TW201206342A - Antibacterial agent - Google Patents

Abstract

Provided is an antibacterial agent which is useful for the removal of pink mold produced in the living environments. The antibacterial agent is obtained by combining a quaternary ammonium salt that is described as the component (A) below and an organic solvent that is described as the component (B) below. (A) One or more quaternary ammonium salts selected from among dialkyl dimethyl ammonium salts and alkyl benzyl dimethyl ammonium salts. (B) One or more organic solvents selected from among aromatic alcohols, aromatic aldehydes and the compounds represented by formulae (1) and (2) (wherein R represents an alkyl group or alkenyl group having 5-10 carbon atoms or a benzyl group; A represents an alkylene group having 1-10 carbon atoms; and n represents a number of 0-5 and the n-numbered A groups may be the same or different).

Description

201206342 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] - The present invention relates to an antibacterial agent useful for preventing adhesion and removing pink scale in the anti-storied living environment. [Prior Art] - In recent years, the demand for keeping the living environment of homes, workplaces, and public facilities more conservative has been gradually increased. On the other hand, however, buildings in recent years, especially in office buildings or high-rise apartments in cities, tend to be dense and easy to accumulate moisture, so they are in an environment where microorganisms such as bacteria or molds are easily propagated. Especially in so-called water use places such as toilets, bathrooms, washrooms, kitchens, etc., microorganisms are more easily propagated due to conditions such as moisture or moisture or temperature. One of the significant stains in a living environment such as a water use place is a pink stain represented by an adherent or mucus which is reddish in red or pink. Pink dirt is particularly noticeable on the bottom of containers such as drains, gaskets, faucets, bathroom floors, ◎ washbasins or shampoo bottles. In addition, since the pink stain is regenerated immediately even if it is cleaned, it is a troublesome dirt for the sweeper. In addition, the pink stain is not only difficult to remove, but also causes a feeling of discomfort to the user of the water use place due to the sense of dissimilarity caused by the sticky feeling and the appearance. It is expected to develop a method of effectively removing pink dirt and keeping it clean in the water. As a fungus isolated from pink soil, RhRd〇t〇rula (erythr yeast) genus yeast, Methylobacteriurn (methyl bacillus) bacterium, BreVUndimonas (Bacillus vesicularis) bacterium, Micr〇bacterium 157492 were reported. .doc 201206342 (Microbacterium) is a bacterium, etc. (patent literature 非, non-patent literature υ. Among them, Rhodotorula genus yeast has a faster proliferation rate than other strains, so it is considered to be the main cause of pink soil (Patent Document 1) In addition, as an antibacterial activity against the Rhodotoruia genus, and effective in inhibiting mucus, it is reported that there are silver-based, zinc-based, Chin-based, and copper-based antibacterial metals. Surfactant-based antibacterial agents such as a sulfonium salt, a di-sinter-di-f-salt salt, a sulphur-salted ammonium salt, an imide (tetra) salt, etc. (Patent Document 丄). ,,,: and there is no such thing as pink In the case of the bacteria of the genus Methylobacterium, the report of the removal of the pink scale is discussed from the viewpoint of suppressing the growth of the bacterium. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Patent No. 20064519 Publication No. 8 [Non-Patent Document] [Non-Patent Document 1] Science of Washing, 2〇〇7, η卷4号, 16~22 pages [Invention] The present invention is the following invention. It is obtained by combining the quaternary ammonium salt represented by the following component (A) and the organic solvent represented by (B): (A) selected from a dialkyl dimethyl ammonium salt and an alkyl benzyl dimethyl ammonium salt One or more quaternary ammonium salts; (B) one or more organic solvents selected from the group consisting of aromatic alcohols, aromatic aldehydes, and compounds represented by the following formulas (1) and (2); [Chem. 1] 157492.doc 201206342 ho-^ao-^r (1) ohc^ao^r (2) [wherein R represents a hospital base or a gynecological base or a base group with a carbon number of 5 to 1 ,, and A represents a carbon number of 1 to 1 G. The stretching base, η represents the number of 〇~5, which may be the same or different. 2) An antibacterial agent composition containing the above antibacterial agent.

3) A method for preventing pink dirt from adhering or removing pink scale, characterized in that the above-mentioned antibacterial agent or antibacterial agent composition is used in a place where microbial contamination is likely to occur. The use of an antibacterial agent which is obtained by combining an quaternary ammonium salt of the following components (Α) and an organic solvent represented by (Β): (Α) is selected from the group consisting of dialkyldicylidene ammonium salts and a quaternary salt of one or more kinds of alkylbenzyldimethylammonium salts; (Β) an organic compound selected from the group consisting of aromatic alcohols, aromatic aldehydes, and compounds represented by the following formulas (1) and (2) Solvent; [Chemical 2] HO-jAO^R d) OHC-^AO^R (2) [wherein, R represents an alkyl or alkenyl group having a carbon number of 5 to 10, or a benzyl group, and A represents a stone anastomosis It is a stretching base of 1 to 1 Torr, η represents the number of 04, and η A may be the same or different. 5) - the use of a combination of the quaternary ammonium salt of the following component (A) and the organic solvent of 157492.doc 201206342 as shown in (B) for the manufacture of an antibacterial agent: (A) selected from a dialkyl group One or more quaternary ammonium salts of a dimethylammonium salt and an alkylbenzyldimethylammonium salt; (B) one or more selected from the group consisting of an aromatic alcohol, an aromatic aldehyde, and a compound represented by the following formulas (1) and (7); Organic solvent; 化0_(Α0)ϊΓρ (1) OHC-^AO^pR (2) [wherein R represents an alkyl or alkenyl group having a carbon number of 5 to 1 Å, or a benzyl group, A represents an alkylene group having a carbon number of 1 to 10, and n represents a number of 〇~5, and "solid eight may be the same or different". 6) An antibacterial method characterized by combining the following components (Α) The fourth-order ammonium salt and the organic solvent shown by (Β) are used: (Α) one or more kinds of four-stage i-ampere salts selected from the group consisting of dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt; One or more organic solvents selected from the group consisting of aromatic alcohols, aromatic aldehydes, and compounds represented by the following formulas (1) and (2); [Chemical 4] H0~(A0)irR (1) OHC^AO^R ( 2) wherein R represents an alkyl or alkenyl group having a carbon number of 5 to 1 Å, or Benzyl, A represents 157492.doc 201206342 Alkene with a carbon number of 1 to 10, n represents the number of 〇~5, 11 can be the same, different]. [Embodiment.] • · · · - . The present invention relates to an antibacterial agent composition useful for preventing pink stain adhesion caused by a hard surface in a living environment, particularly a toilet, a room, a kitchen, etc., and for removing pink scale. The present inventors use Scanning electron microscope (SEM, Scanning 0 Electr〇n Microscope) or a common-focus laser microscope (CLSM,

