JP3150722B2 - Antifungal composition for plastics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to an antibacterial and antifungal agent 2-n-
When octyl-4-isothiazolin-3-one is used for kneading into plastics, it is used for plastics in which zinc oxide is used in combination with zinc oxide for the purpose of preventing decomposition and discoloration caused by the high processing temperature. The present invention relates to an antifungal composition.

[0002]

2. Description of the Related Art

[0003]

Embedded image

2-n-octyl-4-isothiazolin-3-one represented by the formula (1) has excellent antibacterial and antifungal properties and is therefore widely applied to paints and other general industries. The method of using this compound as an antibacterial and antifungal agent,
Emulsified and dispersed in water by dissolving in an organic solvent or adding a surfactant, and then directly adding it to paints and pastes or diluting the solution into textiles, plastic products, wood products, leather products, paper Products, bamboo products, other antibacterial,
For those requiring antifungal properties, treatment has been carried out by a method of penetrating, coating or spraying to the surface or inside. In addition, water resistance and washing resistance are imparted by the combined use of a resin liquid or the like at the time of treatment, so that long-lasting efficacy is maintained. In these methods, as a method for treating plastic, surface treatment has poor absorption of a drug, and it is difficult to maintain efficacy for a long period of time. Therefore, kneading into the interior is conceivable. If it is kneaded inside, a semi-permanent effect can be expected depending on the type of drug, but the temperature at the time of kneading plastic becomes quite high as 200 to 250 ° C or more, so it must withstand that temperature . At present, compounds that can be used at such high temperatures are mainly silver and copper-based inorganic compounds, and there are some arsenic-based compounds, but they have toxicity problems. General organic compounds are relatively weak to heat. In particular, when the temperature exceeds 200 ° C., many of them decompose and change. In addition, when kneading is performed at such a high temperature, a sufficient effect cannot be expected due to volatilization of the compound due to heat.

[0005]

Generally, many organic compounds are susceptible to oxygen, ultraviolet rays and heat. Among them, especially heat, many compounds are colored and decomposed except for specific compounds. Looking at organic compounds structurally, both aliphatic and aromatic compounds contain nitrogen, sulfur, and halogen in their structures, unsaturated compounds with double and triple bonds, esters, aldehydes, and phenols. Compounds and heterocyclic compounds are susceptible. Since such compounds are relatively large in antibacterial and antifungal agents, sufficient care must be taken when using them.

[0006] Decomposition at the time of kneading into plastic,
When the discoloration occurs, the effect is naturally reduced, but the coloration or the change in the physical properties of the plastic is usually observed. In addition, the odor or irritating odor due to the decomposition gas may have a significant effect on the working environment.

2-n-octyl-4-isothiazoline-
When 3-one is used alone, discoloration and malodor due to high temperature are generated, and it cannot be put to practical use due to a decrease in efficacy and coloring of plastic. For this, 2-n
It is desired to use a stabilizer for heat of -octyl-4-isothiazolin-3-one.

[0008]

The present inventors have proposed 2-n-
As a result of research on a heat resistance improver of octyl-4-isothiazolin-3-one, zinc oxide has a great effect as a heat resistance improver in kneading into plastics, and discoloration during kneading of plastics and The inventors discovered that decomposition was suppressed, and completed the present invention.

That is, the present invention relates to 2-n-octyl-
A fungicide composition for plastics, characterized by adding zinc oxide to 4-isothiazolin-3-one.
Zinc oxide has a local astringent effect, a protective effect on the skin, and a mild antiseptic effect.
Used as a raw material for cosmetics. This zinc oxide
Although listed in the list of substances that can be used in food containers and packaging (positive list), it is a substance that can be added to most plastics,
The heat resistance of n-octyl-4-isothiazolin-3-one was 140 to 160 ° C, but when zinc oxide is used in combination, it decomposes and degrades to about 200 to 280 ° C, and the plastic may be colored too much. No antibacterial and antifungal properties were exhibited.

2-n-octyl-4-isothiazoline-
The compounding ratio of 3-one and zinc oxide is 1: 1 to 1:20, preferably 1: 2 to 1:10. When making a master batch with this ratio and kneading it into plastic,
A product with little coloring is obtained. As a method for applying the compound of the present invention to kneading into plastics, either a direct addition method or a method of adding a master batch followed by addition may be used. When kneading, a plasticizer, calcium carbonate and other natural minerals can be used in combination.

