JP2020007283A - Industrial antibacterial and antifungal process - Google Patents
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Abstract
Description
本発明は、工業的抗菌防カビ方法に関し、特に、イソチオシアン酸エステルの新規な用途として、工業的抗菌防カビ剤として使用することからなる。 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.
従来から、含水パルプ、染料、糊料、接着剤、切削油剤、ラテックス類、木材、皮革、繊維、繊維油剤、コーキング剤、樹脂、壁紙、セパレートシート、石膏ボード原紙、オフセット印刷用湿し水などの多くの工業製品または工業用材料において、水を使う領域で、真菌のような微生物によって汚染され、劣化し、その外観や商品価値が低下することが知られている。 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.
本発明者は、先に、イソチオシアン酸エステルのカプセル又はペレット粒子の開発に成功し、その持続的な抗菌力を生かして、食品等の抗菌防黴シートの提供に成功している。 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.
本発明は、先に本発明者が開発したイソチオシアン酸エステルの新規な用途の展開である。特に、水溶性金属加工油の抗菌防カビ方法の提供である。 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 a water-soluble metalworking oil.
上記の点に鑑みてなされた本発明の工業的抗菌防カビ方法は、以下からなる；
１． イソチオシアン酸エステルを、水溶性金属加工油に持続注入若しくは断続注入若しくは断続添加させることからなる水溶性金属加工油の抗菌防カビ方法であって、水溶性金属加工油に、イソチオシアン酸エステルを少なくとも４ｐｐｍ濃度に所望期間中継続的に維持させる水溶性金属加工油の抗菌防カビ方法。
The industrial antibacterial and antifungal method of the present invention made in view of the above points comprises the following:
1. An antibacterial and fungicidal method for a water-soluble metal working oil, comprising continuously injecting or intermittently adding or intermittently adding an isothiocyanate to a water-soluble metal working oil, wherein the water-soluble metal working oil contains at least 4 ppm of an isothiocyanate. An antibacterial and fungicidal method for a water-soluble metalworking oil that is continuously maintained at a desired concentration for a desired period of time.
本発明の工業的抗菌防カビ方法は、イソチオシアン酸エステルをそのまま工業製品又は工業材料の水溶液に添加することからなり、使用が簡便で、必要なときに素早く利用できる便宜性をもち、そのうえ、抗菌防カビに対する格別の効果を発揮した。 The industrial antibacterial and antifungal method of the present invention comprises adding an isothiocyanate ester as it is to an aqueous solution of an industrial product or an industrial material, which is simple to use, has the convenience of being quickly used when needed, and furthermore has the antibacterial property. It has a special effect on mold control.
本発明のイソチオシアン酸エステルとは、常温において揮発性を有する油状物質を意味し、例えば、カラシやワサビの辛味成分であるイソチオシアン酸エステルがこれに該当する。これは植物の抽出物などから得られる天然品であって、人体に対する安全性が高いものである。イソチオシアン酸エステルは優れた抗菌作用を発揮することから衛生上において好適に用いられる。なお、イソチオシアン酸エステルは天然品に限定されるものではなく、自体公知の方法によって合成された合成品であってもよい。 The isothiocyanate of the present invention means an oily substance which has volatility at room temperature, 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.
イソチオシアン酸エステルの具体例としては、イソチオシアン酸アリル、イソチオシアン酸フェニル、イソチオシアン酸メチル、イソチオシアン酸エチル、イソチオシアン酸プロピル、イソチオシアン酸イソプロピル、イソチオシアン酸ブチル、イソチオシアン酸イソブチル、イソチオシアン酸イソアミル、イソチオシアン酸ベンジル、イソチオシアン酸シクロヘキシルなどが挙げられる。 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.
