JP2003277206A - Industrial antibacterial and antifungal agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide at a low cost an antibacterial and antifungal agent which can impart antibacterial and antifungal properties to an industrial material without detriment to the properties of the material. <P>SOLUTION: The industrial antibacterial and antifungal agent contains triflumizole as the active ingredient. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial antibacterial and antifungal agent.

[0002]

2. Description of the Related Art When microorganisms such as bacteria and fungi are generated in industrial materials and products, the aesthetic appearance is deteriorated, and the materials are deteriorated and the quality is deteriorated. As a result, the functions of materials and products are deteriorated, the life is shortened, and the value thereof is significantly reduced. To prevent these, antibacterial and antifungal agents have been conventionally used alone or as a mixture.

Most commonly used compounds are organic compounds because of their strong antibacterial activity. As a specific example, 2-
Benzimidazolylcarbamic acid alkyl esters,
2- (4-thiazolyl) benzimidazole, zinc bis (2-pyridylthio-1-oxide), α- [2-
(4-Chlorophenyl) ethyl] -α- (1,1-) dimethylethyl) -1H1,2,4-triazole-1-
Ethanol, 3-iodo-2-propargyl butyl carbamate, 3-acetyl-6-methyl-2H-pyran-
2,4 (3H) -diones, n-butyl-1,2-benzisothiazolin-3-one, N- (fluorodichloromethylthio) -phthalimide, N, N-dimethyl-N '
-Phenyl-N'-fluorodichloromethylthiosulfamide, 2-n-octylisothiazolin-3-one,
Compounds such as 2,4,5,6-tetrachloroisophthalonitrile are known.

[0004] In addition, although the antibacterial activity is weak, an inorganic compound may be used depending on the application. As a concrete example,
It is known that a metal such as silver or copper is supported on an inorganic compound such as zeolite or zirconium phosphate, or a metal oxide such as zinc oxide or titanium oxide.

However, these antibacterial and antifungal agents do not always exert antibacterial activity against a wide range (many kinds) of microorganisms, and generally, two or three kinds of antibacterial and antifungal agents are appropriately selected each time. I'm using it. In addition, depending on the type, there are some that are decomposed or colored by heat, ultraviolet rays, etc., and the current situation is to actually try and consider the results.

[0006]

Generally, many organic compounds are easily affected by heat and ultraviolet rays, and compounds used as antibacterial and antifungal agents are no exception. When heat is applied during manufacturing or processing of industrial products or during use, the antibacterial and antifungal agent may be decomposed depending on the temperature, and coloring and adverse effects on the physical properties of products may not be negligible.

Particularly when used for plastics such as polyolefins among industrial materials, most of them are decomposed by heat applied during processing and colored except for some compounds.

Further, many compounds are decomposed or colored by ultraviolet rays, and an ultraviolet absorber, a pigment, an antioxidant and the like are used together in order to reduce the influence of ultraviolet rays, but their effects are not always sufficient. .

On the other hand, when water resistance and durability are required, such as construction materials and materials used for equipment around water such as kitchens and bathrooms, the antibacterial and antifungal effect is less durable under these environmental conditions. The compound cannot be used.

On the other hand, although some inorganic compounds have high thermal stability and excellent water resistance, they generally have a weaker antibacterial and antifungal effect than organic compounds, so that the material has a sufficient antibacterial and antifungal effect. It's difficult to get it done.

As described above, the antibacterial and antifungal agents that can be actually used are limited depending on the applications and materials. On the contrary, it can be said that there are very few compounds with high versatility that satisfy various conditions such as heat resistance, ultraviolet resistance and water resistance. Even if these conditions are satisfied, it cannot be used if the effect on the microbial species causing the contamination is weak.

Furthermore, almost no antibacterial and fungicide shows uniform antibacterial and antifungal effects against a wide range of microorganisms. Therefore, antibacterial and antifungal agents are often used in order to obtain a sufficient effect with a drug having a weak effect. There is no choice but to increase the quantity, which also leads to higher costs.

Therefore, the development of an antibacterial / antifungal agent which has an effect on a wider range of microbial species and is highly stable even under various environmental conditions leads to a reduction in cost for prevention and control of damage due to microbial contamination.

