CN103002732B - Antibacterial agent - Google Patents

Antibacterial agent Download PDF

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Publication number
CN103002732B
CN103002732B CN201180034615.0A CN201180034615A CN103002732B CN 103002732 B CN103002732 B CN 103002732B CN 201180034615 A CN201180034615 A CN 201180034615A CN 103002732 B CN103002732 B CN 103002732B
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composition
000ppm
ammonium salt
methylobacterium
dimethyl ammonium
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CN103002732A (en
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矢野刚久
久保田浩美
森井纪行
宫原佳子
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Kao Corp
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Kao Corp
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02Amines; Quaternary ammonium compounds
    • A01N33/12Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/201Monohydric alcohols linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2027Monohydric alcohols unsaturated
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2034Monohydric alcohols aromatic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2072Aldehydes-ketones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Abstract

The invention provides removing the useful antibacterial agent of the pink dirt that produces in living environment.Described antibacterial agent is the antibacterial agent by the quaternary ammonium salt represented by following composition (A) and the organic solvent combination represented by (B).(A) quaternary ammonium salt of more than a kind in dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt is selected from.(B) organic solvent of more than a kind in aromatic alcohols, aromatic aldehyde, following formula (1) and the compound represented by (2) is selected from (in formula, R represents that carbon number is alkyl or thiazolinyl or the benzyl of 5 ~ 10, A represents that carbon number is the alkylidene of 1 ~ 10, n represents the number of 0 ~ 5, and n A is identical or different).

Description

Antibacterial agent
Technical field
The present invention relates to and the attachment of the pink dirt produced in living environment is prevented and remove useful antibacterial agent.
Background technology
In the last few years, people improve keeping the clean requirement of family or the living environment such as job site, communal facility further.But on the other hand, because the office block in building in the last few years, particularly city or apartment seal height easily accumulate moisture, be thus in the environment that the microorganism such as bacterium or mould easily breeds.Particularly in toilet, bathroom, washroom, kitchen etc. use water place, because moisture or the condition such as moisture or temperature microorganism more easily breed.
With in the living environments such as water place, significant a kind of dirty be present the pink dirt that the attachment of red or that pink isogonic is red color or mucus are representative.Pink dirt is remarkable especially in the positions such as the floor in discharge outlet, liner, drinking valve place, bathroom, the bottom of container such as washing bucket or Shampoo bottle etc.Pink dirt can regenerate immediately again after cleaning, is thus very troublesome dirt for cleaning person.In addition, pink dirt is not only difficult to removing, and is brought discomfort because of mucus sense and the difference that looks with the user at water place.Therefore wish that exploitation can remove the clean method at pink dirt, maintenance water place effectively.
As the mushroom separated from pink dirt, report have rhodotorula ( rhodotorula) belong to yeast, Methylobacterium ( methylobacterium) belong to bacterium, Brevundimonas sp ( brevundimonas) belong to bacterium, microbacterium ( microbacterium) belong to (patent document 1, non-patent literatures 1) such as bacteriums.Wherein rhodotorula ( rodotorula) belong to yeast and other bacterial classification phase specific growth rate soon, therefore as the main pathogenic fungi of pink dirt known (patent document 1).Therefore, as rhodotorula ( rhodotorula) belong to the antibacterial activity of yeast high, to the effective composition of the suppression of mucus, report silver-colored class, zinc class, titanium class, the mineral-type antibacterial agent such as antibiotic property metal of copper class, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, zephiran ( benzalkonium) the surfactant-based antibacterial agent such as salt, imidazoline salt etc. (patent document 1).
But, about pink dirt, be not conceived to so far Methylobacterium ( methylobacterium) belong to bacterium, the report of the pink dirt of removing is inquired into from the viewpoint of the growth and breeding suppressing this bacterium.
Prior art document
Patent document
Patent document 1: Japanese patent application laid is willing to 2006-151908 publication
Non-patent literature
Non-patent literature 1: the science of cleaning, 2007,52 volumes No. 4 16 ~ 22 pages
Summary of the invention
The present invention relates to following invention.
1) by the antibacterial agent of the quaternary ammonium salt represented by following composition (A) and the organic solvent combination represented by (B).
(A) quaternary ammonium salt of more than a kind in dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt is selected from.
(B) organic solvent of more than a kind in aromatic alcohols, aromatic aldehyde, following formula (1) and the compound represented by (2) is selected from.
[in formula, R represents that carbon number is alkyl or thiazolinyl or the benzyl of 5 ~ 10, and A represents that carbon number is the alkylidene of 1 ~ 10, and n represents the number of 0 ~ 5, and n A is identical or different.]
2) containing above-mentioned 1) the bactericidal composition of antibacterial agent.
3) attachment of the pink dirt method that prevents or remove, is characterized in that above-mentioned antibacterial agent or bactericidal composition being applied to the place easily producing microbial contamination.
4) combination of the quaternary ammonium salt represented by following composition (A) and the organic solvent represented by (B) is as the use of antibacterial agent.
(A) quaternary ammonium salt of more than a kind in dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt is selected from.
(B) organic solvent of more than a kind in aromatic alcohols, aromatic aldehyde, following formula (1) and the compound represented by (2) is selected from.
[in formula, R represents that carbon number is alkyl or thiazolinyl or the benzyl of 5 ~ 10, and A represents that carbon number is the alkylidene of 1 ~ 10, and n represents the number of 0 ~ 5, and n A is identical or different.]