Confocal Laser Scanning Microscope) analyzed the actual pink stain and found that the main cause of pink stain was not the previously known Rhodotorula genus, but the Methyl 〇bacterium genus. Further, it has been studied for a component which can effectively inhibit or prevent the growth of bacteria of the genus Methylobacterium, and as a result, it has been found that when a specific quaternary ammonium salt is used in combination with an organic solvent, it exerts excellent antibacterial activity against bacteria of the genus Methyl 〇bacterium, It is useful to remove pink dirt.抗菌 The antibacterial agent according to the present invention can be used for sterilization and anti-sweat of the hard surface when used in a living environment, especially a wall of a kitchen or a cold room, a toilet, a washstand, or a hard surface such as a floor device or a machine. Specifically, it is possible to prevent pink dirt from adhering and to easily remove the adhered pink dirt. In the present invention, a dialkyl dimethyl sulphate as a component of a quaternary ammonium salt and a decyl ketone ketone salt are known as antibacterial cationic interfacial surfactants. In the present invention, 'as a dialkyl dimethyl ammonium salt and a dimethyl sulphate salt' are preferably exemplified by a dialkyl group ((: 8_18) dimethyl ammonium salt, a calcination group 157492.doc 201206342 (c8_18) dimethylammonium salt. Here, examples of the alkyl group include a linear alkyl group having a carbon number of 8 to 18, such as an octyl group, an anthracenyl group, a decyl group (lauryl group), and fourteen. A base (soybean base), a base (recording base), a heptadecyl group, an octadecyl group (stearyl group), preferably an octyl group, a decyl group, a dodecyl group. The dialkyl dimethyl ammonium salt is exemplified by a dimercaptodimethylammonium salt, and as the ketone ketone dimethyl ketone salt, an octyl stilbene dimercapto ketone salt and a dodecyl benzyl group are mentioned. a bismuthyl ammonium salt or the like. The salt may be a salt with F-, cr, Br., m^pN〇.qs〇42, etc., preferably a salt with a halide ion, more preferably a chloride. Ionic salt. Octylbenzyl dimethyl vaporized monodecyl dimethyl vaporized ammonium as a more preferred quaternary ammonium salt, and examples thereof include ammonium, dodecylbenzyldimethylammonium chloride, and the like. The quaternary ammonium salt of the component (A) of the present invention can be used. For the method of manufacture, a commercially available product can also be used. For example, Quartamin m〇 (manufactured by Kao Co., Ltd.) can be purchased as a dicalcinyl dimethyl salt to be used as a base for the production of 08 Samsol C (manufactured by Kao Co., Ltd.). The quaternary dimethyl sulfonium salt of the present invention is used. It is known that the quaternary salt of the present invention has excellent antibacterial activity against bacteria and the like when used alone. However, as shown in the later embodiment, E.coli (E. coli), S. read eus (staphylococcus aureus), p-cafe (four) (Pseudomonas aeruginosa) showed sufficient antibacterial concentration, and it was not shown to the Methylobacterium genus.昂, 田囷 showed no anti-halogen activity. If it is not used at a concentration of more than 1〇 times 157492.doc 201206342 for a contact time of 30 minutes or more, it is impossible to confirm the reduction of the number of bacteria in the cockroach. That is, the bacteria of Methyl〇bacterium are identified. For this: the resistance to salt recording is very high. 于 In this case, 'the combination of the four (4) and the organic solvent of the component (8) is found to be significantly improved. The combination of the above components (4) is due to & Level 4 (four) __ An antibacterial agent prepared by using one or more organic solvents of the component (B) as an antibacterial agent for inhibiting (inhibiting) or preventing (sterilizing) growth of a microorganism containing a bacterium belonging to the genus Methyl 〇baeterium, or for preventing life Antibacterials in which pink dirt adheres to or removes pink dirt in the environment. The term "living environment" includes all environments in which a living person or animal exists, such as a family, a workplace, a school, a public facility, etc., preferably The environment with more moisture and the tendency to produce pink dirt can be found in the so-called water use places, drinking fountains, swimming pools, washing equipment, and other plumbing equipment such as bathrooms, washrooms, washrooms, toilets or Weifang. More specifically, the wall or floor of the kitchen or bathroom, toilet, washstand, etc., the bottom of the washbasin, the bottom of the bottle such as shampoo, the drain, the faucet, and the draught in the toilet. A hard surface such as a wire. Further, the term "pink stain" refers to a microbial-derived soil which is microscopically represented by a deposit or a mucus. Here, the reddish color 'containing red' pink, or the intermediate color, for example, may also be the color having the maximum absorption wavelength near 490 nm ("the sticky substance produced in a living environment such as a bathroom", anti-bacterial prevention Ν〇ι, Μ』. 11 5 ρ. 723-728, 1996)° ' . 157492.doc 201206342 Among the organic solvents of the knives (B), as the aromatic alcohol, preferably benzyl alcohol, benzyl Ethoxyethanol, phenoxyethanol, and 1-phenoxy-2-propanol are more preferred to be alcoholic. As the aromatic aldehyde, benzaldehyde, phenylacetaldehyde, 4-methylbenzaldehyde, 2-phenylpropanal or the like is preferable, and among them, benzaldehyde or phenylacetaldehyde is more preferable. The super group compound represented by 弋(), the acid compound represented by the formula (2), and the alkylene group having a carbon number of 1 to 10, preferably a carbon number of 2 or 3. base. The alkyl group or the dilute group having a carbon number of 5 to 10 represented by R may be either a straight chain or a branched chain, but is preferably an alkyl group having a carbon number of 5 to 8, and for example, n-butyl Base, n-hexyl, 2-ethylhexyl and the like. It is 0 3, preferably! 〜3, and further preferably ^ or 2. Furthermore, η A's may be the same or different. Preferred examples of the organic solvent of the component (B) include benzyl alcohol, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, and 2-(2-ethylhexyloxy)ethanol. Ethylene glycol mono-n-butyl ether, diethylene glycol monohexyl ether ' 2 gas oxime (2-ethylhexyloxy) ethoxy] ethanol, 2-benzyloxyethanol, 2-phenoxyethanol, stupid formaldehyde Benzene, 4_mercaptobenzaldehyde, 2-phenylpropanal, hexanal, 2-ethylbutyraldehyde, diethylene glycol monohexyl ether, pentanol, hydrazine-phenoxypropane, and the like. Therefore, 'as a preferred combination of the component (A) and the component (b), the case where the component (A) is selected from the group consisting of octylbenzyldimethylammonium chloride and dodecyl-benzyldimethyl One or more of vaporized ammonium and dimercaptodifluorenyl ammonium sulfate, the soil (B) is selected from the group consisting of benzyl alcohol, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, and 157492.doc -10- 201206342 (2-ethylhexyloxy)ethanol, diethylene glycol mono-n-top, diethylene glycol ether, 2-ethylhexyloxy)ethoxy]ethanol, 2_ethoxyethanol, 2 Milk-based ethanol, benzaldehyde, stupid acetylene, boat, ρ, 甲 丞 甲醛 甲醛 甲醛 、 、 、 、 、 、 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛 甲醛- one or more of phenanthrenyl-2-propanol; the component (Α) is selected from the group consisting of octylbenzylmethyl anthracene ammonium oxide, dodecyl benzyl dimethyl ammonium chloride and dimercapto dimethyl More than one type of ammonium chloride

