JP2005075873A - Treating agent for biofilm - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent which is used for treating biofilms, can simply and efficiently remove the biofilms, has good storage stability, and further has a film adhesion-preventing effect. <P>SOLUTION: This biofilm-treating agent is characterized by comprising (a) 0.5 to 3 mass % of an alkali metal hypochlorite, (b) 0.01 to 0.6 mass % of an alkali metal hydroxide, and (c) 0.1 to 5 mass % of one or more surfactants selected from the group consisting of tertiary alkylamine oxides, alkyl sulfates, alkylbenzenesulfonates, polyoxyethylene alkyl ether sulfates and fatty acid alkali metal salts, wherein the (a)/(b) mass ratio of the component (a) / the component (b) is ≥2. The treating agent for biofilms can simply and efficiently remove the biofilms, has good storage stability, and further has a biofilm adhesion-preventing effect. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a treatment agent for removing a biofilm generated in a bathroom, kitchen, washroom, toilet or the like and preventing biofilm adhesion.

In recent years, buildings with high airtightness and excellent moisture retention have become widespread in single-family houses as well as apartment houses such as apartments due to the extensive use of aluminum sashes and heat insulating materials.
On the other hand, with the improvement of people's living standards, the concept of amenity, that is, “comfort” has spread, and the consciousness of living as cleanly and comfortably as possible in a limited living space has increased. Reflecting these changes in residents' consciousness, slimy biofilms that are generated around bathrooms, kitchens, washrooms, and toilets, which are particularly humid, are regarded as problems. There is an increasing number of cases where residents feel uncomfortable due to the appearance and feel of such biofilms and bring consultations to insurance institutions and management companies as complaints.

  At present, the scientific definition of biofilm is not clear, but bacteria attached to the surface form microcolonies composed of polysaccharides, sometimes including microalgae and protozoa, which interact in complex ways It is regarded as a “place of life” for microorganisms. In homes, bacteria are attached to bathroom tiles, and the attached bacteria are expected to grow and expand while producing viscous substances, growing under high temperature and humidity conditions using organic matter such as human dirt and soap. The In addition, many of the main constituent bacteria are non-aqueous or water-soluble pale red, yellow, yellow-green, green, brown and other chromogenic bacteria, and often exhibit these colors.

  As a method for removing such a biofilm, a method for removing mainly using mandelic acid as a bactericidal agent (see Patent Document 1: Japanese Patent Publication No. 10-511999), a biofilm such as a chelating agent in addition to mandelic acid, etc. A composition having an agent capable of moving a divalent cation existing in the structure (Patent Document 2: Japanese Translation of PCT International Publication No. 2002-529545) has been proposed. In addition, a treatment method utilizing an enzyme has been proposed (Patent Document 3: Japanese Translation of PCT International Publication No. 2001-508677). However, in some cases, it takes a certain amount of time to exhibit the effect in actual use, or a sufficient effect may not be obtained under the use conditions.

  On the other hand, countermeasures for removing microorganisms such as fungi have been proposed for the purpose of removing dirt and sterilizing and fungicidal effects. As such a method, the effect of sterilization and stain prevention by a polymer having a quaternary ammonium group and a bleaching agent is described (Patent Document 4: Japanese Patent Laid-Open No. 2002-161298). In the scene, the agent runs down and it is difficult to expect the durability of the effect. On the other hand, an installation type antifouling molded article containing an inclusion compound composed of an antibacterial agent and a multimolecular host compound and a specific base material has been proposed (Patent Document 5: JP 2001-65020 A). In this method, although it is considered that the effect can be exhibited at a specific place such as a drainage structure, it is not possible to cover all the water surroundings where biofilms may be generated. Moreover, once a biofilm is formed, it is not easy to remove the viscous substance, which is a polysaccharide produced from bacteria, by simply rinsing with water or rubbing.

  From the above, there has been a demand for a biofilm treatment agent that can remove biofilms adhering to various places, has good storage stability, and has an effect of preventing biofilm adhesion.