[0014]

The present inventors have conducted experiments on heat resistance, ultraviolet resistance and water resistance on the basis of research on the efficacy of various antibacterial and antifungal agents against many pollution-causing microorganisms in general industrial applications. Through repeated efforts, we have found an antibacterial and antifungal agent that has excellent stability even under many severe environmental conditions and is effective against a wide range of microbial species.

The drug of the present invention is an antibacterial and antifungal agent which is effective even at low concentrations in antibacterial properties against many microorganisms, and has the property of being highly stable with little coloring even under various environmental conditions. Do you get it.

The present invention is an industrial antifungal agent characterized by containing triflumizole as an active ingredient as described below. By using this chemical for industrial use, it became possible to impart an antibacterial and antifungal effect to a wide range of microorganisms with a small addition amount under severe environmental conditions.

[0017]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention suppresses microbial contamination of industrial materials and products such as bacteria and fungi, and prevents deterioration and quality deterioration of materials caused by the generation of these microorganisms.
(EN) An industrial antibacterial and fungicide which is used for the purpose of maintaining aesthetics, is highly safe, and exerts its effect even in a small amount.

The antibacterial and antifungal agent of the present invention is effective against a wide range of microorganisms. Microorganisms that cause pollution differ depending on the type and application of industrial materials, but since they have a broad antibacterial spectrum, their effects are expected in various applications. That is, since the antibacterial / antifungal agent has very excellent stability against heat and ultraviolet rays and low reactivity, it has become possible to add it to various materials. Furthermore, since it has less influence on physical properties than conventional antibacterial and antifungal agents, it has become possible to add an antibacterial and antifungal agent in an amount sufficient to exert a sufficient effect.

Further, the triflumizole of the present invention is effective at a lower addition amount than the addition amount when other organic antibacterial and antifungal agents are used alone. It was found that the same effect can be obtained even if the amount is reduced. This not only makes it possible to reduce the effects of the combination of antibacterial and antifungal agents, but also
It became possible to exert the effect with a small amount of addition and to reduce the cost.

The present invention is a composition containing triflumizole as an active ingredient. However, the composition is not limited to the composition, and the composition may be used in combination with other antibacterial / antifungal agents. As a result, a stronger antibacterial and antifungal effect is expected by compensating for the drawbacks of other antibacterial and antifungal agents.

Further, as the fields of application of the present invention, polyurethane resins, vinyl chloride resins, polyolefin resins such as polyethylene and polypropylene, plastics such as silicone resins and emulsion adhesives such as vinyl acetate emulsion and acrylic emulsion, starch. It can be considered to be used in a wide range of industrial fields including glue, putty for various applications, bonds, paints, and metal working oils. Further, it can be used as an industrial antibacterial and antifungal agent for materials used in various fields other than the fields described here.

The triflumizole of the present invention is represented by the following chemical structural formula.

[Chemical 1]

It is also conceivable to use triflumizole in combination with other drugs, and the compounding method at that time may be simple mixing of the drugs or mixing of the drugs dissolved in a solvent. Further, if necessary, they may be added separately to the target material.

As described above, the present invention makes it possible to provide an industrial antibacterial and antifungal agent which is extremely versatile as compared with conventional antibacterial and antifungal agents.

Examples of the present invention will be described below, but the present invention is not limited thereto. The antibacterial activity of the antibacterial and antifungal agent of the present invention against various microorganisms is shown below as a comparative example.

[0026]

[Comparative Example] In order to explain the present invention, the antibacterial activity against each microorganism was examined. The results are shown below as comparative examples together with the conventional technique.

1) Drugs used Triflumizole: drug A according to the present invention agent A: 2-benzimidazolylcarbamic acid methyl ester agent B: 2- (4-thiazolyl) benzimidazole agent C: zinc bis (2-pyridylthio-1-oxide) ) Agent D: α- [2- (4-chlorophenyl) ethyl] -α
-(1,1-) Dimethylethyl) -1H1,2,4-triazole-1-ethanol E agent: 3-iodo-2-propargyl butyl carbamate F agent: 3-acetyl-6-methyl-2H-pyran- Two
4 (3H) -diones G agent: n-butyl-1,2-benzisothiazoline-3
-One H agent: N- (fluorodichloromethylthio) -phthalimide, N, N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide I agent: 2-n-octylisothiazolin-3-one

2) Measurement of minimum inhibitory concentration (MIC) for each microorganism Medium used 1% glucose broth liquid medium was used for yeast and bacteria. Potato dextrose medium is used for mold. Culture conditions Yeast and bacteria were cultured at 30 ° C for 3 days. Molds are cultured at 25 ° C for 7 days.