5) combination of the quaternary ammonium salt represented by following composition (A) and the organic solvent represented by (B) is for the manufacture of the use in antibacterial agent.
(A) quaternary ammonium salt of more than a kind in dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt is selected from.
(B) organic solvent of more than a kind in aromatic alcohols, aromatic aldehyde, following formula (1) and the compound represented by (2) is selected from.
[in formula, R represents that carbon number is alkyl or thiazolinyl or the benzyl of 5 ~ 10, and A represents that carbon number is the alkylidene of 1 ~ 10, and n represents the number of 0 ~ 5, and n A is identical or different.]
6) antibiotic method, is characterized in that combinationally using the quaternary ammonium salt represented by following composition (A) and the organic solvent represented by (B).
(A) quaternary ammonium salt of more than a kind in dialkyl dimethyl ammonium salt and alkyl benzyl dimethyl ammonium salt is selected from.
(B) organic solvent of more than a kind in aromatic alcohols, aromatic aldehyde, following formula (1) and the compound represented by (2) is selected from.
[in formula, R represents that carbon number is alkyl or thiazolinyl or the benzyl of 5 ~ 10, and A represents that carbon number is the alkylidene of 1 ~ 10, and n represents the number of 0 ~ 5, and n A is identical or different.]
Accompanying drawing explanation
Fig. 1 is the SEM picture of pink dirt.
Fig. 2 is the confocal laser microscopic iage (confocallasermicroscope) of the FISH using pink dirt.
Embodiment
The present invention relates to and provide for preventing and remove in living environment, particularly toilet, bathroom, the antibacterial agent be attached with of pink dirt that hard surface produces near kitchen etc.
The present inventors use sweep electron microscope (SEM) or confocal laser microscope (CLSM) to analyze actual pink dirt, its found that the main pathogenic fungi producing pink dirt be former known rhodotorula ( rhodotorula) belong to yeast, not equal to be Methylobacterium ( methylobacterium) belong to bacterium.So, for can effectively suppress or stop Methylobacterium ( methylobacterium) composition of growth and breeding that belongs to bacterium inquires into, and finds when combinationally using specific quaternary ammonium salt and organic solvent, can to Methylobacterium ( methylobacterium) belonging to the antibacterial activity that bacterium plays excellence, the removing for pink dirt is useful.
By antibacterial agent of the present invention, on the wall or the hard surface such as floor, apparatus machine of living environment, particularly kitchen or bathroom, toilet, washstand etc. time, sterilization and antifouling can be carried out to this hard surface, specifically can prevent the attachment of pink dirt and the pink dirt easily accompanying by removing.
In the present invention, be as the known compound of antibiotic property cationic surfactant as the dialkyl dimethyl ammonium salt of the quaternary ammonium salt of composition (A) and alkyl benzyl dimethyl ammonium salt.
In the present invention, as dialkyl dimethyl ammonium salt and alkyl dimethyl ammonium salt, can preferably enumerate dialkyl group (C respectively 8-18) dimethyl ammonium, alkyl (C 8-18) dimethyl ammonium.
At this, the straight chained alkyl that carbon number is 8 ~ 18 can be enumerated as alkyl, be such as octyl group, decyl, dodecyl (lauryl), myristyl (myristyl), cetyl (cetyl), heptadecyl, octadecyl (stearyl), be preferably octyl group, decyl, dodecyl.
As preferred dialkyl dimethyl ammonium salt, didecyldimethyl ammonium salt can be enumerated, as alkyl benzyl dimethyl ammonium salt, octyl group benzyl dimethyl ammonium salt, dodecylbenzyl dimethyl ammonium etc. can be enumerated.
Ammonium salt can be enumerated and F -, Cl -, Br -, I -deng halide ion, NO -and SO 4 2-deng salt, be preferably and the salt of halide ion, further preferably and the salt of chloride ion.
As more preferred quaternary ammonium salt, octyl group benzyl chloride, dodecylbenzyl alkyl dimethyl ammonium chloride, DDAC etc. can be enumerated.
The quaternary ammonium salt of the composition (A) of the invention described above can use known method manufacture, also can use commercially available product.Such as can buy QUARTAMIND10(Kao Corp as dialkyl dimethyl ammonium salt to manufacture), SANISOL08, SANISOLC(Kao Corp can be bought as alkyl benzyl dimethyl ammonium salt manufacture) etc. use.
Quaternary ammonium salt of the present invention in general known its shows excellent antimicrbial power to bacterium etc. separately.But, as shown in aftermentioned embodiment, to Escherichia coli ( e.coli), staphylococcus aureus ( s.aureus), pseudomonas aeruginosa ( p.aeruginosa)under showing the concentration of enough antimicrbial powers, to Methylobacterium ( methylobacterium) belong to bacterium do not show antibacterial activity, and must with the concentration of more than 10 times with the time of contact of more than 30 minutes use just can observe significant bacterial population minimizing.That is, distinguish Methylobacterium ( methylobacterium) belong to bacterium very high for the patience of this quaternary ammonium salt.
And find, in these cases, by the organic solvent combination use of this quaternary ammonium salt and composition (B) can be improved its antimicrbial power extraordinarily.Therefore, using more than the a kind antibacterial agent combined of the organic solvent of more than a kind of the quaternary ammonium salt of mentioned component (A) and composition (B) can as suppression comprise Methylobacterium ( methylobacterium) belong to bacterium at the flourish (antibacterial) of interior microorganism or stop the antibacterial agent of its flourish (sterilization) or the antibacterial agent for preventing or remove the pink dirt attachment in living environment.
