JP2018184457A - Industrial antibacterial and fungicidal method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop new use of an isothiocyanate ester developed by the present inventor, and to provide means for an industrial antibacterial and fungicidal method.SOLUTION: An industrial antibacterial and fungicidal method is characterized by adding an isothiocyanate ester to a target industrial product or material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an industrial antibacterial and antifungal method, and in particular, as a novel use of isothiocyanate, as an industrial antibacterial and antifungal agent.

  Conventionally, hydrous pulp, dye, glue, adhesive, cutting oil, latex, wood, leather, fiber, fiber oil, caulking agent, resin, wallpaper, separate sheet, gypsum board base paper, dampening water for offset printing, etc. In many industrial products or industrial materials, it is known that in the area where water is used, it is contaminated and deteriorated by microorganisms such as fungi, and its appearance and commercial value are lowered.

  The inventor of the present invention has first succeeded in developing capsules or pellet particles of isothiocyanate ester, and has succeeded in providing antibacterial and antifungal sheets for foods and the like by taking advantage of its continuous antibacterial activity.

JP 2011-87585 JP JP 2011-30576

  The present invention is a development of a novel use of an isothiocyanate ester previously developed by the present inventor. In particular, the present invention provides an antibacterial and antifungal method for industrial products or materials made of an alkaline aqueous solution using water.

The industrial antibacterial and antifungal method of the present invention made in view of the above points comprises the following:
1. An industrial antibacterial and antifungal method comprising continuously injecting, intermittently injecting, intermittently adding or immersing an isothiocyanate in an aqueous solution of an industrial product or material.
2. An industrial antibacterial and antifungal method according to claim 1, wherein the isothiocyanate is continuously maintained in the aqueous solution at a concentration of 1-1000 ppm for a desired period.
3. Capsule or powder film shape of isothiocyanate can be maintained in aqueous solution, and isothiocyanate ester capsule or powder having the property that isothiocyanate can be gradually released into aqueous solution is encapsulated in pellet particles. The encapsulated pellet particles are added and immersed in an aqueous solution of the target industrial product or industrial material as needed, or the pellet particles are loaded into a net-like bag, and when necessary, the aqueous solution of the target industrial product or industrial material. The industrial antibacterial and antifungal method according to 1 or 2, comprising immersing in
4). The industrial antibacterial and antifungal method according to any one of 1 to 3, wherein the pellet particles have an average particle diameter of 1 to 10 mm.
5. The industrial antibacterial and antifungal method according to any one of 1 to 5, wherein an isothiocyanate is dissolved in an oil or fat.
6). The capsule or powder film-forming agent is at least one selected from the group consisting of capsule (sodium octenyl succinate starch), gum arabic, gelatin, hemicellulose, microbial polysaccharide, and modified starch. The industrial antibacterial and antifungal method according to any one of -5.
7). The industrial antibacterial and antifungal method according to any one of 1 to 6, wherein the ratio of the isothiocyanate contained in the capsule or powder is 1 to 20% by weight.
8). The method according to any one of 1 to 7, wherein the industrial product or industrial material is a water-soluble metalworking oil, a dampening solution for offset, a fiber oil agent, or a starch slurry.

  The industrial antibacterial and antifungal method of the present invention consists of adding an isothiocyanate to an aqueous solution of an industrial product or industrial material, which is convenient to use and has the convenience of being readily available when needed. Demonstrated exceptional effect on mold.

The antibacterial antifungal test result with cutting oil is shown.

  The isothiocyanate ester of the present invention means an oily substance having volatility at normal temperature, for example, isothiocyanate ester which is a pungent component of mustard and wasabi. This is a natural product obtained from plant extracts and the like, and is highly safe for the human body. Isothiocyanate ester is preferably used for hygiene because it exhibits an excellent antibacterial action. The isothiocyanate is not limited to a natural product, and may be a synthetic product synthesized by a method known per se.

  Specific examples of isothiocyanate include allyl isothiocyanate, phenyl isothiocyanate, methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, isopropyl isothiocyanate, butyl isothiocyanate, isobutyl isothiocyanate, isoamyl isothiocyanate, benzyl isothiocyanate, isothiocyanate Examples include cyclohexyl acid.

  In the present invention, an isothiocyanate is added to an aqueous solution of an industrial product or industrial material. Addition consists of continuous injection, intermittent injection, intermittent addition or immersion. Isothiocyanate is an oily substance, is volatile, volatilizes in the air, and decomposes early. For this reason, a sustained release property is essential for use in antibacterial and antifungal agents, and a product prepared by appropriate coating or the like has been provided (Japanese Patent Laid-Open No. 2011-87585). In the present invention, an isothiocyanate ester achieves a highly reliable and efficient antibacterial and antifungal effect by continuously presenting a constant concentration in an aqueous solution of industrial products or industrial materials that could not be used conventionally. I found out.

