JP2000072927A - Antibacterial antimold resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which, in spite of a low content of an antibacterial/antimold agent, can fully and safely exhibit both antibacterial and antimold effects by mixing a resin with an antibacterial/antimold agent being zinc bis(2-pyridylthio-1-oxide). SOLUTION: A resin is mixed with 0.04-0.08 wt.% antibacterial/antimold agent comprising zinc(2-pyridylthio-1-oxide). In order to prevent the deterioration or discoloration of the resin material and to enhance the dispersibility of the antibacterial/antimold agent in the resin, the resin is mixed with 0.3-0.50 wt.% antibacterial/antimold agent containing zinc bis(2-pyridylthio-1-oxide) as an active ingredient and at least one of an ultraviolet absorber, a discoloration preventive, and a dispersant. The discoloration preventive used is, for example, a chelating agent such as ethylenediaminetetraacetic acid disodium salt or sodium acid hezametaphosphate. The dispersant used is exemplified calcium carbonate, talc, or silicon dioxide. The resin used is desirably polyethylene, which is inherently resistant to bacterial attack.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a resin material that can be supplied to various fields including foods, and more particularly to an antibacterial / antifungal resin composition containing a specific antibacterial / antifungal component. Is involved.

[0002]

2. Description of the Related Art Resin materials are used in extremely various fields, and there are many resin products in everyday life. In addition, parts made of a resin material are used in large quantities even in places where they directly touch the human body.

[0003] In food factories and the like, resin boards and containers are used for tables and vessels used in the process of producing food. When food residue adheres to the surface of such a resin plate or container, microorganisms are liable to multiply, and the microorganisms may impair the quality and preservability of the food.

[0004] Further, when resin is used for parts in the manufacturing process of precision equipment, foreign substances such as dust must not be present, and of course, microorganisms are not allowed to propagate. When a resin is used under such conditions, a polyethylene resin in which microorganisms are relatively difficult to grow has been used.

[0005] Further, resins containing an antibacterial agent are also used. Conventionally, antibacterial and antifungal agents used for resins can be classified into inorganic and organic ones. Silver-based antibacterial and antifungal agents are often used as the former inorganic ones. As the latter organic type, an imidazole type is often used.

[0006]

However, even if the polyethylene resin is relatively difficult for microorganisms to grow, microorganisms may grow depending on the surface condition of the resin.
Naturally, when used in food-related factories and the like, the resin is washed after the work is completed, but it is difficult to completely eliminate microorganisms. As a method, there is a method of performing cleaning for a long time using a high-concentration chemical such as sodium hypochlorite aqueous solution of hydrogen peroxide, but this method is not practical because a large amount of labor is required for sanitary management.

[0007] Further, silver-based antibacterial agents, which are inorganic antibacterial agents, have a drawback that they cause discoloration of the resin when kneaded into the resin. No antibacterial and antifungal performance could be obtained. Further, regarding the antifungal property of the silver-based antibacterial and antifungal agent, there is a problem that the antifungal effect is effective only in a limited kind among a large number of fungi.

[0008] On the other hand, the latter organic antibacterial and fungicide have the advantage that a large effect can be obtained with a small amount of addition, are relatively low in toxicity, have high safety, and hardly discolor the resin. For this reason, organic compounds have attracted attention as antibacterial and antifungal agents, among which 2- (4-thiazolyl)
An imidazole-based compound, such as benzimidazole, described above is disclosed in JP-A-58-57367. However, although imidazoles have a certain effect on fungicidal properties, they have little effect on antibacterial properties and can provide both sufficient antibacterial and antifungal properties. Did not.

Accordingly, the present invention provides an organic antibacterial and antifungal agent which can provide a large effect by adding a small amount thereof, is highly safe, and can sufficiently obtain both antibacterial and antifungal effects with a single agent. It is an object of the present invention to provide an antibacterial and antifungal resin composition that can be used.

[0010]

According to the first aspect of the present invention, there is provided an antibacterial and antifungal resin composition having both antibacterial and antifungal effects. The composition is characterized by containing 0.04 to 0.08% by weight of an antibacterial and antifungal agent composed of bis (2-pyridylthio-1-oxide) zinc.

[0011] As described above, by adding bis (2-pyridylthio-1-oxide) zinc to a resin as a specific antibacterial and antifungal agent, a single agent has excellent effects in both antibacterial and antifungal properties. Can be obtained.

According to a second aspect of the present invention, there is provided an antibacterial and antifungal resin composition having both antibacterial and antifungal effects, wherein the resin comprises bis (2-pyridylthio-1-oxide) zinc as an active ingredient and at least ultraviolet rays. Absorbent, anti-tarnish,
0.30 to 0.50% by weight of an antibacterial and fungicide containing a dispersant
An antibacterial and antifungal resin composition characterized by containing.