Japanese National Patent Publication No. 10-511999 Special table 2002-529545 gazette JP-T-2001-508677 JP 2002-161298 A JP 2001-65020 A JP 2002-69494 A Hisao Morisaki, “Biofilm”, Science Forum, Inc., April 10, 2000, p116-120

  The present invention has been made in view of the above circumstances, and provides a treatment agent for a biofilm that can easily and efficiently remove a biofilm, has good storage stability, and has an effect of preventing the adhesion of a biofilm. Objective.

  As a result of intensive studies to achieve the above object, the present inventor has formulated the composition comprising an alkali metal hypochlorite salt, an alkali metal hydroxide, and a predetermined surfactant in a specific amount, whereby It has been found that the object can be achieved, and the present invention has been made.

Accordingly, the present invention provides (I) (a) alkali metal hypochlorite 0.5 to 3% by mass.
(B) Alkali metal hydroxide 0.01-0.6 mass%
(C) One or more surfactants selected from the group consisting of tertiary alkylamine oxides, alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates and fatty acid alkali metal salts 0.1 ~ 5% by mass
And a mass ratio (a) / (b) of the component (a) to the component (b) is 2 or more.
(II) Furthermore, (d) 0.01-15 mass% of inorganic buffer agents which pKa consists of 9 or more are mix | blended, The biofilm processing agent as described in (I) characterized by the above-mentioned.
(III) Further, (e) 1-menthol, menthyl acetate, menthone, isomentone, sapinene hydrate, isopulegol, piperitol, d-camphor, 1,8-cinerol, capsaicin derivative, isothiocyanbutyl, allyl isothiocyanate, alkaloid, (I) or (II) description characterized by comprising one or more compounds selected from the group consisting of pepicine, chapicin, chloroacetophenone, o-chlorobenzylidenemalononitrile, brucine and chloropicrin Biofilm treatment agent.
(IV) The biofilm treatment agent according to claim 3, wherein the amount of component (e) is 0.0005 to 1% by mass.
(V) The biofilm processing agent formed by filling the biofilm processing agent in any one of (I)-(IV) into a spray container.
I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the biofilm processing agent which can remove a biofilm simply and efficiently, has the favorable storage stability, and also has the adhesion prevention effect of a biofilm can be provided.

Hereinafter, the present invention will be described in more detail.
The component (a) of the present invention is an alkali metal hypochlorite and is not particularly limited, and examples thereof include sodium hypochlorite and potassium hypochlorite. These can be used alone or in appropriate combination of two or more. Among these, sodium hypochlorite is preferable.

  (A) The compounding quantity of a component is 0.5-3 mass% in a biofilm processing agent, Preferably it is 1.0-2.5 mass%. If the blending amount is less than 0.5% by mass, it is not possible to obtain a sufficient biofilm removal effect, and there is no particular upper limit on the upper limit. You may feel a strong chlorine odor.

  The component (b) of the present invention is an alkali metal hydroxide and is not particularly limited. Specific examples of the alkali metal hydroxide that can be blended in the biofilm treating agent of the present invention include sodium hydroxide and potassium hydroxide. These can be used singly or in appropriate combination of two or more, among which sodium hydroxide is preferred.

  (B) The compounding quantity of a component is 0.01-0.6 mass% in a biofilm processing agent, Preferably it is 0.01-0.4 mass%. (A) In consideration of the stability of the alkali metal hypochlorite, 0.01% by mass or more is necessary, and when it exceeds 0.6% by mass, the removability of the biofilm in a short time is remarkably lowered. Normally, industrially available (a) alkali metal hypochlorite stabilizes alkali metal hypochlorite by making it strongly alkaline at about pH 13, and therefore a small amount of It is supplied in the form of an aqueous solution containing an alkali metal hydroxide, and the bleaching agent using the same necessarily contains an alkali metal hydroxide. Therefore, in this invention, the compounding quantity of (b) component shall contain content of the alkali metal hydroxide mixed in the hypochlorite alkali metal salt. Further, when NaOH is neutralized by the added substance, the amount is reduced from the content.