At this, " living environment " comprises family, workplace, school, whole environment that the people of the work of communal facility etc. or animal can survive, be preferably, the environment that particularly moisture is many and the environment that pink dirt easily produces, such as, bathroom, washroom, washing chamber, the water place such as toilet or kitchen, drinking water place, swimming pool, cleaning facility, and other water pipe facility periphery, more specifically, kitchen or bathroom can be enumerated, toilet, the wall of washstand etc. or ground, the bottom of washing bucket, bottom the bottle of shampoo etc., discharge outlet, near tap, the hard surface in the water line portion in the closet of toilet etc.
In addition, the dirt from microorganism a little just presenting partially red color that " pink dirt " refers to attachment or mucus is representative.At this, partially red color comprises the Neutral colour of redness, pink or these colors.Such as, can for having the color (mud produced in the living environment such as bathroom: fungi-proofing mildew-resistant vol.24, No.11, p.723-728,1996) of maximum absorption wavelength near 490nm.
In the organic solvent of composition (B), as aromatic alcohols, preferred benzylalcohol, BOE, phenoxetol, 1-phenoxy group-2-propyl alcohol etc., wherein further preferably benzylalcohol.
As aromatic aldehyde, preferred benzaldehyde, phenylacetaldehyde, 4-tolyl aldehyde, 2-benzenpropanal etc., wherein, preferably further benzaldehyde, phenylacetaldehyde.
In hydroxy compounds shown in formula (1), the aldehyde compound shown in formula (2), be the alkylidene of 1 ~ 10 as the carbon number represented by A, be preferably the alkylidene that carbon number is 2 or 3.
As alkyl or thiazolinyl that the carbon number represented by R is 5 ~ 10, can be straight chain also can be side chain, being preferably carbon number be the alkyl of 5 ~ 8, such as, can enumerate normal-butyl, n-hexyl, 2-ethylhexyl etc.
N is the number of 0 ~ 3, is preferably 1 ~ 3, is more preferably 1 or 2.In addition, n A is identical or different.
As the preferred object lesson of the organic solvent of composition (B), such as, can enumerate benzylalcohol, ethylene glycol list n-butyl ether, ethylene glycol ether, 2-(2-ethyl hexyl oxy) ethanol, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, phenylacetaldehyde, 4-tolyl aldehyde, 2-benzenpropanal, hexanal, 2-ethyl butyraldehyde, diethylene glycol single-benzyl ether, amylalcohol, 1-phenoxy group-2-propyl alcohol etc.
Therefore, as the preferred compositions of composition (A) and composition (B), following situation can be enumerated:
Composition (A) is for being selected from octyl group benzyl chloride, more than a kind in dodecylbenzyl alkyl dimethyl ammonium chloride and DDAC, composition (B) is for being selected from benzylalcohol, ethylene glycol list n-butyl ether, ethylene glycol ether, 2-(2-ethyl hexyl oxy) ethanol, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, phenylacetaldehyde, 4-tolyl aldehyde, 2-benzenpropanal, hexanal, 2-ethyl butyraldehyde, diethylene glycol single-benzyl ether, the situation of more than a kind in amylalcohol and 1-phenoxy group-2-propyl alcohol,
Composition (A) is for being selected from more than a kind in octyl group benzyl chloride, dodecylbenzyl alkyl dimethyl ammonium chloride and DDAC, and composition (B) is for being selected from the situation of more than a kind in benzylalcohol, ethylene glycol ether and diethylene glycol list n-butyl ether;
Composition (A) is octyl group benzyl chloride, the situation that (B) is benzylalcohol.
In antibacterial agent of the present invention, mass ratio (A)/(B) of composition (A) and (B) is preferably 200/1 ~ 1/200, and more preferably 10/1 ~ 1/10.
Antibacterial agent of the present invention, only can contain composition (A) and (B), or also can be as required, for the further raising of antibacterial effect or the continuation etc. of effect, and containing other composition, such as, chelating agent, water-soluble solvent, other cationic surfactant, spices, pH adjusting agent etc.In addition, also the material giving above-mentioned various living environment or the product used in living environment or preparation (such as, scrubbing-and-drying unit cleaning agent, discharge outlet cleaning agent, tap age resister, bathing pool cleaning agent, lavatory cleaning agent etc.) antibiotic property can be used as.
At this, as chelating agent, (1) tripolyphosphate can be enumerated, pyrophosphoric acid, orthophosphoric acid, hexa metaphosphoric acid and their alkali metal salt, (2) ethylenediamine tetra-acetic acid, hydroxyl imide base oxalic acid, dihydroxyethylglycin, NTA, HEDTA, diethylene-triamine pentaacetic acid, triethylenetetraaminehexaacetic acid and their alkali metal salt or alkali earth metal salt, (3) ATMP, HEDP, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid, the N-oxide of ATMP and their alkali metal salt or alkali salt, (4) are selected from single polymers or the copolymer of the monomer in acrylic acid and methacrylic acid, acid-co-maleic acid, poly-Alpha-hydroxy acrylic acid and alkali metal salt thereof, (5) are selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, more than a kind in polybasic carboxylic acid in maleic acid and their alkali metal salt, (6) alkyl glycine-N, N-oxalic acid, aspartic acid-N, N-oxalic acid, serine-N, N-oxalic acid, glutamic acid diacetic acid, EDDS or their salt etc.