(Β) is selected from the group consisting of stilbene, ethylene glycol mono(10) and diethylene glycol mono-n-butyl fluorene: more than one species; and the component (Α) is an octyl aryl group in the antibacterial agent of the present invention (Α)/ (Β) is 200/1 ～1/00, sulfhydryl ammonium hydride, and the component (Β) is benzyl alcohol. The quality of the components (Α) and (Β) is preferably from 10/1 to 1/10. The antibacterial agent of the present invention may be only the components (Α) and (8), or may contain other components such as a chelating agent, a water-soluble solvent, and other cationic substances in order to achieve an improvement in the antibacterial effect or the persistence of the effect. Surfactants, perfumes, enthalpy adjusters, etc. can also be used as articles or preparations for use in the above various living environments or in living environment towels (for example, washing and drying machine cleaning agents, drain cleaning agents, faucet care agents, Bathroom detergents, toilet lotions, etc.) give raw materials for antibacterial properties. Here, 'as a chelating agent', there are mentioned: (1) tripolyphosphoric acid, pyrophosphoric acid, normal acid, hexamethylene acid, and the like, (7) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, and Hydroxyethylglycine-nitrilotriacetic acid, hydroxyethylamine-acetic acid, ethylenediamine pentaacetic acid, triamethylenetetramine hexaacetic acid, and the (4) genus or soil test metal salt, (3) amine Tris-methylene squaric acid, 157492.doc 201206342 i-transethylethylene-u-diphosphonic acid, ethylenediaminetetramethylene phthalic acid, diethylenetriamine penta methylene phosphonic acid, amine triamide Oxide of methylphosphonic acid and such metal or soil metal salt, (4) homopolymer or copolymer selected from monomers of propionic acid and methyl acrylate, acrylic acid - maleic acid An acid copolymer, a polyhydroxy acrylic acid and an alkali metal salt thereof, (5) selected from the group consisting of citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, methacrylic acid (IV) And more than one of the above-mentioned metal salts, (6) calcined glycine-N,N-diacetic acid, aspartic acid _N, N- diacetic acid, serine _N, N_: acetic acid, noodles amine Diacetic acid, ethylenediamine-succinic acid or the like, etc. Further, the protest agent of the present invention can be appropriately formulated, for example, by oil, higher fatty acid, poly-money, pH adjuster, tackifier, An antibacterial agent composition of the present invention is prepared by dissolving or dispersing or dissolving an additive such as a suspending agent, a powder component, a natural extract, a coloring matter, a fragrance, etc. Here, as a pH adjusting agent, it may be used singly or in combination. The following components: acid such as hydrochloric acid or sulfuric acid, such as inorganic acid, citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, etc., sodium oxide or hydrogen Potassium oxide, ammonia or a derivative thereof, an amine salt such as monoethanolamine or diethanolamine or diethanolamine, or an alkali agent such as sodium carbonate or potassium carbonate. Alternatively, the acid agent may be used in combination with an alkali agent as a buffer system. Preferably, the anti-agent composition of the present invention is adjusted so that the pH value at 20 ° C is 2 to 12 by the pH adjusting agent, and it is particularly preferable from the viewpoint of antibacterial property. The pH value is 4 to 11. Self-antibacterial activity The ppm of the antibacterial agent composition of the present invention is more preferably 1 〇 to 1 〇, and the content of 00 〇 (A) is preferably 0.1 to 1 〇〇, 〇〇〇 157492.doc • 12- 201206342 ppm ° Further, the content of the component (B) is preferably from 100 ppm to 100,000 ppm, more preferably, from 100 p_pm to 50^00 ppm' _ and further preferably from 2,00 Q to ppm to 2 Q, 00 Q ppm ° ( More specifically, the content of A) and (B) is as an ingredient (A) using an octylbenzyldimethylammonium salt, a dodecylbenzyldimethylammonium salt or a dimercaptodimethylammonium salt. When benzyl alcohol is used as the component (B), for example, the component (A) is 2,000 to 6,000 ppm, the component (B) is 5,000 ppm to 20,000 ppm, and the component (A) is 2,400 to 6,000 ppm. (B) is 5.000 ppm; component (A) is 25 to 400 ppm, and component (B) is 2,000 to 5.000 ppm. Further, as the component (A), an octylbenzyldimethylammonium salt, a dodecylbenzyldimethylammonium salt or a dimercaptodimethylammonium salt is used, and benzyl alcohol or ethylene glycol alone is used. Ether, diethylene glycol mono-n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethylhexyloxy)ethoxy]ethanol, 2-benzyloxyethanol, 2-phenoxy When ethanol, benzaldehyde, diethylene glycol monobenzyl ether, pentanol or 1-phenoxy-2-propanol is used as the component (B), for example, the component (A) is 10 to 10,000 ppm. The component (B) is 4,000 ppm to 760,000 ppm or the like. Further, as the component (A), an octylbenzyldimethylammonium salt, a dodecylbenzyldimethylammonium salt or a dimercaptodimethylammonium salt is used, and diethylene glycol mono-n-butyl ether is used. When ethylene glycol monohexyl ether is used as the component (B), for example, the component (A) is 10,000 to 100,000 ppm, and the component (B) is 100 ppm to 100,000 ppm. Further, as described above, the antibacterial agent of the present invention may be used only with the component (A) and 157492.doc -13 - 201206342 () or may be combined with other ingredients, or may be formulated into articles or preparations for use in various living environments. It is used in any case, and it is preferable to use in such a manner that the concentration of the components (4) and (B) when the microorganism is contacted is in the above range. Therefore, the antibacterial agent composition of the present invention may be a composition which is intended to be diluted to the above range in actual use and which has been subjected to a shrinkage. 6 By adhering the antibacterial agent of the present invention or the antibacterial agent composition containing the same to a place where microbial contamination is likely to occur, it is possible to prevent pink dirt from adhering or removing pink scale. ^, the antibacterial agent of the present invention or the antibacterial agent composition containing the same can easily cause microbial contamination in a living space (bathroom, kitchen, bathroom, toilet, etc.) in which the living environment is high, and the temperature or humidity is likely to become high. The hard surface of the place, such as the wall of the room or bathroom, temple, washstand, etc. or the bottom of the floor, the bottom of the washbasin, the bottom of the bottle, the drain, the faucet, the toilet line in the toilet For example, it is used by coating before or after the generation of pink dirt. Here, the application is not particularly limited, and the composition is directly applied to a target surface, filled in a spray device such as a trigger or a device, and sprayed. [Examples] Hereinafter, the present invention will be described in detail based on examples. Reference Example 1 Analysis of the cause of the pink stains (1) Analysis of the pink stains observed by SEM Analysis of the bacteria from the bathroom of 14 households Using a toothpick to wipe the soil of 39 samples of the bathroom, suspended at 2.5% After the two-pass solution was fixed and fixed, it was washed with a pH::7.6 1 〇0 mM phosphate buffer, and dehydrated by the ethanol ascending system into 157492.doc 201206342. Further, the mixture was freeze-dried, and the surface was subjected to platinum and vanadium vapor deposition, and then observed by a scanning electron microscope (SEM) (S4300SE/N, Hitachi) at 7 to 15 kV. One of the results of the SEM observation is shown in Fig. 1. In all of the samples, most of the bacteria were 3 μηη or less in size, and no bacteria above 5 μπι were confirmed. That is, in all of the samples, bacteria having the size and shape of the bacteria were dominant, and yeast-sized bacteria were not dominant. Therefore, the main cause of the pink scale is not the Rhodotorula genus of yeast. (2) Analysis of pink stains observed by conjugated focal laser microscopy by FISH (Fluorescence in Situ Hybridization) from 13 The bathroom of the family recycles 17 samples of the container with pink dirt attached, while peeling off the pink stain and the part of the pink stain on the container, in 3% (v/v) tripoly aqueous solution (Sigma-Aldrich Japan shares) Limited) fixed in 2 hours. After removing excess water with a paper towel, it was embedded in a polypropylene-brown amine gel. By using a fluorescent probe for detecting bacteria of the genus Methylobacterium (for AGCGCCGTCGGGTAAGA (sequence number 1, Pirttila, A·, M., Laukkanen, H., Pospiech, Η.,