The mass ratio (a) / (b) between the component (a) and the component (b) is 2 or more, preferably 3 or more.
If this mass ratio is less than 2, the removal speed of the biofilm is slow, and an efficient removal force cannot be obtained. The upper limit of the mass ratio is not particularly limited, but is usually 200.

  The component (c) of the present invention is one or more selected from the group consisting of tertiary alkylamine oxides, alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates and fatty acid alkali metal salts. It is a surfactant. The component (c) must be a component that does not impair the stability of the alkali metal hypochlorite of the component (a), and has a structure or functional group such as a hydroxyl group, a double bond, or betaine in the molecule. An activator or the like that does not contain is suitable.

Examples of the tertiary alkylamine oxide include tertiary alkylamine oxides represented by the following general formula (1).
R ¹ R ² R ³ N → O (1)
(In the formula, R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, and R ² and R ³ are preferably linear or branched alkyl groups having 1 to 3 carbon atoms.)

In the general formula (1), R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, and is derived from, for example, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and a natural product. And a mixture of alkyl groups having different carbon numbers. In these, the dodecyl group and the alkyl group derived from coconut oil are preferable. R ² and R ³ are linear or branched, preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.

  Specific examples of the tertiary alkylamine oxide represented by the general formula (1) include coconut oil dimethylamine oxide, lauryl dimethylamine oxide, and the like.

Examples of the alkyl sulfate include alkyl sulfates represented by the following general formula (2).
R ⁴ -OSO ₃ M (2)
(Wherein R ⁴ is an alkyl or alkenyl group having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, and M is a cation.)

Examples of the alkyl benzene sulfonate include linear alkyl benzene sulfonate represented by the following general formula (3).
R ⁵ — (C ₆ H ₄ ) —SO ₃ M (3)
(In the formula, R ⁵ is an alkyl group having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms, and M is a cation.)

  Specific examples of the linear alkyl benzene sulfonate represented by the general formula (3) include sodium lauryl benzene sulfonate.

Examples of the polyoxyethylene alkyl ether sulfate include polyoxyethylene alkyl ether sulfate represented by the following general formula (4).
R ⁶ — (CH ₂ CH ₂ O) _n —SO ₃ M (4)
(Wherein R ⁶ is a monovalent hydrocarbon group of 8 to 18, preferably 12 to 15, M is a cation, n is a mixture of 1 to 7 and includes those in which n exceeds 7. May be.)

Examples of the fatty acid alkali metal salt include fatty acid alkali metal salts represented by the following general formula (5).
R ⁷ COOM (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group having 7 to 17 carbon atoms, preferably 11 to 17 carbon atoms.)

  (C) The compounding quantity of surfactant of a component is 0.1-5 mass% in a biofilm processing agent, Preferably it is 0.2-3 mass%. If the blending amount is less than 0.1% by mass, sufficient detergency cannot be obtained, and even if the amount exceeds 5% by mass, improvement in detergency cannot be expected.

  In the biofilm treatment agent of the present invention, pKa is a system in which the stability of the alkali metal hypochlorite salt of the component (a) is improved in a system with less alkali metal hydroxide of the component (b). It is preferable to blend an inorganic buffer that has 9 or more. In addition, pKa of this invention is a value in 25 degreeC.

  As such an inorganic buffer, for example, one or more selected from carbonic acid, phosphoric acid, diphosphoric acid, tripolyphosphoric acid, silicic acid, and alkali metal salts thereof can be used in appropriate combination. Note that it is not necessary to replace all of the hydrogen ions of the oxoacid with alkali metal ions. For example, in the case of sodium salt of phosphoric acid, use any of monosodium phosphate, disodium phosphate, and trisodium phosphate. Can do.

