JP6633698B2 - Industrial antibacterial and antifungal methods - Google Patents

Description

  The present invention relates to an industrial antibacterial / mildew-proof method, and more particularly, to a novel use of isothiocyanate ester as an industrial antibacterial / mildew-proof agent.

  Conventionally, hydrous pulp, dye, paste, adhesive, cutting oil, latex, wood, leather, fiber, textile oil, caulking agent, resin, wallpaper, separate sheet, gypsum board base paper, dampening solution for offset printing, etc. It is known that many industrial products or materials are contaminated and deteriorated by microorganisms such as fungi in areas where water is used, and their appearance and commercial value are reduced.

  The present inventor has previously succeeded in developing isothiocyanate capsule or pellet particles, and has succeeded in providing an antibacterial and antifungal sheet for foods and the like by utilizing its continuous antibacterial activity.

JP 2011-87585 A JP 2011-30576 A

  The present invention is a development of a novel use of an isothiocyanate ester previously developed by the present inventors. In particular, it is an object of the present invention to provide an antibacterial and antifungal method for an industrial product or an industrial material comprising 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 / mildew-proof method comprising continuously injecting, intermittently injecting, intermittently adding or dipping an isothiocyanate ester into an aqueous solution of an industrial product or an industrial material.
2. 1. An industrial antibacterial / mildew-proof method for maintaining an isothiocyanate ester at a concentration of 1 to 1000 ppm in an aqueous solution for a desired period of time.
3. The isothiocyanate ester is capable of maintaining the capsule or powder film shape in the aqueous solution, and the isothiocyanate ester capsule or powder having the property that the isothiocyanate ester can be slowly released into the aqueous solution is encapsulated in the pellet particles. The encapsulated pellet particles are added and immersed as needed in an aqueous solution of the target industrial product or industrial material, or the pellet particles are loaded in a net-like bag, and, when necessary, an aqueous solution of the target industrial product or industrial material. 3. The industrial antibacterial and antifungal method according to 1 or 2, which is immersed in water.
4. 4. The industrial antibacterial and antifungal method according to any one of 1 to 3, wherein the average particle size of the pellet particles is 1 to 10 mm.
5. 6. The industrial antibacterial and antifungal method according to any one of 1 to 5, wherein the isothiocyanate is dissolved in fats and oils.
6. The capsule or powder film-forming agent is at least one selected from the group consisting of capsul (sodium starch octenylsuccinate), gum arabic, gelatin, hemicellulose, microbial polysaccharides, and modified starch. 6. The industrial antibacterial and antifungal method according to any one of items 5 to 5.
7. 7. The industrial antibacterial and antifungal method according to any one of 1 to 6, wherein the proportion of the isothiocyanate ester contained in the capsule or the powder is 1 to 20% by weight.
8. 8. The method according to any one of 1 to 7, wherein the industrial product or material is a water-soluble metalworking oil, a fountain solution for offset, a fiber oil agent, or a starch slurry.

  The industrial antibacterial and antifungal method of the present invention comprises adding an isothiocyanate ester to an aqueous solution of an industrial product or an industrial material, which is easy to use, has the convenience of being quickly used when required, and furthermore has the antibacterial and antifungal method. It has a special effect on mold.

4 shows the results of an antibacterial and antifungal test using cutting oil.

  The isothiocyanate of the present invention means an oily substance having volatility at normal temperature, and for example, isothiocyanate 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 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 the isothiocyanate include allyl isothiocyanate, phenyl isothiocyanate, methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, isopropyl isothiocyanate, butyl isothiocyanate, isobutyl isothiocyanate, isoamyl isothiocyanate, benzyl isothiocyanate, and isothiocyanate. And cyclohexyl acid.

  In the present invention, an isothiocyanate is added to an industrial product or an aqueous solution of an industrial material. The addition comprises continuous or intermittent injection or intermittent addition or immersion. Isothiocyanates are oily substances, are volatile, evaporate in air, and decompose prematurely. For this reason, sustained release is essential for use in antibacterial and fungicidal protection, and a product prepared with an appropriate coating or the like has been provided (JP-A-2011-87585). In the present invention, the isothiocyanate ester, which has been impossible to use conventionally, achieves an extremely reliable and efficient antibacterial and antifungal effect by continuously maintaining a constant concentration in an aqueous solution of an industrial product or an industrial material. I found that.