Myllyla, R., and Hohtola, Anja_ (2000) "Detection of intracellular bacteria in the buds of Scotch pine (Pinus sylvestris L.) by in situ hybridization." Appl. Envion. Microbiol, vol.66(7):3073- 3077.), the rhodamine X (Rose Red X) modified on the 5' end side is subjected to hybridization treatment, and then, by using a fluorescent probe capable of detecting more bacteria (GCTGCCTCC CGTAGGAGT (SEQ ID NO: 2) , Amann., R., I., Krumholz, L., 157492.doc -15- 201206342 and Stahl, D., A. (1990) "Fluorescent-oligonucleotide probing of whole cells for determinative, phylogenetic, and environmental studies in Microbiology."J Bacteriol. vol. 172(2): 762-770.), after fluorescein isothiocyanate (fluorescent isothiocyanate) modified on the 5' end side, after hybridization treatment, used as CalcoHuor white (BD), a fluorescent reagent stained with a large amount of polysaccharide contained in the fungus, was stained and observed by a co-electron laser microscope (CLSM) (Carl Zeiss LSM®). Further, in the hybridization treatment of the fluorescent probe, an auxiliary probe is used in order to increase the specificity and fluorescence intensity of the probe for detecting bacteria of the Methylobacterium. The probe was an oligonucleotide which was not subjected to fluorescent dye modification, and was designed to be used by designing AGCGCCGTCTGGTAAGA (Sequence No. 3) and CCAACTCCCATGGTGTGACGG (SEQ ID NO: 4). The helper probe has the effect of increasing the specificity of the probe for the binding sequence by binding to a sequence similar to the binding sequence of the probe, or by binding the DNA adjacent to the binding region of the probe to the 3-dimensional structure of the DNA. A change occurs to allow the probe to readily bind to the binding sequence. The auxiliary probes are added simultaneously with the probe in the same molar number as the probe. One of the CLSM images is illustrated in Figure 2. Red indicates bacteria of the genus Methylobacterium, yellowish green indicates other bacteria, and light blue indicates mold and polysaccharide. Among all the 17 samples observed, it was shown that the Methylobacterium genus was dominantly present. Therefore, the main cause of the pink scale is the bacteria of the genus Methylobacterium. (3) Analysis of pink dirt by separation of bacteria 157492.doc 16 201206342 Using Potato Dextrose Agar (PDA, potato glucosamine) (Difco), PDA+Chloramphenicol (chlorinemycin) (50 pg/ml), NuUient Agar (NA, 檐养琼-脂) (Difcct>i or R2A..Agar(Dif&o) as a medium, 17 samples of pink dirt (samples A~Q) collected from 13 family bathrooms The culture was carried out at room temperature for 3 days. In this state, various bacteria were formed on the agar medium to form colonies. Therefore, each colony was picked up with Platinum ear and inoculated on a new medium. At 25 ° C for R2A. Next, the other culture medium was subjected to an operation of culturing in 3 to 7 Torr at 30 ° C to isolate the bacteria, and the bacteria of the Methylobacterium genus were assumed based on the analysis of the biochemical traits using the API test (bioMerieux). The base sequence of the DNA of the 16SrRNA region is determined, and the strain is identified by systematic analysis based on the homology search and the base sequence. In addition to the Rhodotorula genus yeast determined by morphological observation, a large number of The bacteria belonging to the genus Methylobacterium are shown in Table 1. The results of the analysis of the samples A to Q are shown in Table 1. It is shown that both the bacteria and the yeast are present in the pink soil, but most of the bacteria present are occupied by the bacteria of the genus Methylobacterium. [Table 1] Results of the separation FISH As a result, bacterial yeast occupies the largest occupied area of bacteria A 〇Methylobacterium genus B 〇Methylobacterium genus C 〇Methylobacterium genus D 〇Methylobacterium genus 157492.doc -17- 201206342 E 〇〇Methylobacterium genus F 〇Methylobacterium genus G 〇 Methylobacterium is a bacterium 〇〇Methylobacterium genus I 〇〇Methylobacterium genus J 〇Methylobacterium Κ 〇Methylobacterium genus L 〇〇Methylobacterium Μ 〇Methylobacterium Ν 〇Methylobacterium genus 0 〇〇Methylobacterium ΡMethylobacterium It belongs to the bacterium of the genus Q 〇〇Methylobacterium. Note that the bacterium is detected in the table. Reference Example 2 Antibacterial agent of Methylobacterium genus and f-type Using a PDA plate medium (Difco), a pink stain sample from the bath of Reference Example 1 (3) was used. Isolation, identification] \/[.11^30卩11 mountain (:11111 (M. thermophila) FP4 cells were cultured overnight at 30 ° C, using a platinum ear to pick M. mesophilicum FP4 on the medium The cells were suspended in another Potato Dextrose Broth (PDB, potato dextrose broth) and vibrated at 30 ° C for 3 曰. The supernatant was removed by centrifugation (7000 g x 5 min) and suspended in an equal amount of physiology. In the saline solution, the mixture was centrifuged again (7000 gx for 5 min), and the DMSO solution of OD 0.8 was prepared by using physiological saline. The octylbenzyldithiol chlorination diluted with sterilizing water was added to the bacterial solution 10 μΐ. 1 ml of ammonium solution (Sanisol 08, Kao Co., Ltd.), contact for 5 minutes, and add 1/1 of the dilution of LP (Lecithin Polysorbate, egg fat-polysorbate) (Wako Pure Chemical Industries) And dilute 157492.doc -18- 201206342 octylbenzyl dimethyl ammonium chloride, make it inactive, determine the viable cell count by agar smear. Prepare E.coli NBRC3972, S in the same order .aureus NBRC13276, and P.aeruginosa NBRC13275 (all from The bacterial liquid of NBRC (purchased by the biological genetic resources department of the independent administrative legal person product evaluation technology base) was used to determine the number of viable bacteria after the addition of the octylbenzyldifluorenyl ammonium chloride solution. As shown in Table 2, at E. In coli, S. aureus, and P. aeruginosa, by contacting with a solution of octylbenzyldimethylammonium chloride at a concentration of 240 to 480 ppm for 5 minutes, a decrease in the number of bacteria above log2 was observed. In M. mesophilicum, a significant reduction in the number of bacteria was observed only by contact with a solution of octylbenzyldimonium ammonium chloride at a concentration of 6000 ppm for 60 minutes. According to these results, bacteria of the genus Methylobacterium were shown. The resistance to antibacterial agents is very high. Based on the results, it is also shown that the Methylobacterium genus with high viability is the main cause of pink soil. [Table 2] Contact time (min) E.coli NBRC3972 S.aur NBRC • Eus 13276 P.aeruginosa NBRC13275 M.mesophilicum FP4 ”240 ”480 n240 480 ”120 *l240 n6000 5 0.96 4.01 1.76 4.72 0.23 2,38 0.19 10 1.44 4.85 3.16 >5.41 0.35 4.28 0.28 30 1.77 >4.85 >5.41 &g t;5.41 1.23 >5.23 1.15 60 2.89 >4.85 >5.41 >5.41 2.47 >5.23 3.39 〇_,_,_,_ The values in the table indicate the log reduction number of bacteria at various time exposures (cfu/ml 〇157492.doc -19- 201206342 * "octylbenzyldithiol chlorinated concentration (ppm) Example 1 Evaluation of antibacterial activity against bacteria of the genus Methylobacterium (1) M was prepared in the same order as in Reference Example 2. .mesophilicum FP4 bacterial solution. Further, an octylbenzyldimethyl vapor solution (2400-6000 ppm) was prepared in the same manner as in Reference Example 2, and benzyl alcohol (BA, Benzyl Alcohol) was added thereto in a manner of 5000 ppm. This octylbenzyldithiol ammonium + BA solution (1 ml) was added to M. mesophilicum FP4 solution (1 μ μΐ), and contacted with the bacteria for 5 minutes. The results are shown in Table 3. According to Table 3, an extremely high combined effect was obtained by adding BA5000 ppm at a concentration of 2400 to 6000 ppm of octylbenzyldimethylammonium oxide having no antibacterial property at a contact time of 5 minutes alone. — [Table 3] Octylbenzyldimethylammonium vapor concentration BA concentration reduction bacteria number (PPm) (%) (Log cfu/mL) 0.5 0.03 0 1 -0.02 2400 0 0.09 4800 0 0.22 6000 0 0.08 2400 0.5 1.88 4800 0.5 3.9 6000 0.5 > 4.23 Evaluation of the antibacterial activity of the bacterium of the genus Methy 1 obacterium (2) Various bacterial strains of the genus Methylobacterium shown in Table 4 were prepared in the same order as in Reference Example 2. Further, M. fujisawaense (M. faecalis) GP 1 and M. radiotolerans (AP) 157492. doc -20-201206342 were obtained by separating from the bathroom in the same manner as M. mesophilic FP4. The remaining strains were obtained from the RIKEN BioResource Center of the Institute of Physical and Chemical Research. Further, a solution of dodecylbenzyldimethylammonium vapor (39 to 3 13 ppm) was prepared in the same order as in Reference Example 2_, and benzyl alcohol (BA) was added thereto in a manner of 2000 to 5000 ppm. ). Each of the bacterial bacterial liquids (10 μM) was added to the dodecylbenzyldiindenyl ammonium chloride + BA solution (1 ml), and the cells were exposed to the bacteria for 5 minutes. The results are shown in Table 4. In the table, the order of +++>+ + >+ indicates that the increase is strong. Further, - indicates that proliferation has not been confirmed. Therefore, the order of -> + >++> +++ indicates that the antibacterial property is high. According to Table 4, it was confirmed that the antibacterial property was improved by adding anthraquinone to dodecylbenzyldimethylammonium chloride for all the strains. [Table 4]