  Isothiocyanate is an oily substance, and if added directly to an aqueous solution of an industrial product or material, it is not miscible quickly because it is not miscible with water, giving off an irritating odor and having a sufficient effect on mold in the aqueous solution. I can't show it. In the present invention, isothiocyanate is continuously injected, intermittently injected, intermittently added, or immersed in an aqueous solution. Continuous injection means that the isothiocyanate ester is not directly added to the aqueous solution from the top, but is continuously introduced directly into the aqueous solution. Therefore, a very small amount of injection can be considered. By this injection, the isothiocyanate can be kept in a mixed state with the aqueous solution rather than staying floating in the supernatant of the aqueous solution. Intermittent injection means that the isothiocyanate ester is charged directly into an aqueous solution automatically or manually, periodically or at a desired time. The intermittent addition is not directly added to the aqueous solution but automatically or manually, periodically or at a desired time, from the top in the aqueous solution. However, the isothiocyanate ester cannot be miscible with water only by adding it normally, and it is necessary to perform appropriate stirring and liquid flow. Immersion refers to encapsulating an isothiocyanate ester in a suitable capsule or pellet particle, and wrapping it in an aqueous solution directly or in a net or the like.

  In the present invention, the isothiocyanate is added to the aqueous solution so as to have a maintenance concentration of 0.1 to 1000 ppm, preferably 1 to 1000 ppm, more preferably about 10 to 300 ppm. The indicated concentration is maintained continuously for the desired period. The isothiocyanate ester has a higher antibacterial and antifungal effect as the concentration is higher, but it has a severe irritating odor, so it is necessary to set the minimum concentration, especially when it is present in an aqueous solution. It is necessary to set conditions that can be used.

  In the present invention, an effective means for exerting an antibacterial and antifungal effect in an aqueous solution of isothiocyanate is that the isothiocyanate can maintain the capsule or powder film shape in the aqueous solution, and the isothiocyanate can be released slowly. A capsule or powder of an isothiocyanate ester that can flow into an aqueous solution is encapsulated in pellet particles, and the encapsulated pellet particles are added and immersed in an aqueous solution of the target industrial product or industrial material as needed. Alternatively, the pellet particles are loaded in a net-like bag and immersed in an aqueous solution of the target industrial product or industrial material when necessary.

  As the capsule or powder of the present invention, those having the property of forming a film when a water-soluble film forming agent is used and the aqueous solution is dried are used. The water-soluble film-forming agent may be any one as long as it constitutes a capsule or powder that contains isothiocyanate and can release the isothiocyanate from the capsule or powder in an aqueous solution. Examples include capsule (sodium octenyl succinate starch), gum arabic, gelatin, hemicellulose, microbial polysaccharide, modified starch and the like. These may be used singly or in combination of a plurality of types. In particular, the use of Capsule is optimal.

  The capsule or powder of the present invention is prepared by, for example, dissolving and / or dispersing a water-soluble film forming agent and, if necessary, a powder excipient in water, and then adding an isothiocyanate ester and, if necessary, an emulsifier. The emulsion obtained by emulsification can be produced by spray drying and pulverizing.

  Specific examples of the powder excipient include capsule, starch, starch degradation products, dextrin, monosaccharides such as glucose, disaccharides such as lactose, and the like. These may be used singly or in combination of a plurality of types. Suitable powder excipients include capsule, starch and dextrin.

  Emulsifiers can form water-soluble films using substances other than emulsifying substances such as gum arabic and Capsule (CAPSUL: a modified starch available under the name of Nationalstarchandchemical in the United States, which is available in Japan through NSC). It functions effectively when it is used as an agent to prepare an emulsion. Specific examples of the emulsifier include polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester and the like. These may be used singly or in combination of a plurality of types.

  What is necessary is just to perform the emulsification process for preparing an emulsion liquid in accordance with a conventional method. The emulsion is preferably spray-dried at 140 to 180 ° C. If the temperature is lower than 140 ° C, the dry powder may not be obtained because water cannot be sufficiently evaporated. On the other hand, if the temperature is higher than 180 ° C, the isothiocyanate may be volatilized during the process. There is.

  In addition, after dissolving and / or dispersing a water-soluble film forming agent and a powder excipient as necessary in water, the step of adding an isothiocyanate and, if necessary, an emulsifier may be performed at room temperature. However, after dissolving and / or dispersing a water-soluble film forming agent and, if necessary, a powder excipient and / or an emulsifier in water at room temperature, it is once heated to about 60 to 80 ° C. By increasing the solubility of the water-soluble film-forming agent by dissolving and / or dispersing the water-soluble film-forming agent and, if necessary, the powder excipient in water while being heated to about -80 ° C. After the heat sterilization, the isothiocyanate may be added after cooling to room temperature to about 60 ° C. Further, the isothiocyanate ester may be added after being dissolved in edible fats and oils such as medium chain fatty acids typified by refined coconut oil.