本発明において、イソチオシアン酸エステルを、水溶性金属加工油中に添加する。添加は、持続注入若しくは断続注入若しくは継続添加若しくは断続添加させることからなる。イソチオシアン酸エステルは、油状物質であり、揮発性であり、空気中及び水溶液中では、揮発し、早期に分解していく。そのため、抗菌防カビ等に使用するには、継続的に水溶性金属加工油中に一定濃度が必須である。本発明において、イソチオシアン酸エステルは、従来使用が不可能であった、水溶性金属加工油に、そのまま、継続的に一定濃度を存在させることで極めて確実で効率的な抗菌防カビ効果が達成されることを見出した。 In the present invention, the isothiocyanate is added to the water-soluble metalworking oil. The addition consists of continuous or intermittent injection or continuous or intermittent addition. Isothiocyanates are oily substances, are volatile, volatilize in air and aqueous solutions, and decompose early. For this reason, in order to use it for antibacterial and antifungal, a certain concentration is required in the water-soluble metal working oil continuously. In the present invention, the isothiocyanate ester, which has been impossible to use conventionally, has a very reliable and efficient antibacterial and antifungal effect by achieving a constant concentration of the water-soluble metal working oil as it is continuously. I found that.
イソチオシアン酸エステルは、油状物質であり、水溶性金属加工油に直接添加するだけでは、水に混和しないので速やかに分散されず、刺激臭を放ち水溶液中のカビに対して十分な効果を発揮できない。
本発明においては、イソチオシアン酸エステルをそのまま水溶性金属加工油に極微量注入若しくは添加する。イソチオシアン酸エステルの注入若しくは添加量は、イソチオシアン酸エステルの揮発・分解速度を考慮し、対象の水溶性金属加工油量から設定される注入若しくは添加量/分を設定し、対象水溶性金属加工油中での維持濃度を特定する。例えば、イソチオシアン酸エステルを0.01〜0.02ml/分で、水溶性金属加工油保存槽5000〜6000Lに添加する。
又、本発明では、イソチオシアン酸エステル低濃度水溶液、例えば、0.005〜0.05％W/W、好適には0.01〜0.05％W/W、さらに好適には0.02〜0.03％W/W、を調製し、この水溶液を対象である水溶性金属加工油に持続注入若しくは断続注入若しくは継続添加若しくは断続添加してもよい。
持続注入とは、水溶性金属加工油に単に上部から添加するというのではなく、水溶性金属加工油にイソチオシアン酸エステルを連続して投入することを意味し、例えば、イソチオシアン酸エステルをそのままの保存した保存器の小孔から若しくは低濃度水溶液の保存器の小孔から、自動的に連続して極微量の注入が考えられる。この注入により、イソチオシアン酸エステルは水溶性金属加工油の上澄み部に浮かぶように滞留するのではなく水溶性金属加工油と混ざり合った状態が確保できる。
断続注入とは、自動若しくは手動で、定期的に若しくは所望時期に、水溶性金属加工油にイソチオシアン酸エステルをそのまま若しくはイソチオシアン酸エステル低濃度水溶液を小孔等から投入することを意味する。
断続添加とは、自動若しくは手動で、定期的に若しくは所望時期に、水溶性金属加工油に、イソチオシアン酸エステルをそのまま若しくはイソチオシアン酸エステルの低濃度水溶液を上部から添加する。そしてその後、適当な撹拌、液流をおこす。
継続添加とは、連続的に、水溶性金属加工油に、イソチオシアン酸エステルをそのまま若しくはイソチオシアン酸エステルの低濃度水溶液を、上部から添加する。そしてその後、適当な撹拌、液流をおこす。
Isothiocyanate is an oily substance, and if it is added directly to a water-soluble metalworking oil, it will not disperse promptly because it is immiscible with water and will not emit a pungent odor and will not exert sufficient effects on mold in aqueous solution .