  (D) The compounding quantity of the inorganic buffer of a component is 0.01-15 mass% in a biofilm processing agent, Preferably it is 0.03-5 mass%. If the amount of the inorganic buffer is too small, the decomposition of the alkali metal hypochlorite of component (a) proceeds during storage of the biofilm treatment agent. As a result, the alkali metal hypochlorite required for washing after storage. The salt is insufficient and sufficient detergency cannot be obtained. If the amount is too large, further improvement in stability cannot be expected, and precipitation and precipitation of the inorganic buffering agent are likely to occur during storage. The blending amount of the inorganic buffering agent (d) includes (b) a neutralized product of alkali metal hydroxide.

  In addition, the biofilm treatment agent of the present invention contains (e) l-menthol, from the viewpoint of blending a component that suppresses biofilm removal and biofilm generation and adhesion in order to reduce the on-site processing effort. Menthyl acetate, menthone, isomenton, sapinene hydrate, isopulegol, piperitol, d-camphor, 1,8-cinerol, capsaicin derivative, isothiocyanbutyl, allyl isothiocyanate, alkaloid, pepicine, chapicin, chloroacetophenone, o-chlorobenzylidenemalono It is preferable to blend one or more compounds selected from the group consisting of nitrile, brucine and chloropicrin. Among these, l-menthol, capsaicin, and allyl isothiocyanate are preferable. These ingredients induce tears but are highly safe.

  (E) The compounding quantity of a component is 0.0005-1 mass% in a biofilm processing agent, Preferably it is 0.005-0.8 mass%. If the amount is less than 0.0005% by mass, a sufficient biofilm suppressing effect cannot be obtained. On the other hand, the upper limit is not particularly limited, but even if it exceeds 1% by mass and an excessive amount is blended, a special biofilm production suppressing effect cannot be obtained.

  The biofilm treatment agent of the present invention is an antibacterial agent such as benzalkonium chloride, a solvent, a metal ion scavenger, a water-soluble high-concentration compound that is blended in an ordinary bleaching detergent composition to the extent that the intended function is not impaired. Components such as molecules, thickeners such as clay minerals, coloring agents, inorganic salts, and fragrances can be blended.

  The biofilm treatment agent of the present invention can be prepared based on a conventional method, and the pH is preferably in the range of 10 to 14, particularly 10.5 to 13. In addition, the biofilm treatment agent of the present invention is not particularly limited in its dosage form and method of use, but it is prepared as a liquid biofilm treatment agent and is in a liquid or foam form and adheres to the target. It is preferable that In particular, it is preferable to fill the spray container from the viewpoint of simplicity. The spray container includes a discharge device that discharges the biofilm treatment agent, and the discharge device has a sliding portion such as a piston or a cylinder or a fitting portion such as a liquid passage for the pump housing. For example, it can be used without any particular limitation. Examples of spray containers include trigger sprayers.

  The biofilm treatment agent of the present invention is a treatment agent that removes biofilm generated in a bathroom, kitchen, toilet, toilet, etc. and prevents biofilm adhesion. In particular, it is suitable as a treatment agent in the vicinity of the joints of bathrooms and tiles, the bottom of a dish drainer installed in the kitchen, the drain outlet of a wash basin, a place where water is slightly accumulated in a toilet, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition represents mass%, and the ratio represents mass ratio.

[Examples 1-9, Comparative Examples 1-5]
Biofilm treatment agents having the compositions shown in Tables 1 and 2 were prepared according to a conventional method, filled in a light-shielded polyethylene container, and removed by the following method, biofilm removal ability, storage stability (residual rate of sodium hypochlorite) ) Was evaluated. The results are shown in Tables 1 and 2.

Content of the component in a biofilm processing agent was obtained with the following method.
(A) Sodium hypochlorite content The sodium hypochlorite content was determined by the effective chlorine concentration determined by the iodometry method.
(B) Sodium hydroxide (NaOH) content Neutral hydrogen peroxide aqueous solution was added to the raw material sodium hypochlorite aqueous solution to decompose sodium hypochlorite and titrated with hydrochloric acid using phenolphthalein as an indicator. The NaOH concentration in the sodium hypochlorite aqueous solution used as a raw material was calculated. The NaOH concentration in the liquid bleach composition is calculated by calculating the amount of NaOH brought in from the amount of raw material used. If NaOH is added, the amount is added, and the added material further neutralizes the NaOH. If so, it was calculated by subtracting the amount.
(D) Inorganic buffer concentration The salt produced by neutralization was also included in the concentration.