Microorganisms used Real name: Abbreviation (abbreviated as follows) Aspergillus niger : Asp. ni. Aureobasidium pullulans : Aureo. pu. Penicillium funiculosum : Pen. fu. Cladosporium cladosporioides : Cla. cla. Alternating Alternate : Alt. alt Ulocladium botrytis : Ulo. bot. Gllocladium virens : Gl. vi. Saccharomyces cerevisiae : Sac. cer. Torula utilis : Tor. uti. Staphylococcus aureus : Step. au. Escherichia coli : E. coli

Measuring method After sterilizing each medium, various drug mixtures were dissolved or suspended to a predetermined concentration, and 1 platinum loop was inoculated from each of the microorganisms previously cultured on the slant agar medium. The cells were cultured under conditions suitable for the above conditions, and after a certain period of time, the growth was visually observed for the presence or absence of growth.

Judgment The minimum inhibitory concentration was shown in Comparative Tables I to XI based on the situation of each concentration of each drug.

[0032]

[Table 1]

From Comparative Table I, triflumizole showed generally stronger antibacterial activity against various microorganisms than other drugs.

3) Heat resistance, UV resistance, etc. Heat resistance test 1 g of each drug was placed in a test tube, 5 ml of water and 5 ml of propylene glycol were added, and the mixture was shaken well, suspended or dissolved, put on the lid, and 50 The temperature was kept at 10 ° C for 10 hours. afterwards,
The liquid property was visually observed.

UV resistance test 1 g of each drug was placed in a 50 ml conical beaker and water 5 m
l, 5 ml of propylene glycol were added and mixed well by shaking, suspended or dissolved, and covered with a transparent film,
Irradiation was carried out for 1 hour with a xenon lamp fade meter.
Then, the liquid property was visually observed.

Test result

[Table 2]

From Comparative Table II, triflumizole was good in both heat resistance and ultraviolet resistance.

As described above, the antibacterial activity of the various drugs was stronger than those of the other drugs. Also,
It has been confirmed that the light resistance, the UV resistance, and the water resistance, which will be described later, are improved in the functions that were not found in conventional chemicals,
It is submitted here as a new technology.

[0039]

EXAMPLES Examples of application in each industrial field are described below, but the present invention is not limited thereto.

[0040]

Example 1 Application to starch paste In general, starch paste is widely used for household, office and industrial purposes. The raw materials used are potato starch, wheat starch, corn starch, tapioca starch and the like, and processed starch, dextrin or synthetic resin thereof are used as raw materials. The physical properties of the produced starch paste vary depending on the type of these raw materials, and the cost also changes. On the other hand, as a manufacturing method, there are a boiling paste by heating and a cold paste method (apalatin paste) using sodium hydroxide. Various types of starch paste are produced depending on the combination of raw materials and manufacturing method.

1) Production of starch paste Boiled starch Wheat starch was added to water with stirring to prepare 20% starch milk, which was heated with stirring at 60 to 75 ° C for 20 minutes and allowed to cool. The chemicals were added at the time of starch milk in terms of finished starch paste.

Cold paste method (apalatin paste) Wheat starch 60
To 150 parts of water, add 150 parts of water and stir.
While adding a mixed solution of 25 parts of 6 ° Baume) and 25 parts of water, 1
Stir at 5-20 ° C for 1 hour until the whole is clear.
After gelatinization, it was neutralized with nitric acid so as to have a pH of 7-8. After the neutralization, the chemicals were added to each concentration and well stirred to dissolve uniformly.