By including an ultraviolet absorber other than the antibacterial and antifungal component, various physical properties such as discoloration prevention required when used as a resin material can be imparted.

According to a third aspect of the present invention, bis (2-pyridylthio-1-oxide) zinc, an antibacterial and antifungal agent, an ultraviolet absorber, a discoloration inhibitor and a dispersant are dispersed or dissolved in the resin.

By dispersing the components throughout the resin as described above, a resin material having uniform performance throughout can be obtained.

In the present invention, the resin is limited to polyethylene, but polyethylene is a material which is hardly proliferated by bacteria, and a resin composition in which bacteria and mold are hardly generated in combination with the effect of an antibacterial and fungicide. Obtainable.

[0017]

Embodiments of the present invention will be described below.

Desirable conditions required for antibacterial and fungicide, for example, as a resin material used in foods, are that the color of the antibacterial and fungicide itself is white or pale yellow so that the resin is not colored in terms of properties. Powder so that it can be uniformly dispersed or dissolved in the resin.
Being fine particles of a size that can pass through a mesh sieve,
It must be stable even at the resin molding temperature, and be insoluble in water so as not to elute in water.

The antifungal composition of the antibacterial and antifungal agent composition preferably has an antifungal effect according to JIS Z 2911 or ASTM G21-70.

In the present invention, bis (2-pyridylthio-1-oxide) zinc or bis (2-pyridylthio-1-oxide) zinc is used as an active ingredient to satisfy these conditions. An antibacterial and fungicide containing an absorbent, a discoloration inhibitor and a dispersant is used. The antibacterial and antifungal agent containing bis (2-pyridylthio-1-oxide) zinc as an active ingredient satisfies the above-mentioned conditions, and has low toxicity that satisfies the Food Sanitation Law and the Ministry of Health and Welfare Notification No. 20 used for foods. But also.

The antibacterial properties of this antibacterial and antifungal agent are as shown in Table 1 below.

[0022]

[Table 1]

The resin containing the antibacterial and antifungal agent used in the present invention is not particularly limited, but high-density polyethylene (molecular weight of 200,000 to 500,000) and ultra-high molecular weight polyethylene (molecular weight of 3,000,000 to 6,000,000) ), Polyvinylidene fluoride resin, polypropylene resin, polyurethane resin,
Examples include polyester resin, polyacrylic resin, polyamide resin, polystyrene resin, ABS resin, and polyvinyl chloride resin.

However, among these, high-density polyethylene and ultra-high-molecular-weight polyethylene can be said to be materials that are difficult for bacteria to grow and mold to grow.
It is effective and preferable to mix and use an antibacterial and fungicide with these materials.

An ultraviolet absorber is used to prevent the resin material from being deteriorated by the action of ultraviolet light. Specific examples of the ultraviolet absorber include 2- (3-tbutyl-5-methyl). -2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-
2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2)
-Hydroxyphenyl) benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- {2-hydroxy-3,5-
Bis (α, α-dimethylbenzyl) phenyl} -2H-
Benzotriazole-based ultraviolet absorbers such as benzotriazole, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 2,5-bis} A hindered amine-based ultraviolet absorber such as 5'-t-butylbenzooxazolyl (2) thiophene can be used.

Further, the discoloration inhibitor is compounded to prevent discoloration of the active ingredient of the antibacterial and antifungal agent and to prevent the resin material from discoloring. Specific examples of the discoloration inhibitor include: Chelating agents such as disodium ethylenediaminetetraacetate and sodium acid hexametaphosphate can be used.

The above-mentioned bis (2-
(Pyridylthio-1-oxide) Zinc, an ultraviolet absorber, and a discoloration inhibitor are mixed with a resin or an adhesive agent to improve the fluidity or dispersibility of each of these components, thereby improving the fluidity or dispersibility of the components. In the present invention, bis (2-pyridylthio-1)
-Oxide) An ultraviolet absorber and a discoloration inhibitor are added to zinc, and a dispersant is further added to adjust the antibacterial and antifungal agent.

As the dispersant, calcium carbonate, talc, silicon dioxide and the like can be used.

The antibacterial and antifungal agent prepared as described above has a particle size of 50-150 μm passing through a 100-mesh sieve.
m. The composition ratio of the antibacterial and fungicide is not particularly limited, but the bis (2-pyridylthio-1-oxide) zinc is 100 parts by weight, the ultraviolet absorber is 20 to 50 parts by weight, and discoloration prevention is performed. The amount of the agent is preferably 20 to 50 parts by weight, and the amount of the dispersant is preferably 100 to 400 parts by weight.