  The capsules or powders produced as described above are mostly hygroscopic capsules or powders containing spherical isothiocyanate having an average particle diameter of 1 to 100 μm, and contain a high proportion of isothiocyanate. In addition to that (for example, a composition containing 1 to 20% by weight of the isothiocyanate contained), the release stability is ensured. The mixing ratio of the isothiocyanate ester and the water-soluble film forming agent in the capsule or powder of the present invention is preferably 1 to 100 parts by weight of the water-soluble film forming agent with respect to 1 part by weight of the isothiocyanate ester. It is more desirable to be part by weight. In addition, when the powder excipient is used, the blending ratio is desirably 0.5 to 100 parts by weight with respect to 1 part by weight in total of the isothiocyanate ester and the water-soluble film forming agent, and 0.7 to 20 parts by weight. It is more desirable to be part by weight. The average particle size of the capsule or powder is desirably 1 to 100 μm, and more desirably 1 to 50 μm.

  The pellet particles of the present invention are prepared by heating and kneading the obtained capsule or powder with polyethylene. It is desirable that polyethylene is 1 to 100 parts by weight, and more desirably 1 to 20 parts by weight with respect to 1 part by weight of the capsule or powder. In addition, the average particle diameter of the pellet particles is desirably 1 to 20 mm, and more desirably 1 to 10 mm.

  When the pellet particles of the present invention are immersed in an aqueous solution, the isothiocyanate is released from the pellet particles into the aqueous solution without breaking the outer shape. The degree of release can be adjusted by appropriately changing the properties of the membrane, but the amount of isothiocyanate released into the aqueous solution can be adjusted to an appropriate antibacterial / antifungal concentration in the aqueous solution. is necessary.

  In the industrial antibacterial and antifungal method of the present invention, the prepared pellet particles may be added and immersed in an object as needed, but are loaded into a mesh bag as a preferred embodiment. The net is not particularly limited, and may be a net structure in which pellet particles can be held in a bag and may be insoluble in water, oil, or the like. The size of the bag is not particularly limited, and is not particularly limited as long as it can be stored in the outer bag so as not to damage the volatile active ingredient until use. Generally, a size of about 300 ml to 3000 ml is appropriate. The active ingredient-containing reticulated bag is loaded into an aluminum laminated synthetic resin film or a bag-like substance formed of a nonwoven fabric, paper, cloth or the like laminated with an aluminum laminated synthetic resin film.

  In the antibacterial and antifungal method comprising using the isothiocyanate of the present invention, for example, when an isothiocyanate of about 100 ppm in an aqueous solution is maintained at a maintenance concentration, a sufficient antibacterial and antifungal effect is exhibited even when stored for several months. It was done. For example, in the case of the isothiocyanate ester encapsulated in the pellet particles of the present invention, when about 10 g / L of the pellet particles were immersed in an aqueous solution, the antibacterial and antifungal effect was effective for about 3 months or more.

  Thus, the antibacterial and antifungal method using the isothiocyanate of the present invention can be applied to water-soluble metalworking oils, offset dampening water, textile oils, starch slurries, etc. as industrial products or industrial materials, particularly oil-based It is extremely effective as an antibacterial and antifungal method for materials.

  The industrial antibacterial and antifungal method of the present invention will be described in detail with reference to examples, but the present invention should not be construed as being limited to the following description.

Example 1 Preparation of Capsule or Powder and Preparation of Pellet Particles At 60 ° C., 250 g of Capsule as a water-soluble film forming agent and 250 g of starch as a powder excipient and 300 g of dextrin were added to 1500 g of water and mixed and stirred. To the solution cooled to room temperature, 200 g of allyl isothiocyanate was added as an isothiocyanate, and emulsified using an emulsifier (TK homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsion. The obtained emulsion was spray-dried with a spray dryer (drying temperature 150 ° C.) to obtain a light cream capsule or powder. The ratio of allyl isothiocyanate contained in the capsule or powder was 13.8% by weight. When the obtained capsules or powders were observed with a microscope, most of them consisted of spherical capsules or powder aggregates, and the average particle size of the capsules or powders was measured to be about 20 μm. Further, 80 parts by weight of polyethylene was heated and kneaded at 150 ° C. with respect to 20 parts by weight of the obtained capsule or powder, and pellets having an average of about 3 mm were prepared by extrusion molding. The content of allyl isothiocyanate in the obtained pellets was 2.5% by weight. When the pellet particles were stored in an atmosphere of about 60% humidity, the irritating odor of allyl isothiocyanate was hardly felt, but in the atmosphere of about 80% humidity, the irritating odor of allyl isothiocyanate was felt. The pellet particles were found to release allyl isothiocyanate in aqueous solution.