  Isothiocyanate is an oily substance, and if it is added directly to an industrial product or an aqueous solution of an industrial material, it will not disperse promptly because it is immiscible with water, emits a pungent odor and has a sufficient effect on mold in the aqueous solution. I can't show it. In the present invention, the isothiocyanate is continuously injected or intermittently injected, intermittently added, or immersed in an aqueous solution. Continuous injection means that the isothiocyanate ester is continuously introduced directly into the aqueous solution, rather than simply added to the aqueous solution from the top. A very small amount of injection is possible. By this injection, the isothiocyanate ester can be maintained in a state of being mixed with the aqueous solution instead of staying so as to float on the supernatant of the aqueous solution. Intermittent injection means that the isothiocyanate ester is directly or automatically injected into an aqueous solution, periodically or at a desired time. The term “intermittent addition” does not mean direct addition into an aqueous solution, but automatically or manually, periodically or at a desired time, from the top of the aqueous solution. However, the isothiocyanate cannot be miscible with water by merely adding it normally, and it is necessary to cause appropriate stirring and liquid flow. Immersion refers to enclosing an isothiocyanate ester in appropriate capsules or pellet particles, and immersing it in an aqueous solution directly or by wrapping it in a net or the like.

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

  In the present invention, an efficient means for exhibiting an antibacterial and antifungal effect in an aqueous solution of isothiocyanate is that isothiocyanate can be maintained in a capsule or powder film form in an aqueous solution, and isothiocyanate is gradually released. A capsule or powder of an isothiocyanate ester having a property capable of flowing out into an aqueous solution is encapsulated in pellet particles, and the encapsulated pellet particles are added and immersed as needed in an aqueous solution of the target industrial product or industrial material as needed. Alternatively, the method comprises loading the pellet particles in a net-like bag and, if necessary, immersing the pellets in an aqueous solution of the target industrial product or industrial material.

  As the capsule or powder of the present invention, a capsule or powder having a property of forming a film when the aqueous solution is dried by forming a film using a water-soluble film forming agent is used. The water-soluble film forming agent constitutes a capsule or powder containing the isothiocyanate ester, and may be any as long as it can release the isothiocyanate ester from the capsule or powder in an aqueous solution. Examples include capsul (sodium starch octenylsuccinate), gum arabic, gelatin, hemicellulose, microbial polysaccharides, modified starch, and the like. These may be used alone or in combination of two or more. In particular, the use of Capsule is optimal.

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

  Specific examples of powder excipients include capsul, starch, degraded starch, dextrin, monosaccharides such as glucose, and disaccharides such as lactose. These may be used alone or in combination of two or more. Suitable powder excipients include capsule, starch, dextrin and the like.

  The emulsifier is used to form a water-soluble film from substances other than those having an emulsifying action, such as gum arabic and capsul (CAPSUL: a modified starch available from Japan NSC in Japan under the trade name of Nationalstarchandchemical). It functions effectively when an emulsion is prepared by using it as an agent. Specific examples of the emulsifier include polyglycerin fatty acid ester, sucrose fatty acid ester, and sorbitan fatty acid ester. These may be used alone or in combination of two or more.

  The emulsification treatment for preparing the emulsion may be performed according to a conventional method. The spray drying of the emulsion is desirably performed at 140 to 180 ° C. If the temperature is lower than 140 ° C., there is a possibility that a dry powder cannot be obtained because water cannot be sufficiently evaporated. On the other hand, if the temperature is higher than 180 ° C., isothiocyanate may volatilize during the process. There is.

  The step of dissolving and / or dispersing the water-soluble film forming agent and, if necessary, the powder excipient in water, and then adding the isothiocyanate and the emulsifier as necessary 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, the mixture is once heated to about 60 to 80 ° C. 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., the solubility of the water-soluble film-forming agent is increased or the solution is dissolved. And then cooling to room temperature to about 60 ° C., and then adding the isothiocyanate. Further, the isothiocyanate may be dissolved in edible oils and fats such as medium chain fatty acids typified by refined coconut oil and added.

  Most of the capsules or powders produced as described above are made of hygroscopic capsules or powders containing spherical isothiocyanates having an average particle diameter of 1 to 100 μm, and contain a high proportion of isothiocyanates. In addition (for example, a composition containing 1 to 20% by weight of the contained isothiocyanate), its release stability is ensured. The mixing ratio of the isothiocyanate 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. More preferably, it is by weight. When a powder excipient is used, its mixing ratio is preferably 0.5 to 100 parts by weight, and more preferably 0.7 to 20 parts by weight, based on 1 part by weight of the total of the isothiocyanate and the water-soluble film forming agent. More preferably, it is by weight. The average particle size of the capsule or powder is preferably 1 to 100 μm, more preferably 1 to 50 μm.

  The pellet particles of the present invention are prepared by heating and kneading the obtained capsule or powder with polyethylene. The amount of polyethylene is preferably 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 1 part by weight of the capsule or powder. The average particle size of the pellet particles is preferably 1 to 20 mm, and more preferably 1 to 10 mm.

  When the pellet particles of the present invention are immersed in an aqueous solution, they release the isothiocyanate ester 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 it can be adjusted so that the amount of the isothiocyanate released into the aqueous solution has an appropriate concentration for showing antibacterial and antifungal properties in the aqueous solution. is necessary.