Biofilm removal power evaluation method Biofilm preparation method Biofilms with dark brown color collected from a sink installed in a home kitchen are collected, diluted with water, dispersed, dispensed into microplates in 50 μL aliquots, and centrifuged at 3000 rpm for 10 minutes. The supernatant was discarded and used as an evaluation sample.
2. Biofilm removal power 50 μL of each biofilm treatment agent was injected into each hole of the microplate, and the color of the biofilm after 15 minutes was visually evaluated based on the following criteria.
<Evaluation criteria>
1 point: dark brown (equivalent to initial)
2 points: brown 3 points: yellow to light yellow 4 points: light yellow 5 points: transparent

Storage stability (residual rate of sodium hypochlorite) Evaluation method As an accelerated test, a light-shielded polyethylene container is filled with a biofilm treatment agent, stored at 40 ° C. for 1 month, and then hypochlorous acid in each treatment agent. The concentration of the acid alkali metal salt was titrated with a sodium thiosulfate solution using a fully automatic titrator (Hiranuma Sangyo Co., Ltd .: TS-980) and reacted with potassium iodide and acetic acid. This concentration was defined as the residual rate of alkali metal hypochlorite with respect to the initial concentration, and was determined according to the following evaluation criteria.
<Evaluation criteria>
A: Residual rate of alkali metal hypochlorite 60 to 100%
○: Residual rate of alkali metal hypochlorite 40 to less than 60% ×: Residual rate of alkali metal hypochlorite 0 to less than 40%

＊２５℃におけるｐＫａ値は、リン酸（オルトリン酸）は３段解離し、第３段のｐＫａは１２．３５、同様に炭酸は２段で第２段のｐＫａは１０．３３である。

* The pKa value at 25 ° C. is that phosphoric acid (orthophosphoric acid) is dissociated in three steps, the third step pKa is 12.35, similarly the carbonic acid is two steps and the second step pKa is 10.33.

Anti-adhesion effect of biofilm The biofilm treatment agent of Examples 6 to 9 on a half surface of a household strainer, and the composition obtained by removing the component (e) from Examples 6 to 9 as a reference example on the other side After spraying 25g, lightly rinse, install, and determine the occurrence of biofilm after one month of use at the kitchen drainage of 4 households, visually determine the generation area in the total area, and the average of 4 households evaluated. The results are shown in Table 3.

Claims (5)

(A) Alkali metal hypochlorite 0.5-3 mass%
(B) Alkali metal hydroxide 0.01-0.6 mass%
(C) One or more surfactants selected from the group consisting of tertiary alkylamine oxides, alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates and fatty acid alkali metal salts 0.1 ~ 5% by mass
And a mass ratio (a) / (b) of the component (a) to the component (b) is 2 or more.   Furthermore, (d) 0.01-15 mass% of inorganic buffer agents which pKa consists of 9 or more are mix | blended, The biofilm processing agent of Claim 1 characterized by the above-mentioned.   Further, (e) l-menthol, menthyl acetate, menthone, isomentone, sapinene hydrate, isopulegol, piperitol, d-camphor, 1,8-cinerol, capsaicin derivative, isothiocyanbutyl, allyl isothiocyanate, alkaloid, pepicine, chapicine A biofilm treatment agent according to claim 1 or 2, comprising one or more compounds selected from the group consisting of chloroacetophenone, o-chlorobenzylidenemalononitrile, brucine and chloropicrin. .   4. The biofilm treatment agent according to claim 3, wherein the amount of component (e) is 0.0005 to 1% by mass. The biofilm processing agent formed by filling the biofilm processing agent of any one of Claims 1-4 in a spray container.