The amount of the antibacterial and fungicide to be added to the resin is 0.04 to less than the amount of bis (2-pyridylthio-1-oxide) zinc as an active ingredient in the antibacterial and fungicide.
0.30 to 0.50% by weight to be 0.08% by weight
It is preferable to set the value within the range. If the compounding amount of the antibacterial and antifungal agent is less than 0.1% by weight, it is difficult to impart sufficient antibacterial and antifungal performance, deterioration prevention by ultraviolet rays, and discoloration prevention effect, particularly for applications in which food is directly placed.

Conversely, if the compounding amount exceeds 1.0% by weight, the resin may react with other additives in the resin at the time of extrusion molding of the resin, causing discoloration of the resin and causing bloom on the resin surface. However, improvement of antibacterial and antifungal effects cannot be expected.

When adding and kneading the resin with an antibacterial and fungicide, a dispersant is blended, so that each component of the antibacterial and fungicide is uniformly dispersed or dissolved in the resin, and The effect, the effect of preventing ultraviolet-ray deterioration and the effect of preventing discoloration are effectively exhibited. Hereinafter, the present invention will be described specifically with reference to Examples.

[0033]

EXAMPLES (Example 1) An antibacterial and antifungal agent as a fine powder passing through a 100 mesh sieve was prepared by mixing the following components. 100 parts by weight of bis (2-pyridylthio-1-oxide) zinc 30 parts by weight of 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 20 disodium ethylenediaminetetraacetate 20 Parts by weight ・ 300 parts by weight of calcium carbonate

Next, 0.3% by weight of the above antibacterial and antifungal agent and 0.001% by weight of the coloring agent were added to high-density polyethylene powder and dry-blended. Extruded into a shape.

Example 2 The same high-density polyethylene powder as in Example 1 was added with 0.5% by weight of the same antibacterial and antifungal composition as in Example 1 and 0.001% by weight of a coloring agent, and dry blended. This is put into the extruder and the thickness is 20m
m and extruded into a plate shape.

(Comparative Example 1) Only the same high-density polyethylene powder as in Example 1 was charged into an extruder, and the thickness was 20 mm.
And extruded into a plate.

Comparative Example 2 The same polyethylene powder as in Example 1 was added with 0.15% by weight of the same antibacterial and fungicide as in Example 1 and 0.001% by weight of a coloring agent, followed by dry blending. This was put into an extruder and extruded into a plate having a thickness of 20 mm.

Comparative Example 3 0.3% by weight of the same antibacterial and fungicide as in Example 1, 0.001% by weight of a coloring agent and 0.05% by weight of liquid paraffin were added to high-density polyethylene pellets.
Was added and mixed, and the mixture was charged into an extruder to obtain a thickness of 20.
It was extruded into a plate having a thickness of 2 mm.

From the plates prepared in Examples 1 and 2 and Comparative Examples 1 to 3 as described above, test pieces having dimensions of 40 mm × 40 mm were taken and subjected to an antibacterial test and a mold resistance test.

The antibacterial test was performed using Escheric as a strain.
hia coli (E. coli) and Staphylococ
Using Cus aureus (Staphylococcus aureus), this strain was transplanted to an NA medium and cultured at 37 ° C for 20 hours (pre-preculture). One platinum loop of the previously cultured bacteria was transplanted to a NA medium and cultured at 37 ° C. for 20 hours.

This was diluted with a 1/500 concentration NB medium (pH
7.0), and this was used as a test bacterial solution. A certain amount of this was inoculated on the test surface of the test piece, and a coating film was placed thereon, followed by constant temperature and humidity at 37 ° C. and 98% RH. 24 in the vessel
After culturing for a period of time, the bacteria adhering to the coating film were washed out in a Petri dish with an SCDLP medium, and the number of bacteria remaining in the washing solution was measured. Table 2 shows the results.

[0042]

[Table 2]

The mold resistance test was performed using Asper as a strain.
gillus niger, Penicillium
funiculosum, Gliocladium v
irrens, Chaetomium globosu
In accordance with ASTM G21-70, a test piece is placed on an agar plate medium (Nutrient Salt Agar medium) using Aureobasidim pullulans, and a mixed spore suspension of the above strain is applied to the front and back of the test piece. Spray 0.5 ml uniformly, 30 ° C, 98% RH
Culture was performed in a thermo-hygrostat under the following conditions.