  In the industrial antibacterial and antifungal method of the present invention, the prepared pellet particles may be added to and immersed in the object as needed, but is loaded into a net-like bag as a preferred embodiment. The mesh is not particularly limited as long as the mesh has a mesh structure capable of holding the pellet particles in the bag and is 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 until the volatile active ingredient is not damaged until use. Generally, a size of about 300 ml to 3000 ml is appropriate. The net bag containing the active ingredient 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 the aluminum-laminated synthetic resin film.

  In the antibacterial / mildew-proofing method comprising using the isothiocyanate of the present invention, for example, when the isothiocyanate is maintained at a concentration of about 100 ppm in an aqueous solution, a sufficient antibacterial / mildew-proof effect is exhibited even when stored for several months. Was done. For example, in the case of the isothiocyanate ester encapsulated in the pellet particles of the present invention, when the pellet particles of about 10 g / L 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 metal working oils, offset fountain solutions, fiber oil agents, starch slurries, etc. as industrial products or industrial materials, especially oil-based products. Very effective as an antibacterial and antifungal method for materials.

  EXAMPLES 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., to 1500 g of water, 250 g of Capsule as a water-soluble film-forming agent, 250 g of starch as a powder excipient and 300 g of dextrin were mixed and stirred. To the solution cooled to room temperature, 200 g of allyl isothiocyanate as an isothiocyanate was added 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 drier (drying temperature: 150 ° C.) to obtain a pale cream capsule or powder. The proportion of allyl isothiocyanate contained in this capsule or powder was 13.8% by weight. When the obtained capsule or powder was observed with a microscope, most of the capsule or powder was composed of aggregates of spherical capsules or powder. The average particle size of the capsule or powder was 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 at a humidity of about 60%, almost no pungent odor of allyl isothiocyanate was sensed, but under an atmosphere of about 80% humidity, a pungent odor of allyl isothiocyanate was felt. The pellet particles were found to release allyl isothiocyanate in the 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 obtained by dissolving 200 g of allyl isothiocyanate in 100 g of purified coconut oil was added to the solution cooled to room temperature, and a large number of spherical capsules or powder aggregates having an average particle diameter of 20 μm were obtained in the same manner as in Example 1. Obtained. The proportion of allyl isothiocyanate contained in this 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 content of allyl isothiocyanate in the obtained pellet particles was 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 obtained by dissolving 150 g of allyl isothiocyanate in 150 g of purified coconut oil was added to the solution cooled to room temperature, and a large number of spherical capsules or powder aggregates having an average particle diameter of 20 μm were obtained in the same manner as in Example 1. Obtained. The proportion of allyl isothiocyanate contained in this 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 content of allyl isothiocyanate in the obtained pellet particles was 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 a large amount of spherical capsules or powder aggregates having an average particle diameter of 7 mm were obtained in the same manner as in Example 1. The proportion of allyl isothiocyanate contained in this 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 content of allyl isothiocyanate in the obtained pellet particles was 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, an aggregate of spherical capsules or powders, most of which had an average particle diameter of 7 mm, was obtained. The proportion of allyl isothiocyanate contained in this 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 content of allyl isothiocyanate in the obtained pellet particles was 2.4% by weight.

Experimental example 1
The used cutting oil was collected and used as a test liquid. The test product was prepared by adding the pellet preparation (0.5% W / V) prepared in Example 2 to the test solution, and the target product was a non-added product. These were left at room temperature and the number of aerobic bacteria was measured over time. The used cutting oil was an emulsion type (Chemicool E-3110S), and 4 months had passed after dilution adjustment.
The results are as shown in FIG. 1. The test article stably maintained its state after the bacterial count rapidly decreased. The appearance was milky liquid and no off-flavor was observed. On the other hand, in the target product, the number of bacteria showed an increasing tendency until the 30th day, and the color changed to light brown and emitted an off-flavor.

  ADVANTAGE OF THE INVENTION According to this invention, the pellet particle | grains containing a high ratio of isothiocyanate can provide a novel industrial antibacterial / fungicidal method, and provide an industrial antibacterial / antifungal method excellent in usability.

Claims (1)

An antibacterial / mildew-proofing method for a water-soluble metalworking oil, which comprises continuously injecting or intermittently adding or intermittently adding an isothiocyanate to a water-soluble metalworking oil. In an antibacterial and antifungal method for a water-soluble metalworking oil continuously maintained at a concentration of 300 ppm for a desired period of time
Isothiocyanate is automatically and continuously injected into the water-soluble metalworking oil so as to have a concentration of 10 to 300 ppm or automatically or manually from the top, continuously or intermittently, An antibacterial and antifungal method for water-soluble metalworking oil that causes stirring or liquid flow .

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