JP2007254349A - Germicide composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new germicide composition having an excellent degree of freedom of mixing and high germicidal power even in the presence of stain such as organic material, etc. <P>SOLUTION: The germicide composition comprises (A) a mono- or polyglycerin mono-fatty acid ester and (B) one or more kinds of chelating agents selected from the group consisting of an organic phosphonic acid-based chelating agent and a polymer-based chelating agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a bactericidal composition, and in particular, a bactericidal composition that has excellent bactericidal power and its durability, can maintain a stable bactericidal power even in the presence of various soils in the environment, and has excellent blending freedom. About.

  Chloric disinfectants such as sodium hypochlorite and oxygen-based disinfectants such as ozone and hydrogen peroxide, which are widely used for industrial hygiene management, show a significant decline in disinfecting power due to contamination with organic substances such as proteins. . This creates a difference in sterilization power between the experimental sterilization evaluation and the on-site sterilization evaluation, allowing the bacteria to grow and causing infection. As a countermeasure, the actual use concentration is specified as a concentration much higher than the sterilization concentration obtained in the experimental system. However, even if the concentration is high, even bacteria present in strong dirt cannot be sterilized, and the living body and environment. It is not preferable from the viewpoint of safety. There are few bactericides that take organic soils into account, and even if they exist, they are only for antibacterial and antiseptic purposes, and do not have enough bactericidal power to be used as bactericides.

Representative examples of agents that do not lose sterilization and antibacterial activity even during organic soiling include ethanol, polylysine, sugar ester, glycerin fatty acid ester and the like. Among them, glycerin fatty acid ester is a surfactant that is widely used for antiseptic purposes because it is highly safe and has high antibacterial properties and durability. However, there is a drawback that it does not have antibacterial properties against gram-negative bacteria (see Non-Patent Document 1). Therefore, ethylenediaminetetraacetic acid, which is a chelating agent having bactericidal activity against gram-negative bacteria, is used in combination to compensate for the disadvantages of glycerin fatty acid esters (see Patent Documents 1, 2, and 3).
"Science of antiseptic and bactericides", edited by John J. Kabbalah, translated by Koichi Yoshimura and Hirofumi Takigawa, Fragrance Journal, Inc. Published April 10, 1990, pages 249-263 JP-A-9-278610 Special table 2003-528820 gazette Japanese Patent Laid-Open No. 62-269673

  However, ethylenediaminetetraacetic acid reacts with hypochlorous acid or a salt thereof to reduce the effective chlorine concentration, resulting in a decrease in bactericidal power, and there is a problem in the degree of freedom of blending such that the combination of blending is limited. . There is a demand for a bactericidal agent that solves the above-mentioned problems and that has a high degree of freedom in blending and stably maintains high bactericidal power.

  An object of the present invention is to provide a novel bactericidal composition having a high bactericidal power even in the presence of dirt such as an organic substance and having an excellent blending degree.

  The present invention comprises (A) mono- or polyglycerin mono-fatty acid ester (hereinafter referred to as component (A)), and (B) one or more selected from the group consisting of organic phosphonic acid chelating agents and polymer chelating agents. The present invention relates to a bactericide composition containing a chelating agent (hereinafter referred to as component (B)).

  ADVANTAGE OF THE INVENTION According to this invention, the bactericide composition which has a high immediate effect bactericidal power with respect to Gram negative and positive bacteria, and shows a bactericidal effect continuously to the spore which Bacillus cereus etc. form is obtained. Such a high bactericidal effect is exhibited even in the presence of dirt such as organic matter.

  As the component (A), those having a degree of glycerol polymerization of 1 to 10 are preferable because suitable sterilizing power can be obtained. For example, monoglycerin monofatty acid ester, diglycerin monofatty acid ester, triglycerin monofatty acid ester, tetraglycerin monofatty acid ester, pentaglycerin monofatty acid ester, hexaglycerin monofatty acid ester, heptaglycerin monofatty acid ester, octaglycerin monofatty acid ester, Nonaglycerin monofatty acid ester, decaglycerin monofatty acid ester, a mixture thereof, or a mixture containing unreacted fatty acid and unreacted glycerin generated in the ester synthesis process. Preferably, the number of carbon atoms of the fatty acid is 8 to 12. For example, glycerin monocaprylate, glycerin monocaprynate, glycerin monolaurate, or a mixture thereof, or an unreacted fatty acid or unreacted glycerin generated in the ester synthesis process. The mixture containing is mentioned. Preferably, monoglycerol monolaurate, diglycerol monolaurate, or a mixture containing 25% or more of the total glycerol fatty acid ester weight is used.