In addition, antibacterial agent of the present invention can be as required, suitable coordinating example is as additives such as oil content, higher fatty acid, silicone, pH adjusting agent, tackifier, suspension, powdered ingredients, natural extract, pigment, spices, be uniformly mixed and make it dispersing and dissolving, thus manufacture antimicrobial composition of the present invention.
At this, can separately or the inorganic acid such as compound use hydrochloric acid or sulfuric acid as pH adjusting agent, or the sour agent such as organic acid such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, or sodium hydroxide or potassium hydroxide, ammonia or derivatives thereof, MEA or the amine salt such as diethanol amine, triethanolamine etc., the alkaline agent such as sodium carbonate, potash.In addition, these sour agent can also be combined and alkaline agent uses as system buffer.
PH at 20 DEG C is adjusted to 2 ~ 12 from the viewpoint of antibiotic property preferably by above-mentioned pH adjusting agent by the antimicrobial composition of the invention described above, is particularly preferably adjusted to pH4 ~ 11.
The content of the composition (A) in antimicrobial composition of the present invention, from the view point of antibiotic property, is preferably 0.1 ~ 100,000ppm, more preferably 10 ~ 10,000ppm.
In addition, the content of composition (B) is preferably 100ppm ~ 100,000ppm, more preferably 100ppm ~ 50, and 000ppm, is more preferably 2,000ppm ~ 20,000ppm.
Specifically, the content of composition (A) and (B), octyl group benzyl dimethyl ammonium salt, dodecylbenzyl dimethyl ammonium or didecyldimethyl ammonium salt is being used as composition (A), such as, and when using benzylalcohol as composition (B), can enumerate composition (A) is 2,000 ~ 6,000ppm, composition (B) is 5,000ppm ~ 20,000ppm; Composition (A) is 2,400 ~ 6,000ppm, and composition (B) is 5,000ppm; Composition (A) is 25 ~ 400ppm, and composition (B) is 2,000 ~ 5,000ppm etc.
In addition, octyl group benzyl dimethyl ammonium salt is being used as composition (A), dodecylbenzyl dimethyl ammonium or didecyldimethyl ammonium salt, and use benzylalcohol as composition (B), ethylene glycol ether, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, when amylalcohol or 1-phenoxy group-2-propyl alcohol, such as, can enumerate composition (A) is 10 ~ 10, 000ppm, composition (B) is 4, 000 ~ 760, 000ppm etc.
In addition, octyl group benzyl dimethyl ammonium salt, dodecylbenzyl dimethyl ammonium or didecyldimethyl ammonium salt is being used as composition (A), and when using diethylene glycol list n-butyl ether or ethylene glycol mono hexyl ether as composition (B), such as can enumerate composition (A) is 10,000 ~ 100,000ppm, composition (B) is 100ppm ~ 100,000ppm etc.
In addition, as mentioned above, antibacterial agent of the present invention can only by composition (A) and (B), or together with other composition, or be matched with in the product or preparation used in various living environment and use, no matter but under what circumstances, all preferred mode of concentration in above-mentioned scope with the composition when contacting with microorganism (A) and (B) uses.Therefore, antimicrobial composition of the present invention also can be estimate dilution in practical usage situations for the composition concentrated further in above-mentioned scope.
Antibacterial agent of the present invention or the bactericidal composition containing this antibacterial agent can be prevented the attachment of pink dirt by being applied to the place easily producing microbial contamination or removing pink dirt.
Specifically, antibacterial agent of the present invention or the antimicrobial composition containing this antibacterial agent can in living environments, particularly (the bathroom, living space that easily raises of temperature or humidity, kitchen, washroom, toilet etc.) etc. easily produce the hard surface in the place of microbial contamination, such as, for kitchen or bathroom, toilet, the wall of washstand etc. or floor, the bottom of washing bucket, the bottle bottom of shampoo etc., discharge outlet, near tap, water line portion etc. in the closet of toilet, before the pink dirt of generation or after producing, use by being coated with.At this, coating method is not particularly limited, and can enumerate directly to be applied in object surface by composition, to be filled in the sprayer units such as trigger (Trigger) or aerosol and to spray etc.
Embodiment
Below, based on embodiment, the present invention is further elaborated.
The analysis of the pathogen of the pink dirt of reference example 1
(1) analysis carrying out the pathogen of pink dirt is observed by SEM
From the bathroom of 14 families, wipe the pink dirt getting 39 sample bathrooms with toothpick, the glutaraldehyde solution with 2.5% cleans with the 100mM phosphate buffer of pH7.6, dewaters by rising graded ethanol system after being suspended and fixing.After freeze-dried further more on the surface after evaporation platinum vanadium, scanning electron microscope (SEM) (S4300SE/N, Hitachi) is used to observe under 7 ~ 15kV.An example of SEM observed result is shown in Fig. 1.
In whole sample, all bacteriums are all the size of less than 3 μm substantially, do not observe the bacterium of more than 5 μm.That is, in whole samples, there is advantage in the bacterium with bacterium size and shape, and the bacterium of yeast size does not exist advantage.Therefore, represent the main pathogenic fungi of pink dirt be not yeast rhodotorula ( rhodotorula) belong to.