In the present invention, a very small amount of isothiocyanate is directly injected or added to the water-soluble metalworking oil. The injection or addition amount of the isothiocyanate ester is determined by considering the volatilization / decomposition rate of the isothiocyanate ester, and the injection or addition amount / minute is set based on the amount of the target water-soluble metal processing oil. The maintenance concentration in the medium. For example, isothiocyanate is added at 0.01 to 0.02 ml / min to 5000 to 6000 L of a water-soluble metal working oil storage tank.
Further, in the present invention, a low-concentration aqueous solution of isothiocyanate, for example, 0.005 to 0.05% W / W, preferably 0.01 to 0.05% W / W, more preferably 0.02 to 0.03% W / W, This aqueous solution may be continuously injected or intermittently injected or continuously added or intermittently added to the target water-soluble metalworking oil.
Continuous injection means that the isothiocyanate is continuously added to the water-soluble metalworking oil instead of simply added to the water-soluble metalworking oil from above, for example, preserving the isothiocyanate as it is It is conceivable to automatically and continuously inject a very small amount from the small hole of the preserved container or from the small hole of the low concentration aqueous solution reservoir. By this injection, the isothiocyanate ester can be maintained in a state of being mixed with the water-soluble metal working oil, instead of staying in the supernatant of the water-soluble metal working oil.
The term “intermittent injection” means that the isothiocyanate ester is directly or automatically added to the water-soluble metalworking oil or a low-concentration aqueous solution of the isothiocyanate ester through a small hole, automatically or manually.
The intermittent addition is to add the isothiocyanate as it is or a low-concentration aqueous solution of the isothiocyanate to the water-soluble metal working oil, automatically or manually, at regular or desired times. Thereafter, appropriate stirring and liquid flow are performed.
In the continuous addition, the isothiocyanate ester or a low-concentration aqueous solution of the isothiocyanate ester is continuously added to the water-soluble metalworking oil from above. Thereafter, appropriate stirring and liquid flow are performed.
本発明において、イソチオシアン酸エステルは対象水溶性金属加工油中に維持濃度として少なくとも４ｐｐｍ、好適には４〜１０００ｐｐｍ、さらに好適には４〜１００ｐｐｍ、もっと好適には４〜１０ｐｐｍ程度になるように添加する。示適濃度は、所望期間中継続的に維持させる。イソチオシアン酸エステルは、濃度が濃いほど抗菌防カビ効果は、優れるが、ひどい刺激臭があることから、必要最小限の濃度設定が必要であり、特に、水溶性金属加工油中に存在する状態で抗菌防カビ効果が発揮できる条件の設定を必要とする。 In the present invention, the isothiocyanate is added to the target water-soluble metalworking oil so as to have a maintenance concentration of at least 4 ppm, preferably 4 to 1000 ppm, more preferably 4 to 100 ppm, and even more preferably about 4 to 10 ppm. I do. 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 a water-soluble metalworking oil. It is necessary to set conditions under which the antibacterial and antifungal effects can be exhibited.
本発明のイソチオシアン酸エステルを使用することからなる抗菌防カビ方法において、例えば、水溶性金属加工油中に４ｐｐｍ程度のイソチオシアン酸エステルを維持濃度にした場合、数か月保存においても十分な抗菌防カビ効果が発揮された。 In the antibacterial and antifungal method comprising using the isothiocyanate of the present invention, for example, when the maintenance concentration of about 4 ppm of the isothiocyanate in the water-soluble metalworking oil is sufficient, the antibacterial and antifungal can be sufficiently stored for several months. A mold effect was exhibited.
かくして、本発明のイソチオシアン酸エステルによる抗菌防カビ方法は、工業製品又は工業材料として、水溶性金属加工油、特に油系材料の抗菌防カビ方法として極めて優れた効果を発揮する。 Thus, the antibacterial and antifungal method using the isothiocyanate of the present invention exerts an extremely excellent effect as an antibacterial and antifungal method for water-soluble metal working oils, particularly oil-based materials, as industrial products or industrial materials.