  The composition of the present invention preferably contains 0.005 to 50% by weight, more preferably 0.1 to 10% by weight of component (A). The composition of the present invention is used after diluting with water or the like at the time of use. The concentration of the component (A) in the diluted solution (concentration at the time of use) is 0.0005 to 10% by weight, and further 0.0001. ˜1% by weight is preferred.

  The organic phosphonic acid chelating agent and polymer chelating agent of component (B) are any organic phosphonic acid chelating agent and polymer chelating agent as long as bactericidal power against Gram-negative bacteria can be obtained by combination with component (A). May be used.

  The organic phosphonic acid-based chelating agent refers to organic phosphonic acid and phosphonate. In addition to obtaining a suitable bactericidal power, not only adjusting the state of water but also imparting fat dispersibility. Such useful phosphonic acids include mono-, di-, tri- and tetraphosphonic acids which can also contain groups capable of forming anions under alkaline conditions such as carboxy, hydroxy, thio and the like. The phosphonic acid may comprise, for example, a low molecular weight phosphonopolycarboxylic acid having about 2 to 4 carboxylic acid moieties and about 1 to 3 phosphonic acid groups. Such acids include 1-phosphono-1-methylsuccinic acid, phosphonosuccinic acid and 2-phosphonobutane-2,2,4-tricarboxylic acid. Of these, aminotrimethylenesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, alkali metal salts thereof (for example, sodium or potassium), or partial salts are particularly preferred.

  The composition of the present invention preferably contains 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, of an organic phosphonic acid chelating agent as the component (B). The concentration of the organic phosphonic acid chelating agent in the diluting solution (concentration when in use) is preferably 0.0005 to 10% by weight, more preferably 0.0001 to 1% by weight.

  Polycarboxylic acid type polymers, sulfonic acid type polymers and the like are used as the polymer chelating agent capable of obtaining suitable bactericidal power, and polycarboxylic acid type polymers are preferred. As the polycarboxylic acid type polymer, polyacrylic acid, polymaleic acid, polymethacrylic acid, acrylic acid copolymer, maleic acid copolymer, and methacrylic acid copolymer (the copolymer may contain an amide bond) can be used. . More preferably, 1 type (s) or 2 or more types chosen from polyacrylic acid, a maleic acid type polymer (for example, polymaleic acid), and an acrylic acid-maleic acid copolymer are used. Some or all of these may be salts, and the salt is preferably an alkali metal salt such as sodium or potassium or an organic amine salt. The weight average molecular weight of polyacrylic acid is preferably 1,000 to 20,000, and particularly preferably 2,000 to 15,000. The maleic acid-based polymer is a maleic acid polymer, a copolymer with other monomers copolymerizable with maleic anhydride, or a water-soluble salt thereof, and has a structure represented by the following general formula (I): What has is preferable.

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, an alkoxy group, or a carboxyl group, and M represents a hydrogen atom or an alkali. It is a metal or an organic amine, x / y (molar ratio) = 1/10 to 10/1, and the weight average molecular weight is 1,000 to 100,000. ]

  In the above general formula (I), x / y (molar ratio) is 1/10 to 10/1, preferably 3/7 to 7/3. The weight average molecular weight of the maleic acid polymer represented by the formula (I) is 1,000 to 100,000, preferably 1,000 to 20,000. Among the polymers having the structure represented by the general formula (I), acrylic acid-maleic acid copolymers are preferable as the maleic acid copolymer.

  In order to obtain a suitable bactericidal power, it is desirable that the calcium chelate stability constant pKCa of a 1% by weight aqueous solution of the composition at 25 ° C. is 4.0 or more. The chelate stability constant is a standard indicating the strength of the binding force between the chelating agent and the metal. For the definition, see “Metal Chelate Compound (A.E.Martell, M. Calvin, Michio Kobayashi, Masatoshi Fujimoto, Kunihiko Mizumachi” Mainly for reference. pKCa is the negative logarithm of the equilibrium constant of the reaction between calcium and the carboxyl group of the chelating agent. The calcium chelate stability constant varies depending on the pH. At the above pH, the chelate stability constant is 4.0 or more.