(2) analysis by the microscopical pink dirt of the confocal laser of FISH is used
The bathroom of 13 families reclaims 17 samples being attached with the container of pink dirt, pink dirt on this container and simultaneously cutting with the part of pink dirt is taken off, is placed on 3%(v/v) fix 2 hours in the paraformaldehyde aqueous solution (Sigma-AldrichJapanK.K.).After removing unnecessary moisture with paper handkerchief, be embedded in polyacrylamide gel.By this embedded samples be used for detecting Methylobacterium ( methylobacterium) belong to the fluorescence probe of bacterium (to AGCGCCGTCGGGTAAGA(sequence number 1, Pirttila, A., M., Laukkanen, H., Pospiech, H., Myllyla, R., andHohtola, Anja. (2000) " DetectionofintracellularbacteriainthebudsofScotchpine ( pinussylvestrisl.) byinsituhybridization. " Appl.Envion.Microbiol.vol.66 (7): 3073-3077.), the probe of rhodamine (rhodamine) X has been modified at 5 ' end side) carry out hybridization process, next again with fluorescence probe (the GCTGCCTCCCGTAGGAGT(sequence number 2 that can detect most bacterium, Amann, R., I., Krumholz, L., andStahl, D., A. (1990) " Fluorescent-oligonucleotideprobingofwholecellsfordetermi native, phylogenetic, andenvironmentalstudiesinmicrobiology. " JBacteriol.vol.172 (2): 762 – 770.), modified the probe of fluorescein isothiocyanate (fluoresceinisothiocyanate) at 5 ' end side) carry out hybridization process after, fluorometric reagent Calcofluorwhite(BD with being used in particular for dyeing containing more polysaccharide in fungi) dye, observe with confocal laser microscope (CLSM) (CarlZeissLSMMETA).In addition, in the hybridization process of fluorescence probe, in order to improve Methylobacterium ( methylobacterium) belong to the specificity of Bacteria Detection probe and fluorescence intensity and use assist probes.Probe is the oligonucleotides not modifying fluorchrome, design AGCGCCGTCTGGTAAGA(sequence number 3) and CCAACTCCCATGGTGACGA(sequence number 4) use.Assist probes passes through and the sequence similar with the binding sequence of probe is combined and improves the specificity of the binding sequence to probe, or, by and probe calmodulin binding domain CaM near DNA combine and change the three-dimensional structure of DNA, thus play and make probe easily be incorporated into effect on binding sequence.Assist probes adds with the mode of molal quantity identical with probe and probe simultaneously.An example of CLSM picture as shown in Figure 2.Red expression Methylobacterium ( methylobacterium) belong to the bacterium that bacterium, yellow green represent other, light blue expression mould and polysaccharide.
In observed whole 17 samples, implied Methylobacterium ( methylobacterium) belong to bacterium exist advantageously.Thus hint produce the main pathogenic fungi of pink dirt be Methylobacterium ( methylobacterium) belong to bacterium.
(3) analysis of the pink dirt undertaken by the separation of bacterium
By the pink dirt (sample A ~ Q) of 17 samples gathered in the bathroom from 13 families, use potato dextrose agar (PotatoDextroseAgar, PDA) (Difco), PDA+ chloramphenicol (Chloramphenicol) (50 μ g/ml), nutrient agar (NutrientAgar, NA) (Difco) is as medium, at room temperature cultivates within 3 days.In this state, because various bacterium can form overlapping bacterium colony on agar medium, therefore, use each bacterium colony of platinum loop picking, be inoculated on new medium, to R2A at 25 DEG C, at 30 DEG C, cultivated 3 ~ 7 day time to other medium, and repeatedly repeats this operation, isolate mushroom.To be estimated as by the analysis of biochemical proterties using API to test (bioMerieux) Methylobacterium ( methylobacterium) belong to the bacterial classification of bacterium, determine the base sequence of the DNA in its 16SrRNA region, by homology search and the qualification carrying out bacterial classification based on the network analysis of base sequence.
Except judged by morphologic observation rhodotorula ( rhodotorula) belong to beyond yeast, also isolated a lot of Methylobacterium ( methylobacterium) belong to bacterium.
The analysis result of sample A ~ Q is as shown in table 1.Result is presented in pink dirt not only exists bacterium but also there is yeast, but in the bacterium existed substantially by Methylobacterium ( methylobacterium) belong to occupied by bacterium.
[table 1]
Note) table in zero represent this bacterium be detected.
Reference example 2 Methylobacterium ( methylobacterium) belong to the antibacterial agent patience of bacterium
Will from reference example 1(3) be separated in the bathroom pink dirt sample F that records qualification addicted to middle temperature Methylobacterium ( m.mesophilicum) FP4 thalline use PDA plating medium (Difco) at 30 DEG C, cultivate a night, on picking one platinum loop medium addicted to middle temperature Methylobacterium ( m.mesophilicum) thalline of FP4, be suspended in other potato dextrose broth (PotatoDextroseBroth, PDB) at 30 DEG C, shake cultivation 3 days.After its centrifugation (7000g × 5min.) is removed supernatant, make it to be suspended with the physiological saline of equivalent.Centrifugation again afterwards (7000g × 5min.), is modulated into the bacterium liquid of OD0.8 with physiological saline.Relative to this bacterium liquid of 10 μ l, that adds 1ml uses sterilizing water-reducible octyl group benzyl chloride solution (SANISOL08, Kao Corp), makes it contact 5 minutes.Then to be that the amount of 1/10th adds dilution octyl group benzyl chloride relative to lecithin-polysorbate (LP, LecithinPolysorbate) dilution (pharmaceutical worker's industry pure with light), make it inactivation, try to achieve surviving bacteria number by agar semar technique.According to same step modulation Escherichia coli ( e.coli) NBRC3972, staphylococcus aureus ( s.aureus)nBRC13276 and pseudomonas aeruginosa ( p.aeruginosa)nBRC13275(is by Biological Genetic Resources department of NBRC(independent administrative corporation product evaluation technical foundation mechanism) buy) bacterium liquid, try to achieve octyl group benzyl chloride solution add after surviving bacteria number.