本発明の工業的抗菌防カビ方法について実施例により詳細に説明するが、本発明は以下の記載に何ら限定して解釈されるものではない。 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.
実施例１：イソチオシアン酸エステル低濃度水溶液の調製
室温にて、水500ｍｌに対して、イソチオシアン酸エステルとしてイソチオシアン酸アリル0.1ｇの割合で混合させ、イソチオシアン酸エステル0.02％W/W水溶液を調製した。
Example 1 Preparation of Isothiocyanate Low Concentration Aqueous Solution At room temperature, 500 g of water was mixed as isothiocyanate at a ratio of 0.1 g of allyl isothiocyanate to prepare a 0.02% w / w aqueous solution of isothiocyanate.
実施例２：イソチオシアン酸エステルの直接注入
イソチオシアン酸アリルをそのまま0.01〜0.02ml/分で、水溶性金属加工油保存槽5000〜6000Lに注入した。
Example 2: Direct injection of isothiocyanate Allyl isothiocyanate was directly injected into a water-soluble metal working oil storage tank at 5000 to 6000 L at 0.01 to 0.02 ml / min.
実施例３：
実施例２のイソチオシアン酸エステルを、水溶性金属加工油に小孔から注入した。水溶性金属加工油量及びイソチオシアン酸エステルの注入・揮発・分解量率から、水溶性金属加工油中でのイソチオシアン酸エステルの維持濃度を4ppmに設定し、持続注入量率を特定した。
Example 3
The isothiocyanate of Example 2 was injected into the water-soluble metalworking oil through small holes. Based on the amount of the water-soluble metal working oil and the injection / volatilization / decomposition rate of the isothiocyanate, the maintenance concentration of the isothiocyanate in the water-soluble metal working oil was set at 4 ppm, and the continuous injection rate was specified.
実施例４：
実施例３において、水溶性金属加工油を、自動的に若しくは断続的に撹拌した。撹拌速度は、イソチオシアン酸エステルの揮発性を考慮し、極緩やかのものとした。
Example 4:
In Example 3, the water-soluble metalworking oil was stirred automatically or intermittently. The stirring speed was extremely slow in consideration of the volatility of the isothiocyanate.
実施例５
マシニングセンタ（DMGMORI製 切削油タンク600L）8台と切削油の濃度調整及び循環供給を行う曹（600L 調整循環曹）からなる一連の装置群にイソチオシアン酸アリルを持続注入（山善(株)製マイクロセラムポンプMSP）し切削油の腐敗防止を行った。
切削油は切削物に付着して減少するが調整循環曹で自動的に調整して補充されるので、切削油総量は約5500Lで一定している。更にこの一連の装置群は24時間稼働しているので、イソチオシアン酸アリルも24時間持続注入を行った。
種々検討の結果イソチオシアン酸アリルを0.0127ml/分の速度で調整循環層に注入した。注入開始時と10日後のマシニングセンタ内の切削油に含まれるイソチオシアン酸アリル濃度（(株)ガステック製 メタクリル酸メチル検知管 通気法）及び一般生菌数を菌数測定キット（JNC株式会社製 MCメディアパッド）で測定した。
マシニングセンタの切削油中のイソチオシアン酸アリル濃度は4ppmになっており十分菌の成育抑制濃度に達していた。それに伴って一般生菌は試験開始時の3.1×106cfu/mlから10日後は6.4×103cfu/mlと明らかに減少していた。また、嗅覚的に臭気も減少する結果が得られた。
Example 5
Continuous injection of allyl isothiocyanate into a series of equipment consisting of eight machining centers (600 liters of DMGMORI cutting oil tank) and a soda (600 liter adjusting circulating soda) for adjusting and circulating the supply of cutting oil (Micro Serum manufactured by Yamazen Corporation) Pump MSP) to prevent cutting oil from spoiling.