The measuring method of pKCa is shown below. All the following measurements are performed at 25 ° C. 0.1 g of the bactericidal composition of the present invention is precisely weighed, MES buffer (pH 6.0 to 8.0), Tris-HCl buffer (pH 8.0 to 10.0) or NH ₄ Cl—NH ₄ OH A total of 100 g of aqueous solution is prepared with a buffer (pH 10.0 to 12.0). After inserting a calcium ion electrode into this aqueous solution, while stirring with a magnetic stirrer, an amount of CaCl ₂ aqueous solution (pH 6.0 to 12.0) corresponding to 20000 ppm in terms of CaCO ₃ was dropped, and calcium ion in the liquid was measured with an ion analyzer. Measure ions. Plot the relationship between appropriate quantity and residual calcium ion concentration, and find the inflection point.

  The composition of the present invention preferably contains 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, of a polymer chelating agent as the component (B). Further, the concentration of the polymer chelating agent in the diluted solution (concentration at the time of use) is preferably 0.0005 to 10% by weight, more preferably 0.001 to 1% by weight.

  In order to obtain a more suitable sterilizing power, it is preferable to adjust the pH. In the composition of the present invention, the pH of a 1% by weight aqueous solution of the composition at 25 ° C. is preferably 6 to 10, and more preferably 7 to 9. In order to achieve such pH, it is preferable to contain a pH adjuster [hereinafter referred to as component (C)] in the composition of the present invention. As the component (C), any acidic source or alkaline source may be used. It is preferable to combine them so as to have a buffering capacity and to stabilize them at a target pH.

  As the acid source used as the component (C), strong acids and various weak acids are used. Preferably, hydrochloric acid, acetic acid, tartaric acid, lactic acid, oxalic acid, citric acid, boric acid, phosphoric acid and succinic acid are used, and citric acid, boric acid and acetic acid are particularly preferred.

  In addition, as alkaline sources used as component (C), there are sodium and potassium chlorides, and useful ones include hydrochloride, silicate, hydroxide (sodium hydroxide, potassium hydroxide, etc.), carbonate Borate, phosphate, citrate, tartrate, lactate, acetate, succinate are particularly preferred.

  These acidic sources and alkaline sources used as the component (C) can be used singly or in combination of acidic sources, alkaline sources, or acidic sources and alkaline sources. To be elected.

  The composition of the present invention preferably contains 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, of a pH adjuster as the component (C). Moreover, the total concentration (concentration at the time of use) of the component (C) in the diluted solution can be used at 0.0001 to 20% by weight, and the diluted solution is adjusted to pH 6 to 10 within this range. More preferably, the component (C) is used at a total concentration of 0.001 to 10% by weight in the diluted solution and adjusted to pH 7 to 9.

  As a weight ratio of the preferable component (A) and component (B) for obtaining a suitable sterilizing power, (A) / (B) is 1/100 to 10/1, more preferably (A) / ( B) is 1/25 to 5/1. Moreover, as a preferable density | concentration in the dilution liquid at the time of use, the total density | concentration of (A) and (B) is 0.001 to 5 weight%, More preferably, it is 0.005 to 3 weight%.

  The weight ratio of the component (C) to the component (A) and the component (B) for obtaining a suitable sterilizing power is such that [(A) + (B)] / (C) is 1 / 10000-100 / 1, more preferably 1/1000 to 50/1.

  In order not to impair the effects of the present invention, (D) hypochlorous acid or a salt thereof (hereinafter referred to as “component (D)”) is used in order not to impair the effects of the present invention in order to give a high immediate effect bactericidal power to spores formed by Bacillus cereus May be.

  In the composition of the present invention, hypochlorous acid, or a sodium salt or potassium salt thereof can be used as the component (D). The composition of the present invention preferably contains 0.005 to 15% by weight, more preferably 0.1 to 10% by weight of component (D). Moreover, it is preferable to use at the density | concentration (concentration at the time of use) of (D) component in a dilution liquid at 0.0001 to 10 weight%, Furthermore, it is preferable to use at 0.0005 to 5 weight%.