As shown in table 2, Escherichia coli ( e.coli), staphylococcus aureus ( s.aureus), pseudomonas aeruginosa ( p.aeruginosa)in contact 5 minutes by the octyl group benzyl chloride solution of the concentration with 240 ~ 480ppm, can observe more than log2 bacterial population reduce, in contrast, addicted to middle temperature Methylobacterium ( m.mesophilicum) in by contacting 60 minutes with the octyl group benzyl chloride solution of 6000ppm concentration when, can observe significant bacterial population reduce.By this result, display Methylobacterium ( methylobacterium) belong to pre biooxidation for antibacterial agent, there is very high patience.
By this result also imply Methylobacterium that survival ability is high ( methylobacterium) belong to the main pathogenic fungi that bacterium is pink dirt.
[table 2]
*the log value of the minimizing bacterial population (c.f.u./ml) after the numeric representation contact each time in table.
* 1) octyl group benzyl chloride concentration (ppm)
Embodiment 1 pair of Methylobacterium ( methylobacterium) belong to the evaluation (1) of antimicrbial power of bacterium
According to reference example 2 same step modulation addicted to middle temperature Methylobacterium ( m. mesophilicum) FP4 bacterium liquid.In addition, according to step modulation octyl group benzyl chloride solution (2400 ~ 6000ppm) same with reference example 2, benzylalcohol (BA) is added wherein to 5000ppm.This octyl group benzyl chloride+BA solution (1ml) is added to addicted to middle temperature Methylobacterium ( m.mesophilicum) contact 5 minutes with bacterium in FP4 bacterium liquid (10 μ l).Result is as shown in table 3.
As shown in Table 3, being used alone and not having the octyl group benzyl chloride concentration of antibiotic property to be in the solution of 2400 ~ 6000ppm in 5 minute contact time, by adding BA5000ppm, high combined effect can be obtained.
[table 3]
Embodiment 2 pairs of Methylobacterium ( methylobacterium) belong to the evaluation (2) of antimicrbial power of bacterium
According to shown in the step modulomenter 4 same with reference example 2 various Methylobacterium ( methylobacterium) belong to Bacteria liquid.In addition, according to addicted to middle temperature Methylobacterium ( m. mesophilicum) the same method of FP4 is separated and obtains from bathroom m.fujisawaensegP1 and the Methylobacterium of resistance to ray ( m.radiotolerans) AP2.Other bacterial strain is buied by Physical Chemistry Inst's Biological Resource Center (BioResourceCenter).In addition, and step modulation dodecylbenzyl dimethylammonium chloride ammonium salt solution (39 ~ 313ppm) that reference example 2 is same, add benzylalcohol (BA) wherein to 2000 ~ 5000ppm.This dodecylbenzyl alkyl dimethyl ammonium chloride+BA solution (1ml) is added in each Bacteria liquid (10 μ l) and contacts 5 minutes with bacterium.Result is as shown in table 4.Represent with the order of " +++ ﹥ ++ ﹥+" in table and confirm there is vigorous propagation.On the other hand, "-" expression does not find that there is breeding.Therefore, represent that antibiotic property is high with the step of "-﹥+﹥ ++ ﹥ +++ ".
Confirming for whole bacterial strains by table 4, can antibiotic property be improved by adding BA in dodecylbenzyl alkyl dimethyl ammonium chloride.
[table 4]
Addicted to middle temperature Methylobacterium (M.mesophilicum) FP4
M.fujisawaenseGP1
The Methylobacterium of resistance to ray (M.radiotolerans) AP2
Addicted to middle temperature Methylobacterium (M.mesophilicum) JCM2829
Turn round demethylation bacillus (M.Extorquens) JCM2805
The Methylobacterium of resistance to ray (M.radiotolerans) JCM2805
Embodiment 3 pairs of Methylobacterium ( methylobacterium) belong to the evaluation (3) of antimicrbial power of bacterium
According to reference example 2 same step modulation addicted to middle temperature Methylobacterium ( m. mesophilicum) FP4 bacterium liquid.In addition, according to step modulation octyl group benzyl chloride solution (10 ~ 10000ppm) same with reference example 2, the concentration shown in various organic solvents to table 5 shown in table 5 is added wherein.This octyl group benzyl chloride+organic solvent solution (1ml) is added into addicted to middle temperature Methylobacterium ( m.mesophilicum) contact 5 minutes with bacterium in FP4 bacterium liquid (10 μ l).Result is as shown in table 5.
Can confirm by table 5, be used alone as solvent for benzylalcohol, ethylene glycol ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, diethylene glycol single-benzyl ether, amylalcohol, 1-phenoxy group-2-propyl alcohol, benzaldehyde, diethylene glycol list n-butyl ether, or under being used alone the concentration without antibiotic property with octyl group benzyl chloride, have with octyl group benzyl chloride and effect.