2) Test conditions The prepared cooked paste and apalatin paste were filled in a petri dish, the lid was left open for 24 hours at room temperature, and the lid was closed (sealed).
The condition was observed by keeping the temperature at ℃. Further, these petri dishes were irradiated with a fade meter of a xenon lamp for 1 hour, and the situation was visually observed. The drug used is
1,2-benzisothiazolin-3-one (hereinafter referred to as BIT), p-oxybenzoic acid methyl ester (hereinafter referred to as p-OBE), which has been generally used for starch paste,
It was potassium sorbate (hereinafter referred to as SAK) and triflumizole of the present invention.

3) Results of storage stability and UV resistance

[Table 3]

From Table A, as compared with the prior art, in the test group using triflumizole which is the technique of the present invention,
It showed a remarkably excellent effect on storage stability and UV resistance.

[0046]

Example 2 Application to Vinyl Acetate Adhesive A vinyl acetate adhesive is an adhesive containing vinyl acetate emulsion as a main component and starch paste and other natural pastes. It is widely used for bonding paper, woodwork, plastics, etc.

According to the same manner as in Example 1, two kinds of vinyl acetate adhesives for woodworking (without using an antibacterial and antifungal agent) were tested for storage stability and UV resistance. The chemicals used were p-chloro m-xylenol (hereinafter referred to as PCMX), 2-bromo-2-nitropropane-1,3-diol (hereinafter referred to as BNPD), N ( Fluorodichloromethylthio) phthalimide (hereinafter referred to as FP), 2- (4-thiazolyl) -benzimidazole (hereinafter referred to as TBZ) and Formulation 15, Formulation 77, and Agent A according to the present invention were used. A fixed amount of each drug was added and mixed well to be uniformly dissolved or suspended.
The storage method and the determination method were carried out according to Example 1, and the results are shown in Table B.

[0048]

[Table 4]

From Table B, the triflumizole of the present invention is
Compared with the drugs used conventionally, the addition of a small amount showed a storage effect, and the coloring effect by ultraviolet rays was also small, and the effect was excellent.

[0050]

[Example 3] Application to joint cement and mortar Generally, joint cement is used when tiles are applied, and mortar is used for the exterior, but both are strongly alkaline during construction, and bacteria and mold are unlikely to occur. However, when it is neutralized with the lapse of time and particularly dirt is attached, bacteria and fungi are gradually generated.

In particular, since the mortar-based or plaster-based adhesive is porous, it is easily soiled, and thus microorganisms are likely to propagate. In addition, a cellulose derivative, polyvinyl alcohol, etc., which are blended as a water retention agent, serve as a nutrient source for microorganisms. Due to such severe conditions, not only the surface is often contaminated by the generation of bacteria and mold but also the adhesive function is deteriorated.

Each test material had a general formulation, that is, for joint cement, the composition was 40 parts of cement, 50 parts of aggregate, 0.2 part of water reducing agent, 0.3 part of water retention agent and 40 parts of water, and mortar. For the composition of 100 parts of cement, 80 parts of silica sand, 0.2 parts of water-soluble cellulose ether and 40 parts of water, and for plaster bond, lime plaster 20
The chemicals were added at the time of mixing in a composition of 0 part, 20 parts of Shirasu, 30 parts of calcined diatomaceous earth, 20 parts of vinyl acetate powder resin and 270 parts of water. After air drying, they were neutralized in a desiccator filled with carbon dioxide. JIS them
Tested according to Z-2911-2000 mold resistance test method and the results are shown in Table C. Incidentally, the microorganisms used are further fungi for use in the test method Ul
o. bot. Bacteria and Alt. alt. Bacteria were added.
The drugs used are A agent, B agent, C agent, D agent, E agent and G agent.
Agent and triflumizole according to the invention. The test results are shown in Table C-1 and Table C-2.

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

From Table C, prior art agents A, B, C,
Compared to agents D, E and G, triflumizole according to the present invention showed much stronger mold resistance.

[0057]

[Example 4] Application to joint cement and GL bond There are two types of joint cement, gypsum-based and calcium carbonate-based, but the ones used this time are 100 parts of gypsum, 1 part of polyvinyl alcohol, 5 parts of stone powder, and some others. It was prepared by adding a thickener and 73 parts of water and mixing. On the other hand, as the GL bond, a commercially available one without a fungicide was used.