M.mesophilicum FP4 12-base benzyl dihydrazino gasification (ppm) 313 156 78 39 BA (%) 0.5 - - - +++ 0.4 - ++ ++ +++ 0.3 + ++ +++ +10+ 0.2 + +++ +++ +++ M.fujisawaense GP1 Dodecylbenzyldimethylammonium hydride (ppm) 313 156 78 39 BA(°/〇) 0.5 - - ++ ++ 0.4 ++ ++ ++ 0.3 ++ +++ +++ +++ 0.2 -Η-Ί- +++ +++ +++ 157492.doc •21- 201206342 M.radiotolerans AP2 12th base section Dimethyl gasification bond (ppm) 313 156 78 39 BA(°/〇) 0.5 - - + +++ 0.4 - + +++ +++ 0.3 + + +++ +++ 0.2 -Η- + -Η- +++ +++ M.mesophilicum JCM2829 Dodecyl benzyl dihydrazylated gas (ppm) 313 156 78 39 ΒΑ(%) 0.5 - - + + 0.4 - - + + 0.3 - - + + 0.2 - + + + M.extorquens JCM2805 Dodecylbenzyl dimethyl chloride (ppm) 313 156 78 39 BA(%) 0.5 - - - - 0.4 - - - + 0.3 - - - + 0.2 - - + + M.radiotolerans JCM2805 Dodecylbenzyl dimethylammonium chloride (ppm) 313 156 78 39 BA(%) 0.5 - - ++ +++ 0.4 - - ++ + ++ 0.3 - - ++ +++ 0.2 - + +++ +++ Example 3 against Methylobacterium The same order was prepared in Reference Example 2 to evaluate the strength of (3) M.mesophilicum FP4 bacteria solution. Further, an octylbenzyldimethyl gas 157492.doc •22-201206342 ammonium salt solution (10 to 10000 ppm) was prepared in the same manner as in Reference Example 2, and a table was added thereto in such a manner as to be the concentration disclosed in Table 5. Various organic solvents shown in 5. This octylbenzyldimethylammonium chloride-electrolyte solution (1 ml) was added to .M, mesop!iilicuni FP4 solution (10 μM), and contacted with the bacteria for 5 minutes. The results are shown in Table 5. According to Table 5, regarding benzyl alcohol, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethylhexyloxy)ethoxy]ethanol, 2-benzyloxyethanol, 2-phenoxyethanol, diethylene glycol monobenzyl ether, pentanol, 1-phenoxy-2-propanol, benzaldehyde, diethylene glycol mono-n-butyl ether, in solvent alone, octylbenzyl The effect of the combined use of octylbenzyldimonyl ammonium chloride was confirmed at a concentration at which the indenyl ammonium chloride alone did not have an antibacterial property. [table 5]