[table 5]
Embodiment 4 pairs of Methylobacterium ( methylobacterium) belong to the evaluation (4) of antimicrbial power of bacterium
According to reference example 2 same step modulation addicted to middle temperature Methylobacterium ( m. mesophilicum)fP4 bacterium liquid.In addition according to step modulation octyl group benzyl chloride solution (10000 ~ 100000ppm) same with reference example 2, add various organic solvent shown in table 6 wherein to described concentration.By add in this octyl group benzyl chloride+organic solvent solution (1ml) addicted to middle temperature Methylobacterium ( m.mesophilicum) FP4 bacterium liquid (10 μ l) makes it contact 1 minutes.Result is as shown in table 6.
Can be confirmed by table 6, be used alone as solvent for using diethylene glycol list n-butyl ether, ethylene glycol ether, or be used alone with octyl group benzyl chloride the concentration that do not show antibiotic property and under time of contact, have with octyl group benzyl chloride and effect.
[table 6]
Embodiment 5 pairs of Methylobacterium ( methylobacterium) belong to the evaluation (5) of antimicrbial power of bacterium
According to embodiment 2 same step modulation addicted to middle temperature Methylobacterium ( m. mesophilicum)fP4 bacterium liquid.In addition according to the quaternary ammonium salt solution (25ppm or 400ppm) shown in the step modulomenter 7 same with reference example 2, add benzylalcohol wherein to 5000ppm.This quaternary ammonium salt+benzyl alcohol solution (1ml) is added into addicted to middle temperature Methylobacterium ( m.mesophilicum)5 minutes are contacted with bacterium in FP4 bacterium liquid (10 μ l).Result is as shown in table 7.
Can be confirmed, except octyl group benzyl chloride, in dodecylbenzyl alkyl dimethyl ammonium chloride or DDAC, also to there is very high combined effect by table 7.
[table 7]
*in table, BA+ represents the system that with the addition of BA, and BA-represents the system of not adding BA.
Embodiment 6 is for the clean-up performance evaluation of model pink dirt
According to reference example 2 same step modulation addicted to middle temperature Methylobacterium ( m. mesophilicum) FP4 bacterium liquid (OD0.8).Next, by 10 × 10 × 2(mm) fibre reinforced composites (FiberReinforcedPlastics, being called for short FRP) section use UV radiation sterilization after impregnated in ethanol, cuts into slices to loading this FRP in microtiter plates (Microtiterdish), interpolation 1mL bacterium liquid.By its quiescent culture 6 days at 30 DEG C, only FRP section is transplanted in 24 new orifice plates, a dry late analogue formation pink dirt at 30 DEG C.
At octyl group benzyl chloride (10000ppm) solution or octyl group benzyl chloride (10000ppm)+BA(5000ppm) dipping is attached with the FRP section of model dirt in solution, after leaving standstill 5 minutes, by the test tube of the LP dilution of section dislocation 1mL in dispensing, by peeling off bacterium by vortex mixer high degree of agitation, make it dispersion, measure the bacterial population of stripping, dispersed bacterium.FRP section after stripping, disperse bacterial again loaded in microtiter plates in addition, quiescent culture at 30 DEG C, measures the time that bacterium breeds again.Result is as shown in table 8 and table 9.
Impregnated in the addition of in octyl group benzyl chloride BA solution for Methylobacterium ( methylobacterium) belong to bacterium have in the solution of high degerming ability FRP section in, bacterial population greatly reduces.And breed again to the upper bacterium of section and need the plenty of time.On the other hand, in the FRP section that impregnated in octyl group benzyl chloride solution, bacterial population does not reduce, and finds breeding again of bacterium rapidly.
[table 8]
*in table, BA+ represents the system that with the addition of BA, and BA-represents the system of not adding BA.
[table 9]
Water Octyl group benzyl chloride Octyl group benzyl chloride+BA
2 days 6/6 3/6 0/6
3 days 6/6 5/6 0/6
5 days 6/6 6/6 1/6
6 days 6/6 6/6 3/6
*pollute the time of needs after the test of antibiotic property shown in table again, in table, denominator represents the sum of pilot region, point subrepresentation polluted test region number again.

Claims (19)

1. pink dirt prevent attachment or a removing method, wherein,
Bactericidal composition is applied to easily produce Methylobacterium ( methylobacterium) belong to the place of germ contamination,
Described bactericidal composition contains: 25 ~ 400ppm is selected from the quaternary ammonium salt of more than a kind in didecyldimethyl ammonium salt and dodecylbenzyl dimethyl ammonium as composition (A), and 2, the benzylalcohol of 000 ~ 5,000ppm is as composition (B);
Or,
Described bactericidal composition contains: 10 ~ 100, the octyl group benzyl dimethyl ammonium salt of 000ppm is as composition (A), and 100 ~ 100,000ppm be selected from the organic solvent of more than a kind in benzylalcohol, ethylene glycol ether, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, amylalcohol and 1-phenoxy group-2-propyl alcohol as composition (B).
2. pink dirt as claimed in claim 1 prevent attachment or removing method, wherein,
Easy generation Methylobacterium ( methylobacterium) to belong to the place of germ contamination be more than 1 place being selected from bathroom, kitchen, washroom, toilet.
3. pink dirt as described in claim 1 or 2 prevent attachment or removing method, wherein,
Subject is ground or the wall at more than 1 place being selected from bathroom, kitchen, washroom, toilet, or is selected from bottom the bottom of washing bucket, bottle, near discharge outlet, tap, more than 1 place in the water line portion of the closet of toilet.