The test pieces on the 7th and 28th days of culture were observed, and "0" indicates no mold on the test piece, "1" indicates less than 10% of the mold area of the test piece, and "1" indicates the mold area of the test piece. 10-3
0% was evaluated as “2”, the mold area of the test piece 30 to 60% was evaluated as “3”, and the mold area of the test piece 60% or more was evaluated as “4”. Table 3 shows the results. (The mold resistance test is AS
(According to TM method)

[0045]

[Table 3]

As shown in Table 2, in Comparative Example 1 in which the antibacterial and fungicide was not added, the number of bacteria was larger than the initial number of bacteria and Comparative Example 2 in which the amount of the antibacterial and fungicide was not appropriate.
And Comparative Example 3 using polyethylene pellets, although the number of bacteria was smaller than the initial number of bacteria, while a considerable number of bacteria remained, whereas bis (2-pyridylthio-1-)
In Examples 1 and 2 in which an appropriate amount of an antibacterial and antifungal composition containing (oxide) zinc as an active ingredient was blended, the number of bacteria was considerably reduced as compared with the number of initial bacteria, and the antibacterial effect was recognized.

As shown in Table 3, in Comparative Example 1 in which no antibacterial and antifungal agent was blended, generation of mold was observed, but antibacterial containing bis (2-pyridylthio-1-oxide) zinc as an active ingredient was observed. Examples 1 and 2 in which the antifungal composition was blended
Is confirmed that no mold is generated on the test piece,
High antifungal effect is observed.

[0048]

According to the first aspect of the present invention, in an antibacterial and antifungal resin composition having both antibacterial and antifungal effects, 100 parts by weight of a resin contains bis (2-pyridylthio-1-).
Oxide) An antibacterial and fungicide consisting of zinc in an amount of from 0.04 to 0.1%.
It is characterized in that it is contained in an amount of 08% by weight.

As described above, by adding bis (2-pyridylthio-1-oxide) zinc to the resin as a specific antibacterial and antifungal agent, a single agent is excellent in both antibacterial and antifungal properties. Can be obtained.

According to a second aspect of the present invention, there is provided an antibacterial and antifungal resin composition having both antibacterial and antifungal effects, the resin comprising bis (2-pyridylthio-1-oxide) zinc as an active ingredient and at least ultraviolet rays. Absorbent, anti-tarnish,
0.30 to 0.50% by weight of an antibacterial and fungicide containing a dispersant
An antibacterial and antifungal resin composition characterized by containing.

By including an ultraviolet absorber other than the antibacterial and antifungal components, various physical properties such as discoloration prevention required when used as a resin material can be imparted.

In the present invention, bis (2-pyridylthio-1-oxide) zinc as an antibacterial and antifungal agent, an ultraviolet absorber, a discoloration inhibitor and a dispersant are dispersed or dissolved in the resin.

By dispersing the components throughout the resin as described above, a resin material having a uniform performance can be obtained.

In claim 4, the resin is limited to polyethylene, but polyethylene is a material from which bacteria are unlikely to proliferate, and in combination with the effect of an antibacterial and antifungal agent, a resin composition in which bacteria and mold are extremely unlikely to be produced. Obtainable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C07D 213/89 C07D 213/89 F term (reference) 4C055 AA17 BA02 BA47 BB13 CA01 DA01 4H011 AA02 AA03 BA01 BB09 BB18 BC19 DH02 4J002 AA001 BB031 BB121 BC031 BD041 BD141 BG031 BN151 CF001 CK001 CL001 DE239 DH058 DJ019 DJ049 EN118 EU046 EU077 EU177 EV056 EV307 EZ006 FD057 FD186 FD208 FD209

Claims (4)

[Claims] 1. An antibacterial and fungicide resin composition having both antibacterial and antifungal effects, wherein the resin contains an antibacterial and fungicide comprising bis (2-pyridylthio-1-oxide) zinc in an amount of from 0.04 to 0. An antibacterial and antifungal resin composition characterized by containing 0.08% by weight. 2. An antibacterial and antifungal resin composition having both antibacterial and antifungal effects, comprising bis (2-pyridylthio-1-oxide) zinc as an active ingredient in a resin, and at least an ultraviolet absorber, An antibacterial / antifungal resin composition comprising 0.30 to 0.50% by weight of an antibacterial / antifungal agent containing a discoloration inhibitor and a dispersant. 3. The resin according to claim 2, wherein bis (2-pyridylthio-1-oxide) zinc, an antibacterial and antifungal agent, an ultraviolet absorber, a discoloration inhibitor, and a dispersant are dispersed or dissolved. An antibacterial and antifungal resin composition. 4. The antibacterial and antifungal resin composition according to claim 1, wherein the resin is polyethylene.