In each case, the test agents were mixed well so as to be uniform. This is JIS Z
-2911-2000 Mold resistance was tested according to the test method. Instead of putting the sample on the medium, make a depression in the medium,
Joint cement or GL bond was embedded in this and observed.

The agents used are C agent, D agent as in the prior art.
Agents, E agents, F agents, G agents and PCMX, and further triflumizole as the technique of the present invention. Incidentally, the microorganisms used in the test, further fungi for use in the test method U
lo. bot. Bacteria and Alt. alt. Additional fungi were tested. Table D shows the test results of the preservation effect.

[0060]

[Table 8]

From Table D, the prior art agents C, D, E,
Compared to agents F and G and PCMX, triflumizole according to the present invention exhibited far stronger antifungal properties.

[0062]

Example 5 Application to Vinyl Chloride Wallpaper and PVC Flooring Vinyl chloride wallpaper is manufactured by adding auxiliary materials such as plasticizer to vinyl chloride resin and is widely used as a wall material for houses. . On the other hand, PVC flooring materials are manufactured using a small amount of plasticizer, filler and the like.

Samples each prepared with the following composition that is usually used (untreated) and one sample prepared by soaking in running water for 1 week at room temperature and then air-dried (water-treated) were prepared.
Each test was conducted according to the mold resistance test method used in Example 4, and the results are shown in Table E.

The agents used are A agent, B agent, C agent, E agent and triflumizole.

Composition of vinyl chloride wallpaper 100 parts of paste resin (product GH623), plasticizer (D
OP) 60 parts, filler (calcium carbonate) 120 parts, extender pigment (titanium oxide) 15 parts, foaming agent (ADCA) 3
Parts, secondary plasticizer 5 parts, stabilizer 3 parts, diluent 10 parts

PVC flooring (for cushion floor foam layer)
Composition paste resin (product name PQHC) 70 parts, blend resin (product name PBZXA) 30 parts, plasticizer (DOP) 40
Parts, plasticizer (DBP) 10 parts, filler (calcium carbonate) 30 parts, extender pigment (titanium oxide) 5 parts, foaming agent (A
DCA) 3 parts, kicker (zinc oxide) 1.5 parts, epoxidized soybean oil 3 parts

[0067]

[Table 9]

From Table E, in the vinyl chloride wallpaper,
The triflumizole of the present technology showed much stronger mold resistance as compared with the agents A and B of the prior art. In addition, it has been confirmed that the triflumizole of the present invention exhibits a stronger mold resistance than the conventional agents D and E in the case of hard vinyl chloride flooring material, which is an excellent technique.

[0069]

INDUSTRIAL APPLICABILITY The present invention is an industrial antibacterial and antifungal agent characterized by containing triflumizole as an active ingredient as shown in Reference Examples and Examples.

It was confirmed that it has a number of characteristics such as strong antibacterial activity, excellent light resistance and water resistance, which cannot be easily estimated from the conventional techniques. As a result, when adding antibacterial and antifungal properties to each industrial material, the antibacterial and antifungal effect is exhibited with a low addition amount, so the cost can be reduced by reducing the addition amount and the physical properties of the industrial materials can be improved. It is possible to minimize the effect of.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 103/00 C09J 103/00 201/00 201/00 // C04B 103: 69 C04B 103: 69 F term ( Reference) 4H011 AA02 BB09 4J002 BD031 EU106 FD206 4J040 HC16 HC24 KA29

Claims (6)

[Claims] 1. An industrial antibacterial and antifungal agent comprising triflumizole as an active ingredient. 2. An antibacterial and antifungal agent for starch paste-based adhesives, which comprises triflumizole as an active ingredient. 3. An antibacterial and antifungal agent for synthetic resin adhesive, which contains triflumizole as an active ingredient. 4. An antibacterial and antifungal agent for joint cement and mortar containing triflumizole as an active ingredient. 5. An antibacterial and antifungal agent for plaster, joint cement and mortar, which contains triflumizole as an active ingredient. 6. An antibacterial and antifungal agent for vinyl chloride wallpaper and vinyl chloride flooring, which contains triflumizole as an active ingredient.