  The weight ratio of the component (D), the component (A), the component (B), and the component (C) for obtaining an immediate bactericidal power against spores is [(A) + (B) + (C)] / (D) is preferably 1/100 to 500/1, more preferably 1/20 to 100/1.

  A major weakness of fungicides is that they easily react with organic substances such as proteins and lose their activity. Since the disinfectant composition of the present invention overcomes this weakness and has a broad disinfection spectrum, it is useful to be used in the food / food processing field where organic contamination is significant.

Examples 1-22, Comparative Examples 1-7
A fungicidal composition having the composition shown in Table 1 was prepared, and Escherichia coli NBRC3972 (hereinafter referred to as E. coli), Pseudomonas aeruginosa NBRC13275 (hereinafter referred to as Pseudomonas aeruginosa), Staphyllococcus aureus NBRC13276 (hereinafter referred to as Staphylococcus aureus) as test strains. ), Bacillus cereus ATCC9139 spores (hereinafter referred to as Bacillus cereus spores), and the bactericidal activity was measured by the following method.

The bactericidal composition is added to Luria-Bertani medium (hereinafter referred to as LB medium) so as to be diluted 100 times (hereinafter, the LB medium to which the bactericidal composition is added is referred to as LB test solution). Here, the composition of the LB medium is Tryptone peptone 10 g / l, Yeast Extract 5 g / l, NaCl 5 g / l, the balance is water, and the pH is 7.2. In order to evaluate the bactericidal power in the presence of organic soil, in this bactericidal test, the fungus and the bactericide composition are brought into contact in an LB medium which is a model of organic soil. Using a 10 ml plastic test tube, 100 μl of various bacterial solutions of 5.0 × 10 ⁸ CFU / ml are added to 5 ml of LB test solution, and the concentration of various bacteria is 1.0 × 10 ⁷ CFU / ml. A bacterial suspension LB test solution was obtained. The bacterial suspension LB test solution is shaken at 120 rpm at 25 ° C., and applied to a standard agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) at regular intervals, and the number of surviving bacteria (CFU / ml) is measured by colony counting did. The bactericidal effect is defined as follows.
Bactericidal effect (log reduction) = log ₁₀ (1.0 × 10 ⁷ / number of surviving bacteria after bactericidal treatment)
The results are shown in Table 1.

The components in the table are as follows.
Monoglycerin laurate: Sunsoft 750H [85% or more monoglycerol laurate, small amount of polyglycerol laurate; manufactured by Taiyo Kagaku Co., Ltd.]
Diglycerin laurate: Sunsoft Q-12D [manufactured by Taiyo Kagaku Co., Ltd.]
・ Organic phosphonic acid-based chelating agent (1): Diquest 2016 (sodium 1-hydroxyethylidene-1,1-diphosphonate; manufactured by Solusia Co., effective 30% by weight) has the concentration in the table in terms of effective content. Used as follows.
・ Organic phosphonic acid chelating agent (2): Diquest 2010 (1-hydroxyethylidene-1,1-diphosphonic acid; manufactured by Solusia, effective 60% by weight) so as to have the concentration in the table in terms of effective content. Used for.
Organic phosphonic acid-based chelating agent (3): Diquest 7000 (phosphonic acid tricarboxylic acid; manufactured by Sorcia Co., Ltd., effective 50% by weight) was used so as to have a concentration in the table in terms of effective content.
-Polymeric chelating agent (1): Socalane CP5 (acrylic acid-maleic acid copolymer; manufactured by BASF)
-Polymeric chelating agent (2): Socalane CP7 (acrylic acid-maleic acid copolymer; manufactured by BASF)
-Polymeric chelating agent (3): oligomer D [polyacrylic acid; manufactured by Kao Corporation]
Diglycolic acid: manufactured by Wako Pure Chemical Industries, Ltd.Acetic acid-sodium acetate: a buffer solution using glacial acetic acid and sodium acetate [both manufactured by Wako Pure Chemical Industries, Ltd.] The pH at the time of use of the disinfectant composition (pH of 1% by weight aqueous solution of the disinfectant composition at 25 ° C.) was adjusted to 5.5 or 8.0.