Although the cutting oil adheres to the cuttings and decreases, it is automatically adjusted and replenished by the adjusting circulating soda, so the total amount of cutting oil is constant at about 5500L. Furthermore, since this series of devices was operating for 24 hours, allyl isothiocyanate was also continuously injected for 24 hours.
As a result of various studies, allyl isothiocyanate was injected into the circulating bed at a rate of 0.0127 ml / min. At the start of injection and 10 days after, the concentration of allyl isothiocyanate in the cutting oil in the machining center (Methyl methacrylate detector tube manufactured by Gastech Co., Ltd., aeration method) and the number of general viable bacteria were measured using a bacteria count kit (MC manufactured by JNC Corporation). Media pad).
The concentration of allyl isothiocyanate in the cutting oil of the machining center was 4 ppm, which was sufficient for the growth inhibitory concentration of bacteria. Along with that, the general viable bacteria clearly decreased from 3.1 × 10 6 cfu / ml at the start of the test to 6.4 × 10 3 cfu / ml 10 days later. Moreover, the result that the odor was reduced olfactoryly was obtained.
実験例 １
使用中の切削油を採取し試験液とした。試験品は試験液に実施例１で調製した水溶液（0.02％Ｗ/Ｖ）を加えたもの、また、対象品は無添加の物を用いた。イソチオシアン酸エステルの濃度は、２，４，６，８，１０ｐｐｍとした。試験液を密封容器にいれ、３５℃で２４時間保温して一般生菌数を菌数測定キット（ＭＣメデイアパッドＪＮＣ株式会社）で測定した。使用した切削油はエマルジョン型（ケミクールE-311S）で希釈調整後４か月経ていた。
結果は、図１の通りで、イソチオシアン酸エステルの４ｐｐｍ以上で確実に菌数を抑制し又外観変化もみられない。
Experimental example 1
The used cutting oil was collected and used as a test liquid. The test product was prepared by adding the aqueous solution (0.02% W / V) prepared in Example 1 to the test solution, and the target product was used without addition. The concentration of the isothiocyanate was 2, 4, 6, 8, and 10 ppm. The test solution was placed in a sealed container, kept at 35 ° C. for 24 hours, and the number of general viable cells was measured using a cell count kit (MC Media Pad JNC). The cutting oil used was an emulsion type (Chemicool E-311S) and had been diluted for 4 months.
The results are as shown in FIG. 1. As shown in FIG. 1, when the amount of isothiocyanate is 4 ppm or more, the number of bacteria is surely suppressed and there is no change in appearance.
本発明によれば、イソチオシアン酸エステルは、新規な工業的抗菌防カビ方法が提供でき、使いやすさに優れた工業的抗菌防カビ方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the isothiocyanate ester can provide a novel industrial antibacterial and fungicide method, and an industrial antibacterial and fungicide method excellent in usability is provided.
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|---|---|---|---|---|
| JPH03154688A (en) * | 1989-11-09 | 1991-07-02 | Minato Sangyo Kk | Method for sterilizing water |
| WO2000010394A1 (en) * | 1998-08-25 | 2000-03-02 | Nissan Chemical Industries, Ltd. | Industrial, anti-bacterial and -fungal agents, algicides and bioadhesion inhibitors, containing phenyl isothiocyanates |
| JP2017031082A (en) * | 2015-07-30 | 2017-02-09 | 株式会社Ｐｒｄ | Industrial antibacterial and fungicidal method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03154688A (en) * | 1989-11-09 | 1991-07-02 | Minato Sangyo Kk | Method for sterilizing water |
| WO2000010394A1 (en) * | 1998-08-25 | 2000-03-02 | Nissan Chemical Industries, Ltd. | Industrial, anti-bacterial and -fungal agents, algicides and bioadhesion inhibitors, containing phenyl isothiocyanates |
| JP2017031082A (en) * | 2015-07-30 | 2017-02-09 | 株式会社Ｐｒｄ | Industrial antibacterial and fungicidal method |
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