layer resin structure. Wherein said adjacent layers and the inner layer antibacterial multilayer resin structure according to claim 1, characterized in that a collection layer between. Wherein the inner surface of the container side of the adjacent layer, according to claim 1 or claim 2, characterized in that a gas barrier resin layer
The antibacterial multilayer resin structure described. 4. The quaternary ammonium salt-based drug is selected from alkyldimethylbenzylammonium salts (alkyl groups having C _{8 to} C ₁₈ ) and alkylpyridinium salts (alkyl groups having C _{8 to} C ₁₈ ). claim, characterized in that the a single or a plurality of substances 1 to claim 3
An antibacterial multilayer resin structure according to any one of 1. 5. The content concentration of the quaternary ammonium salt-based drug is 0.02 to 2.
The antibacterial multilayer resin structure according to claim 4, which is 5% by weight. 6. The thiazoline-based compound is 2-octyl-4-isothiazolin-3-one .
The antibacterial multilayer resin structure according to any one of claims 1 to 5 . 7. The content concentration of the thiazoline compound is
Claims characterized by being 0.005-0.5% by weight
Item 7. The antibacterial multilayer resin structure according to item 6 . 8. An ultraviolet absorber, at least the adjacent layer,
The antibacterial multilayer resin structure according to any one of claims 1 to 7, which is made of a resin to which or / and a light / heat stabilizer is added. 9. The antibacterial multilayer resin structure according to claim 8, wherein the ultraviolet absorber is a benzotriazole compound. 10. The light / heat stabilizer is a hindered amine-based compound, as claimed in claim 8 or claim 9.
The antibacterial multilayer resin structure described. Wherein said benzotriazole compound is 2
10. (3-T-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, the content concentration of which is 0.005 to 1.0% by weight. Antibacterial multilayer resin structure. 12. The hindered amine compound is a dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, the content concentration of which is 0.1. The antibacterial multilayer resin structure according to claim 10, which is 005 to 1.0% by weight. 13. The structure of the antibacterial multilayer resin structure is
The antibacterial multilayer resin structure according to any one of claims 1 to 12, which is a low-molded product .