  From the results in Table 1, monoglycerin laurate and diglycerin laurate show bactericidal activity against Gram-positive bacteria such as Staphylococcus aureus and Bacillus cereus spores in the presence of a large amount of organic substances. By adding the organic phosphonic acid chelating agent Diquest 2016, Diquest 2010, Diquest 7000 or the polymer chelating agents Sokaran CP5, Sokaran CP7, and oligomer D to them, the sustained bactericidal power against Gram-positive bacteria Is increasing. Further, when the pH is raised to 8 by the component (C) (pH adjusting agent), if pKCa is 4.0 or more, immediate effects against Gram-negative bacteria such as Escherichia coli and Pseudomonas aeruginosa are obtained.

Examples 23-30, Comparative Examples 8-11
The fungicidal composition shown in Table 2 was prepared, and albumin was used as an organic soil model, and Escherichia coli NBRC3972 (hereinafter referred to as E. coli) and Bacillus cereus ATCC9139 spores (hereinafter referred to as Bacillus cereus) were used as test strains. In the measurement of bactericidal activity in Example 1, etc., except that 1% by weight albumin aqueous solution was used instead of the LB medium, the LB test solution was the albumin test solution, and the bacterial suspension LB test solution was the bacterial suspension albumin test. Bactericidal power was measured. The results are shown in Table 2.

  In order to confirm the degree of freedom of blending, the remaining sodium hypochlorite concentration in the albumin test solution was measured by the effective chlorine concentration. The potassium iodide titration method was used for measuring the effective chlorine concentration. The results are shown in Table 2.

The components in the table are as follows.
Monoglycerin laurate: Sunsoft 750H [85% or more monoglycerol laurate, small amount of polyglycerol laurate; manufactured by Taiyo Kagaku Co., Ltd.]
Diglycerin laurate: Sunsoft Q-12D [manufactured by Taiyo Kagaku Co., Ltd.]
・ Organic phosphonic acid-based chelating agent (1): Diquest 2016 (sodium 1-hydroxyethylidene-1,1-diphosphonate; manufactured by Solusia Co., effective 30% by weight) has the concentration in the table in terms of effective content. Used as follows.
-Polymeric chelating agent (1): Socalane CP5 (acrylic acid-maleic acid copolymer; manufactured by BASF)
EDTA-2Na: Clewat N [ethylenediaminetetraacetic acid disodium; manufactured by Teikoku Chemical Industry Co., Ltd.]
・ Sodium hypochlorite: manufactured by Nankai Chemical Co., Ltd. ・ Albumin: bovine serum albumin (BSA, manufactured by Sigma-Aldrich)
-Acetic acid-sodium acetate: A buffer solution using glacial acetic acid and sodium acetate (both manufactured by Wako Pure Chemical Industries, Ltd.), and changing the ratio of both, the pH at the time of use of the disinfectant composition (at 25 ° C The pH of a 1% by weight aqueous solution of the fungicide composition was adjusted to 5.5 or 8.0.

  From the results in Table 2, it can be seen that when EDTA-2Na is used as the chelating agent, the sodium hypochlorite concentration is immediately decomposed. On the other hand, by using an organic phosphonic acid chelating agent or a polymer chelating agent, the effective chlorine concentration is kept stable without reacting even in the presence of highly reactive sodium hypochlorite. When albumin was added thereto, in Examples 23 to 30, a 4-digit bactericidal effect was observed after 1 minute of bactericidal treatment, and an immediate bactericidal power against spores by adding sodium hypochlorite could be confirmed.

Claims (7)

  A disinfectant composition containing (A) mono- or polyglycerin mono-fatty acid ester, and (B) one or more chelating agents selected from the group consisting of organic phosphonic acid chelating agents and polymer chelating agents.   The disinfectant composition according to claim 1, further comprising (C) a pH adjuster.   The fungicidal composition according to claim 1 or 2, further comprising (D) hypochlorous acid or a salt thereof.   The disinfectant composition according to any one of claims 1 to 3, wherein (A) has a glycerol polymerization degree of 1 to 10 and a fatty acid carbon number of 8 to 12.   The disinfectant composition according to any one of claims 1 to 4, wherein the pH of the 1 wt% aqueous solution of the composition at 25 ° C is 6 to 10.   The fungicidal composition according to any one of claims 1 to 5, wherein a calcium chelate stability constant (pKCa) of a 1 wt% aqueous solution of the composition at 25 ° C is 4.0 or more.   The disinfectant composition according to any one of claims 1 to 6, which is used for food or food processing equipment.