4. an antibiotic method, wherein,
Quaternary ammonium salt represented by following composition (A) and the organic solvent represented by (B) are applied to easily produce Methylobacterium ( methylobacterium) belong to the place of germ contamination,
(A) more than a kind 25 ~ 400ppm in didecyldimethyl ammonium salt and dodecylbenzyl dimethyl ammonium is selected from,
(B) benzylalcohol 2,000 ~ 5,000ppm;
Or,
(A) octyl group benzyl dimethyl ammonium salt 10 ~ 100,000ppm,
(B) organic solvent 100 ~ 100,000ppm of more than a kind in benzylalcohol, ethylene glycol ether, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, amylalcohol and 1-phenoxy group-2-propyl alcohol is selected from.
5. antibiotic method as claimed in claim 4, wherein,
Composition (A) is 10 ~ 10, the octyl group benzyl dimethyl ammonium salt of 000ppm, composition (B) is 4, the aromatic alcohols being selected from benzylalcohol, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, amylalcohol and 1-phenoxy group-2-propyl alcohol of 000 ~ 20,000ppm.
6. antibiotic method as claimed in claim 4, wherein,
Composition (A) is the octyl group benzyl dimethyl ammonium salt of 2,000 ~ 6,000ppm, and composition (B) is the benzylalcohol of 5,000 ~ 20,000ppm.
7. antibiotic method as claimed in claim 4, wherein,
Composition (A) is the dodecylbenzyl dimethyl ammonium of 25 ~ 400ppm, and composition (B) is the benzylalcohol of 2,000 ~ 5,000ppm.
8. antibiotic method as claimed in claim 4, wherein,
Composition (A) is the octyl group benzyl dimethyl ammonium salt of 10,000 ~ 100,000ppm, and composition (B) is the ethylene glycol ether of 100 ~ 100,000ppm; Or composition (A) is the octyl group benzyl dimethyl ammonium salt of 10,000ppm, composition (B) is the diethylene glycol list n-butyl ether of 76,000 ~ 100,000ppm.
9. antibiotic method as claimed in claim 4, wherein,
The didecyldimethyl ammonium salt that composition (A) is 25ppm, composition (B) is the benzylalcohol of 5,000ppm.
10. as the antibiotic method in claim 4 ~ 9 as described in any one, wherein,
Salt is the salt with chloride ion.
11. antibiotic methods as claimed in claim 4, wherein,
Easy generation Methylobacterium ( methylobacterium) to belong to the place of germ contamination be more than 1 place being selected from bathroom, kitchen, washroom, toilet.
12. as the antibiotic method in claim 4 ~ 9 as described in any one, wherein,
Subject is ground or the wall at more than 1 place being selected from bathroom, kitchen, washroom, toilet, or is selected from bottom the bottom of washing bucket, bottle, near discharge outlet, tap, more than 1 place in the water line portion of the closet of toilet.
13. compositions containing the quaternary ammonium salt represented by following composition (A) and the organic solvent represented by (B) as purposes Methylobacterium (Methylobacterium) being belonged to the antibacterial agent of bacterium,
(A) more than a kind 25 ~ 400ppm in didecyldimethyl ammonium salt and dodecylbenzyl dimethyl ammonium is selected from,
(B) benzylalcohol 2,000 ~ 5,000ppm;
Or,
(A) octyl group benzyl dimethyl ammonium salt 10 ~ 100,000ppm,
(B) organic solvent 100 ~ 100,000ppm of more than a kind in benzylalcohol, ethylene glycol ether, diethylene glycol list n-butyl ether, diethylene glycol monohexyl ether, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, amylalcohol and 1-phenoxy group-2-propyl alcohol is selected from.
14. purposes as claimed in claim 13, wherein,
Composition (A) is 10 ~ 10, the octyl group benzyl dimethyl ammonium salt of 000ppm, composition (B) is 4, the aromatic alcohols being selected from benzylalcohol, 2-[2-(2-ethyl hexyl oxy) ethyoxyl] ethanol, 2-BOE, 2-phenoxetol, benzaldehyde, diethylene glycol single-benzyl ether, amylalcohol and 1-phenoxy group-2-propyl alcohol of 000 ~ 20,000ppm.
15. purposes as claimed in claim 13, wherein,
Composition (A) is the octyl group benzyl dimethyl ammonium salt of 2,000 ~ 6,000ppm, and composition (B) is the benzylalcohol of 5,000 ~ 20,000ppm.
16. purposes as claimed in claim 13, wherein,
Composition (A) is the dodecylbenzyl dimethyl ammonium of 25 ~ 400ppm, and composition (B) is the benzylalcohol of 2,000 ~ 5,000ppm.
17. purposes as claimed in claim 13, wherein,
Composition (A) is the octyl group benzyl dimethyl ammonium salt of 10,000 ~ 100,000ppm, and composition (B) is the ethylene glycol ether of 100 ~ 100,000ppm; Or composition (A) is the octyl group benzyl dimethyl ammonium salt of 10,000ppm, composition (B) is the diethylene glycol list n-butyl ether of 76,000 ~ 100,000ppm.
18. purposes as claimed in claim 13, wherein,
The didecyldimethyl ammonium salt that composition (A) is 25ppm, composition (B) is the benzylalcohol of 5,000ppm.
19. as the purposes in claim 13 ~ 18 as described in any one, wherein,
Salt is the salt with chloride ion.
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