Solvent solvent concentration (ppm) octylbenzyl dimethyl ammonium carbonate concentration (ppm) reduced bacteria count (Log cfu / mL) no 0 3000 0 0 5000 0.06 0 10000 -0.07 diethylene glycol mono-n-butyl ether 76000 0 0.34 76000 10000 >4.23 Diethylene glycol monobenzyl ether 9812 0 0.44 20000 0 -0.08 9812 3000 2.47 20000 10000 2.12 2-benzyloxyethanol 7610 0 1.01 20000 0 0.41 7610 3000 3.64 20000 10000 >4.43 Benzyl alcohol 5000 0 0.14 20000 0 0.33 5000 2000 2.16 157492.doc -23- 201206342 5407 5000 3.59 10000 1000 3.45 10000 2000 4.15 20000 10 2.57 20000 50 >4.45 2-phenoxyethanol 6908 0 0.96 15000 0 0.07 6908 1000 2.04 6908 2000 4.74 15000 10000 >4.43 pentanol 4408 0 1.06 12500 0 0.18 4408 3000 3.08 4408 5000 >4.84 12500 10000 >4.43 1-phenoxy-2-propanol 7610 0 0.69 10000 0 0.13 7610 1000 >4.84 10000 10000 &gt ;4.43 Diethylene glycol monohexyl ether 5000 0 0.36 5000 500 3.96 5000 1000 4.59 Stupid formaldehyde 5306 0 0.36 5306 3000 2.41 5306 5000 4.26 Ethylene glycol monohexyl ether 5000 0 0.04 5000 500 4.32 2-[2-(2-B Hexyloxy Ethyloxy]ethanol 5000 0 1.87 5000 1000 4.59 Evaluation of the antibacterial activity of the bacterium of the genus Methylobacterium in Example 4 (4) The M. mesophilicum FP4 bacterium was prepared in the same manner as in Reference Example 2. Further, an octylbenzyldimethyl chloride-24-157492.doc 201206342 ammonium salt solution (10,000 to 100,000 ppm) was prepared in the same manner as in Reference Example 2, and the concentration shown in Table 6 was added thereto in such a manner as to reveal the concentration. A variety of organic solvents. The octylbenzyl dihydrazide gasified hydrazine + organic solvent solution (1.ml) was added to M. mesophilicunl·FP4 (10 μM) for 1 minute. The results are shown in Table 6. According to Table 6, regarding diethylene glycol mono-n-butyl ether and ethylene glycol monohexyl ether, in the solvent alone, octylbenzyldimethylammonium chloride alone does not show the antibacterial concentration and contact time, confirm and The combined effect of octylbenzylammonium chloride. [Table 6] Solvent solvent concentration (ppm) octylbenzyl diindenyl ammonium sulfide concentration (Ppm) Reduced bacterial count (Log cfu/mL) No 0 10000 -0.07 0 50000 0.61 0 100000 1.23 Monoethylene glycol single positive Dibutyl ether 100000 0 -0.01 100000 10000 1.13 Ethylene glycol monohexyl ether 100 0 0 100 50000 2.12 100 100000 2.06 Example 5 Evaluation of the antimicrobial activity of bacteria of the genus Methylobacterium (5) M was prepared in the same order as in Reference Example 2. Mesophilicum FP4 bacterial solution. Further, a quaternary ammonium salt solution (25 ppm or 400 ppm) shown in Table 7 was prepared in the same manner as in Reference Example 2, and benzyl alcohol was added thereto in a manner of 5000 ppm. This quaternary ammonium salt + benzyl alcohol solution (1 ml) was added to M. mesophilicum FP4 solution (10 μM) and contacted with the bacteria for 5 minutes. The results are shown in Table 7. According to Table 7, in addition to octylbenzyldimethylammonium chloride, it is also confirmed for dodecane 157492.doc -25- 201206342 benzyl benzyl dimethyl ammonium chloride or dimercapto fluorenyl ammonium hydride. High and use the effect. [Table 7] Reduced bacterial count (log cfu/ml) BA+ BA-400 ppm dodecylbenzyldithiocarbamate ammonium 6.56 < -0.11 25 ppm dimercaptodithiocarbamate ammonium sulfate 6.06 < 0.08 * In the table, BA+ represents the system in which BA is added, and BA- represents the system in which BA is not added. Example 6 Evaluation of Cleaning Performance of Model Pink Soil In the same procedure as Reference Example 2, the bacterial solution of M. mesophilicum FP4 was prepared (OD0.8). ). Then, FRP (Fiber Reinforced Plastics) of l〇xl〇x2 (mm) was immersed in ethanol and irradiated with UV (Ultraviolet) to sterilize. The FRP slice was placed in a microtiter plate (Microti ter Dish). In addition, add 1 mL of bacterial solution. The cells were allowed to stand at 30 ° C for 6 days, and only the FRP sections were transferred to a new 24-well plate and dried overnight at 30 ° C to prepare a model pink stain. The FRP section to which the model soil is attached is immersed in a solution of octylbenzyldimethylammonium chloride (10, 〇〇〇ppm) or octylbenzyldimethylammonium chloride (10,000 ppm) + BA (5,000 In the solution of the ppm), after standing for 5 minutes, the sections were placed in a test tube of 1 mL of the LP dilution solution, and the mixture was vigorously stirred by a vortex mixer to separate and disperse the bacteria, and the bacteria which were peeled and dispersed were measured. number. Further, the FRP sections obtained by peeling and dispersing the bacteria were again placed in a microtiter plate, and the cells were allowed to stand at 30 ° C, and the cells were allowed to stand until the bacteria regenerated. 157492.doc -26-201206342. The results are shown in Tables 8 and 9. The amount of bacteria in the FRP section in a solution obtained by adding BA solution to octylbenzyldimethylammonium methoxide having a high ability to remove bacteria from the genus Methylobacterium was greatly reduced. Also, it takes a lot of time until the bacteria re-emerge in the sections. On the other hand, in the FRP sections impregnated with the octylbenzyldifluorenyl chloride recording solution, the number of bacteria was not reduced, and it was found that the bacteria rapidly repopulated. [Table 8] Number of viable cells (1〇 g c.f.u/ml) BA+ BA-octylbenzyl diindenyl ammonium sulfate 3.68 1.28