[0011] The present invention further comprises an insect repellent, a bactericidal fungicide,
Deodorants, flavors, coloring agents, ultraviolet absorbers, and antioxidants can be added. Plastics containing 2-n-octyl-4-isothiazolin-3-one as described above can be used for household appliances and daily necessities, clothing, fishing nets, ropes, awnings, sheets, packaging films, OA equipment, and computers. Plastics used in related parts cause molds and cause major failures. In addition, it is used for covering general electric wires or agricultural films, PVC pipes used for water supply, underground cables, etc., as well as underground roads, tunnels, inside subways, underground shopping centers in cities, etc., where mold is easily generated. The application range is immeasurable, for example, it is possible to prevent the embrittlement of materials by preventing the generation of mold on plastics. In addition, the effect is not only hygienic by preventing the generation of bacteria and fungi, but also extends the service life.

[0012]

When a plastic is kneaded with 2-n-octyl-4-isothiazolin-3-one as an antibacterial and antifungal agent, yellowing occurs due to partial decomposition caused by the melting temperature of the plastic. This causes the plastic to be colored. When the decomposition proceeds further, the working environment is deteriorated due to the bad odor and the irritating odor due to the volatile substances generated by the decomposition, and the degree of coloring of the plastic also increases.
Such a phenomenon results in a loss of commercial value with a decrease in physical properties of the plastic. In addition, it is clear that the degradation is accompanied by a decrease in antibacterial and antifungal properties even though it is partial. 2-n-octyl-4-isothiazoline-3
The amount of -ON added to the plastic is 0.01 to 0.1% by weight (hereinafter, all shown in% by weight).
When 10 times the amount of zinc oxide is added and kneaded into plastic, there is almost no coloring and there is no influence on the physical properties. In addition, antibacterial,
It is also expected to have a fungicidal effect enhancing effect.

As the plastic, polyethylene resin,
It can be widely applied to polypropylene resin, polyurethane resin, polyester resin, polyacryl resin, polyamide resin, polystyrene resin, polyvinyl chloride resin and the like.

[0014]

The present invention will be described below by way of examples. Example 1 2-n-octyl-4-isothiazolin-3-one 1
0 parts are 60 parts of fine powder zinc oxide and 30 parts of calcium carbonate.
After adding the portions, the well mixed in advance is smashed in a mortar and mixed well. One part of this mixture was added to 99 parts of polypropylene pellets, and a 30-micron thick film was trial-produced at a temperature of 200 to 220 ° C. using an extruded film production tester of Labo Plastmill (Toyo Seiki Seisaku-sho, Ltd.). 2-n-octyl-
With respect to 10 parts of 4-isothiazolin-3-one, 30 parts of zinc oxide, 60 parts of calcium carbonate and 0 parts of zinc oxide were used, and the remaining 90 parts were all made as calcium carbonate to prepare a film under the same conditions. Table 1 shows the results of examining the degree of coloring at the time of kneading for the prototype.

[0015]

[Table 1]

A comparative test of antibacterial and antifungal properties was conducted using the above-mentioned prototype film. The test method is as follows. Antibacterial test method: According to JIS L 1902 halo method. Bacterial species used for the test staphylococcus aureus ATCC 6538P Antifungal test method: According to JIS Z 2911. Molds subjected to the test Aspergillus niger FERM s-1 Penicillum citrinum FERM s-5 Cladosporinum herbarum FERM s-8 The antibacterial test results by the above test are as shown in Table 2, and the antifungal test results are shown in Table 3. It is as follows.

[0017]

[Table 2]

[0018]

[Table 3]

The judgment values of the above-mentioned mold-proof test are based on the indication method of the mold-proof test shown in Table 4.

[0020]

[Table 4] (Note) In the display method of the mold resistance test (JIS Z-2911), when there is an additional stop band in display 3, the size of the stop band is displayed on the right side in mm.

Example 2 Under the same conditions as in Example 1, soft vinyl chloride pellets were used instead of polypropylene pellets,
At 170 ° C., a 30 micron thick film was prototyped.

Table 5 shows the degree of coloring and the results of antibacterial tests of the above-mentioned prototypes when kneading, and Table 6 shows the results of the antifungal test. In addition, antibacterial,
The antifungal test method was performed according to Example 1.