Example 2: Preparation of capsule or powder and preparation of pellet particles (Part 2)
At 60 ° C., 700 g of Capsule was added to 1500 g of water and mixed and stirred. A solution prepared by dissolving 200 g of allyl isothiocyanate in 100 g of purified coconut oil was added to the solution cooled to room temperature, and in the same manner as in Example 1, spherical capsules or powder aggregates having an average particle diameter of 20 μm were mostly formed. Obtained. The ratio of allyl isothiocyanate contained in the capsule or powder was 15.8% by weight. Further, 80 parts by weight of polyethylene was heated and kneaded at 150 ° C. with respect to 20 parts by weight of the obtained capsule or powder, and pellets having an average of about 3 mm were prepared by extrusion molding. The pellet particles obtained had an allyl isothiocyanate content of 2.6% by weight.

Example 3: Preparation of capsule or powder and preparation of pellet particles (Part 3)
At 80 ° C., 700 g of Capsule was added to 1500 g of water and mixed and stirred. A solution prepared by dissolving 150 g of allyl isothiocyanate in 150 g of purified coconut oil was added to the solution cooled to room temperature, and in the same manner as in Example 1, spherical capsules or powder aggregates having an average particle diameter of 20 μm were obtained. Obtained. The ratio of allyl isothiocyanate contained in the capsule or powder was 12.5% by weight. Further, 80 parts by weight of polyethylene was heated and kneaded at 150 ° C. with respect to 20 parts by weight of the obtained capsule or powder, and pellets having an average of about 3 mm were prepared by extrusion molding. The resulting pellet particles had an allyl isothiocyanate content of 2.1% by weight.

Example 4: Preparation of capsule or powder and preparation of pellet particles (Part 4)
At 80 ° C., 850 g of Capsule was added to 1500 g of water and mixed and stirred. To the solution cooled to room temperature, 150 g of allyl isothiocyanate was added, and in the same manner as in Example 1, spherical capsules or powder aggregates having an average particle diameter of 7 mm were obtained. The ratio of allyl isothiocyanate contained in the capsule or powder was 13.2% by weight. Further, 80 parts by weight of polyethylene was heated and kneaded at 150 ° C. with respect to 20 parts by weight of the obtained capsule or powder, and pellets having an average of about 3 mm were prepared by extrusion molding. The pellet particles obtained had an allyl isothiocyanate content of 2.2% by weight.

Example 5: Preparation of capsule or powder and preparation of pellet particles (Part 5)
At room temperature, 700 g of Capsule was added to 1500 g of water and mixed and stirred. Next, a solution in which 200 g of allyl isothiocyanate was dissolved in 100 g of purified coconut oil was added, and in the same manner as in Example 1, spherical capsules or powder aggregates having an average particle diameter of 7 mm were obtained. The ratio of allyl isothiocyanate contained in the capsule or powder was 16.4% by weight. Further, 80 parts by weight of polyethylene was heated and kneaded at 150 ° C. with respect to 20 parts by weight of the obtained capsule or powder, and pellets having an average of about 3 mm were prepared by extrusion molding. The pellet particles obtained had an allyl isothiocyanate content of 2.4% by weight.

Experimental example 1
The cutting oil in use was collected and used as a test solution. The test product was obtained by adding the pellet preparation (0.5% W / V) prepared in Example 2 to the test solution, and the target product was an additive-free product. These were allowed to stand at room temperature, and the number of aerobic bacteria was measured over time. The cutting oil used was an emulsion type (Chemicourt E-3110S), and it was 4 months after dilution adjustment.
The result is as shown in FIG. 1, and the test product maintained its state stably after the number of bacteria rapidly decreased. The appearance was milky white liquid and no off-flavor was observed. On the other hand, the target product showed an increasing tendency in the number of bacteria until the 30th day, and the color changed to light brown and gave off a strange odor.

  According to the present invention, pellet particles containing a high proportion of isothiocyanate can provide a new industrial antibacterial and antifungal method, and an industrial antibacterial and antifungal method excellent in usability is provided.

Claims (1)

An antibacterial and antifungal method for water-soluble metalworking oil comprising continuously injecting, intermittently injecting, or intermittently adding isothiocyanate to water-soluble metalworking oil, wherein In an antibacterial and antifungal method of a water-soluble metalworking oil that is continuously maintained at a concentration of 1000 ppm for a desired period of time,
Use the isothiocyanate ester as it is without pelletizing the capsule or powder, and automatically or manually add a trace amount to the water-soluble metalworking oil so that the isothiocyanate ester concentration is 1 to 1000 ppm. Antibacterial and antifungal method of water-soluble metalworking oil, injecting continuously or intermittently, or injecting trace amount automatically or manually from above, continuously or intermittently, causing stirring or liquid flow .

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