In the table, BA+ indicates a system in which B A is added, and BA- indicates a system in which B A is not added. [Table 9] Water octyl benzyl dimethyl vaporized ammonium octylbenzyl dimethyl vaporized ammonium + BA 2 曰 6 / 6 3 / 6 0 / 6 3 曰 6 / 6 5 / 6 0 / 6 5曰6/6 6/6 1/6 6曰6/6 6/6 3/6 The table shows the time required for recontamination after the antibacterial test. The denominator in the table indicates the total number of test areas, and the numerator indicates the recontamination test. The number of districts. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an SEM image of pink soil; and Fig. 2 is a conjugated-focus laser microscope image of pink soil using FISH. 157492.doc -27- 201206342 Sequence Listing <110> Kao Corporation <120> Antibacterial Agent <130> KS1149 <140> 100124998 <141> 2011-07-14 <150> JP 2010-159992 <151> 2010-07-14

<160> 4 <170> Patentln version 3.1 <210> 1 <211>17 <212> DNA <213> Artificial sequence <220><223> Oligonucleotide probe <400> 1 agcgccgtcg ggtaaga 17 <210> 2 <211> 18 <212> DNA <213>Artificial sequence<220><223> Oligonucleotide probe <400> 2 gctgcctccc gtaggagt 18