[0023]

[Table 5]

[0024]

[Table 6]

Example 3 Under the same conditions as in Example 1, polyethylene pellets were used instead of polypropylene pellets, and the temperature was 160-18.
At 0 ° C., a 30 micron thick film was prototyped.

Table 7 shows the degree of coloration and antibacterial test results of the above-mentioned prototype when kneading, and Table 8 shows the antifungal test results. The antibacterial and antifungal test methods were performed according to Example 1.

[0027]

[Table 7]

[0028]

[Table 6]

Example 4 After mixing 20 parts of the drug used in Example 1 with 80 parts of polyethylene pellets, the mixture was melted at 180 to 200 ° C., homogenized, and then a master batch was prepared. This master batch was added to polyethylene, and a film was prototyped in the same manner as in Example 1. The trial production conditions were as follows: master batch addition amount 0.5, 1.5, 3.5, 5.0, 10.0 each weight%,
At a temperature of 160 to 180 ° C., a film having a thickness of 30 μm was experimentally produced.

Table 9 shows the degree of coloring and the results of the antibacterial test of the above-mentioned prototypes when kneading, and Table 10 shows the results of the antifungal test. The antibacterial and antifungal test methods were performed according to Example 1.

[0031]

[Table 9]

[0032]

[Table 10]

Example 5 One part of the drug used in Example 1 was added to 99 parts of pellets for molding polyethylene terephthalate, and then added to 270 to 2 parts.
The mixture was heated and melted at 90 ° C., stirred well, and made uniform, and then a 1.0 mm-thick plate was prototyped.

Table 11 shows the degree of coloring and the results of the antibacterial test of the above-mentioned prototype when kneading.
Table 12 shows the results of the antifungal test. The antibacterial and antifungal test methods were performed according to Example 1.

[0035]

[Table 11]

[0036]

[Table 12]

Example 6 One part of the drug used in Example 1 was added to 99 parts of a polystyrene molding pellet, heated and melted at 240 to 260 ° C., and thoroughly stirred so as to be uniform. .5mm
A prototype plate was made.

Table 13 shows the degree of coloring and the results of the antibacterial test for the above prototypes when kneading.
Table 14 shows the results of the antifungal test. The antibacterial and antifungal test methods were performed according to Example 1.

[0039]

[Table 13]

[0040]

[Table 14]

Example 7 When kneaded into a plastic, 2-n-octyl-4 was used.
-The ratio of isothiazolin-3-one to ZnO was changed from 1: 1 to 1:20 as shown in Table 15, and this was added to polypropylene, and the temperature was 220 to 250 ° C.
A film having a thickness of 30 μm was experimentally produced by the method shown in FIG.

An antibacterial and antifungal test was conducted on the above prototype. The test method was performed according to Example 1. Table 16 shows the results of the antibacterial test, and Table 17 shows the results of the antifungal test.

[0043]

[Table 15]

[0044]

[Table 16]

[0045]

[Table 17]

[0046]

The present invention has excellent effects as an antibacterial and fungicide 2
When -n-octyl-4-isothiazolin-3-one is applied to kneading of plastic, zinc oxide exerts an excellent effect as one for preventing decomposition and coloring at the melting temperature of plastic. Thus, all damages caused by molds of plastics can be prevented.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 3:22 5:46) (72) Inventor Norio Someya 303 Ogawamachi Heights 1-7 Kanda Ogawamachi, Chiyoda-ku, Tokyo (56 References JP-A-2-225548 (JP, A) JP-A-3-84066 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08K 3/00-13/08 C08L 1/00-101/16 A01N 25/22 A01N 43/80

Claims (4)

(57) [Claims] 1. A fungicide composition for plastics comprising zinc oxide added to 2-n-octyl-4-isothiazolin-3-one. 2. The antifungal composition for plastics according to claim 1, wherein the plastic is a polyethylene resin, a polypropylene resin, a polyurethane resin, a polyester resin, a polyacryl resin, a polyamide resin, a polystyrene resin, or a polyvinyl chloride resin. 3. The temperature at the time of kneading the plastic is 160
The antifungal composition for plastics according to claim 1, wherein the temperature is from 300 to 300 ° C. 4. The antifungal composition for plastics according to claim 1, wherein the compounding ratio of 2-n-octyl-4-isothiazolin-3-one and zinc oxide is 1: 1 to 1:20.