<210> 3 <211> 17 <212> DNA <213>Artificial sequence<220><223> Oligonucleotide probe <400> 3 agcgccgtct ggtaaga 17 <210> 4 < 21 <212> DNA <213>Artificial sequence<220><223> Oligonucleotide probe <400> 4 ccaactccca tggtgtgacg g 157492 - Sequence Listing.doc

Claims (1)

201206342 VII. Patent application scope: Antibacterial Qiqi' is a combination of the quaternary ammonium salt shown in the following component (A) and the organic solvent shown in (B): (A) selected from dialkyl dimethyl ammonium a salt of a salt or an alkylbenzyl dimethyl sulfonium salt; or a salt of a quaternary salt of the above formula (1) or (7) Solvent; [Chemical 5] 〇 / , HO-fAO^R (1) OHC^AO-^r (2) [wherein, R represents an alkyl or alkenyl group having a carbon number of 5 to 10, or a benzyl group, A The number of the anastomoses is 1 to 1 Å, and η is the number of 〇~5. The same can be used for the same, or different. For example, the antibacterial agent of Item 1 wherein the organic solvent of the component (B) is selected from the compounds represented by the formulae (1) and (2), wherein A is an alkylene group having a carbon number of 1 to 3, An organic solvent of one or more of the compounds of 〇 2 . For example, the fungicide of the claim 1 wherein the organic solvent of the component (B) is selected from the group consisting of benzyl alcohol, ethyl alcohol, monoethylene glycol, diethylene glycol mono-n-butyl, diethylene glycol monohexyl ether 2-[ 2-(2-ethylhexyloxy)ethoxy]ethanol, 2-benzyloxyethanol, 2: phenoxyethyl yeast, benzofural, diethylene glycol monobenzyl ether, pentanol and One or more of oxy-2-propanol. 4_ The antibacterial agent of claim 1, wherein the organic solvent of the component (B) is benzyl alcohol. 5. The antibacterial agent according to any one of claims 4 to 4, wherein the quaternary ammonium 157492.doc 201206342 salt of the component is selected from the group consisting of octylbenzyldimethylammonium salt and dodecylbenzyldimethylammonium salt. One or more of a salt and a dimercaptodimethylammonium salt. 6. The antibacterial agent of claim 5, wherein the ammonium salt is a salt with a vaporized ion. 7. The anti-halogen agent of claim 1, wherein the fourth-order salt of the component (a) is octyl benzyl ammonium chloride, and the organic solvent of the component (B) is benzyl alcohol. 8. The antibacterial agent according to any one of claims 1 to 7, which has an antibacterial effect on the fine elimination of Methyl〇bacteHum (methyl bacterium). An antibacterial agent composition comprising the antibacterial agent according to any one of claims 1 to 8. 10. The antibacterial agent composition of claim 9, wherein the composition comprises a component (Α) 0·1 to 100,000 ppm 'component (B) 1 〇〇 ppm~1〇〇 〇〇〇 . 11. The antibacterial agent composition according to claim 1, wherein an octylbenzyldimethylammonium salt, a dodecylbenzyldimethylammonium salt or a dimercaptodimethylammonium salt is used as a component ( A) When benzyl alcohol is used as the component (B), the component (A) is 2,000 to 6,000 ppm, the component (8) is 5 〇〇〇 ppm to 2 〇〇〇〇 ppm, or the component (a) is 2,400 to 6,000 ppm. , ingredient (B) 5,000 ppm ' or contains ingredients (A) 25~400 ppm, ingredient (B) 2,000-5,000 ppm 〇12 · A method to prevent pink dirt from adhering or removing pink dirt, characterized by: The antibacterial agent according to any one of items 1 to 8 or the toughening agent composition according to any one of claims 9 to 11 is used in a place where microbial contamination is likely to occur. 13. Use of an antibacterial agent which is obtained by combining the quaternary ammonium salt represented by the following component (A) and the organic solvent represented by (B): 157492.doc 201206342 (A) selected from a dialkyl group a quaternary ammonium salt of one or more of a methylammonium salt and an alkyl benzyl dimethylammonium salt; (B) selected from the group consisting of a scented aromatic alcohol, an aromatic bee, and the following formulas (1) and (2) One or more organic solvents of the compound; [Chemical 6] Η0^Α0)κΗ (1) OHC-^AO^R (2) wherein R represents an alkyl or alkenyl group having a carbon number of 5 to 1 Å, or a benzyl group, A represents a stretching group having a carbon number of 1 to 10, and n represents 〇~ 5, 11 A can be the same, or different]. 14. The use of a combination of a quaternary ammonium salt represented by the following component (A) and an organic solvent represented by (B) to produce an antimicrobial agent: (A) is selected from the group consisting of dialkyldidecyl ammonium salts and One or more quaternary ammonium salts of an alkylbenzyldimethylammonium salt; the bismuth (B) is selected from the group consisting of an aromatic alcohol, an aromatic aldehyde, and a compound represented by the following formulas (1) and (2); Organic solvent; [Chemical 7] HO" (AOkR (1) OHC-^AO^-R (2) [wherein, R represents an alkyl or alkenyl group having a carbon number of 5 to 10, or a benzyl group, and VIII represents The number of carbon atoms is from 1 to 10, η represents the number of 〇~5, ηA can be the same, 157492.doc 201206342 can also be different. 15. An antibacterial method characterized by combining the following components (4) The quaternary ammonium salt and the ugly organic solvent are used: (4) a quaternary salt selected from the group consisting of a dialkyl dimethyl ammonium salt and an alkyl benzyl dimethyl ammonium; (B) of the formula (1) and (2) is selected from one or more organic solvents of an aromatic alcohol or an aromatic aldehyde compound; [Chemical 8] HO^AO^R (1) ohc-(ao^r (2) Wherein R represents an alkyl group having a carbon number of 5 to 10 Alkenyl or benzyl, A represents an alkylene group having a carbon number of from 1 to 10, n represents the number of 〇~5, and 11 of eight may be the same or different.] 16. The antibacterial method of claim 15 It inhibits or prevents the growth of microorganisms containing bacteria of the genus Methylobacterium. 157492.doc