CN100399895C - Preservative blends containing quaternary ammonium compounds - Google Patents

Abstract

The present invention provides a biocidal composition comprising a synergistic mixture of certain quaternary ammonium biocides and one or more ketone acids, aromatic carboxylic acids, salts thereof, or mixtures thereof.

Description

The preservative blends that contains quaternary ammonium compound

The application is that application number is dividing an application of 02805821.6 patent application.

It is the right of No. the 60/345th, 878, U.S. Provisional Application No. the 60/279th, 082, the U.S. Provisional Application in March 1 calendar year 2001 and the applying date being October 19 calendar year 2001 that the application requires the applying date, and above-mentioned provisional application is all incorporated this paper by reference into.

FIELD OF THE INVENTION

The present invention relates to contain the antimicrobial compositions of following material: (a) (i) quaternary ammonium compound, (ii) polymeric quaternary ammonium compound, or (iii) its mixture and (b) (i) ring-type or acyclic ketone acid or its salt, (ii) aromatic carboxylic acids or its salt, or (iii) its mixture.

The background of invention

Known many quaternized and things (for example benzethonium chloride) are effective as antimicrobial and preservative.But benzethonium chloride and many other quaternary ammonium compounds are expensive.In addition, when quaternary ammonium compound is sneaked in the anionic preparaton, its effect generally will be lowered.Therefore, exist antimicrobial and anticorrosive composite that improves the quaternary ammonium compound that contains low concentration and the demand that continues of keeping its effect in the anionic preparaton.

The general introduction of invention

The applicant has been found that ketone acid, aromatic carboxylic acids and salt thereof can work in coordination with the performance that strengthens some ammonium.The applicant also has been found that, although these ammonium often do not have activity in the anionic preparaton, the mixture that contains at least a these ammonium and ketone acid, aromatic carboxylic acids, its salt or its mixture has activity in the anionic preparaton.

The invention provides the composition that contains following material:

(a) (i) has a structural formula N ⁺R ¹R ²R ³R ⁴X ^-Ammonium, R wherein ¹And R ²Be not replace or the straight chain of hydroxyl replacement or the C of branching independently ₁-C ₄Alkyl ,-(CH ₂CH ₂O) _mCH ₂CH ₂OH or-(CH ₂CHCH ₃O) _mCH ₂CHCH ₃OH (wherein m is 1 to 10); R ³C for replacement or unsubstituted benzyl, ethylbenzyl, methyl naphthyl or straight chain or branching ₁-C ₂₂Alkyl; R ⁴Be-R ⁵(O) _n(C ₆H ₄) R ⁶(wherein n is 0 or 1); R ⁵Be to replace or unsubstituted C ₁-C ₈Alkyl or C ₁-C ₈Alkoxyalkyl; R ⁶Be the C of hydrogen or replacement or unsubstituted, straight chain or branching ₁-C ₁₂Alkyl; And X ^-Be the anion of chloride, acetate, borate, propionate, carbonate, bicarbonate or hydroxide for example,

(ii) polymeric quaternary biocide, or

(iii) its mixture; And

(b) (i) ketone acid or its salt,

(ii) aromatic carboxylic acids or its salt, or

(iii) its mixture.

The preferred cyclic ketones acid of ketone acid.Said mixture has the Synergistic effect.

Another implementation of the present invention be by use antimicrobial or anticorrosion on effectively the composition of the present invention of amount suppress the method for the growth of microorganism on matrix.

The detailed description of invention

Except as otherwise noted, the term " replacement " that herein uses includes but not limited at least a in the following substituting group: C ₁-C ₁₂Alkyl (C for example ₁-C ₄Alkyl), halogen (for example chlorine), nitro and hydroxyl.

Term " biocide " includes but are not limited to bactericide, fungicide, insecticide and suppresses the growth of microorganism and insect and/or with its medicament of killing.

The term of Shi Yonging " anionic preparaton " refers to comprise the preparaton of one or more anionic compounds (for example anion surfactant) herein.

Described ketone acid or aromatic carboxylic acids can strengthen the biocidal effect of ammonium.These compositions can be used as antimicrobial, fungicide and bactericide and as in papermaking, weaving, agricultural and coatings industry and personal nursing, family, industry and the mechanism's articles for use as preservative.Said composition can be sneaked in the matrix that is subject to the growth of microorganism influence as preservative system.For example, preservative system can be sneaked into or as personal care product's (for example shampoo, hair care agent, face cream, washing lotion, cosmetics or soap), household supplies (for example fabric softener, cloth-washing detergent and hard surface cleaner) or industrial goods (paint, timber, textile, adhesive, sealant, leather, rope, paper pulp, plastics, fuel, oil, rubber working fluid, metal working fluids, starch or mineral slurry (for example clay, calcium carbonate or titanium oxide (TiO for example ₃) slurry)).

The applicant finds that also although ammonium (for example benzethonium chloride) does not often have activity in the anionic preparaton, in the presence of ketone acid, aromatic carboxylic acids and its salt, they have activity in this type of preparaton.

Generally speaking, preservative system fast-acting of the present invention (for example, typically, in a hour, count of bacteria being reduced 95,99,99.9 or 99.99%) and in long-time (for example at least 28 days) keep its effect (for example keeping) less than 10cfu/g.

Ammonium

According to a preferred implementation, R ⁵Be-CH ₂CH ₂OCH ₂CH ₂-.More specifically, R ⁴Be [2-[2-(4-diisobutylphenoxy base) ethyoxyl] ethyl].According to another preferred implementation, R ⁴It is benzyl.

The salt (benzyl ethoxy ammonium salt is otherwise known as) that preferred ammonium includes but not limited to benzyl ethoxy ammonium ([2-[2-(4-two isobutylphenyls) ethyoxyl] ethyl] dimethyl benzene ammonium methyl) for example benzethonium chloride (can be Hyamine available from the Lonza Inc. trade mark of N.J. Fair Lawn

1622) and the salt of benzalkonium, for example benzalkonium (can be Barquat available from the Lonza Inc. trade mark of N.J. Fair Lawn

MB-50 and MB-80 obtain).Preferred benzalkonium salt includes but not limited to (C ₁₂-C ₁₈) alkyl benzyl dimethyl ammonium salt (chlorination (C for example ₁₂-C ₁₈) alkyl benzyl dimethyl ammonium).

According to another preferred implementation of the present invention, anion X ^-It is the anion of carbonate.

Can (but not must) use any method known in this field that ammonium is encapsulated to increase its solvability in desirable solvent or preparaton.For example, ammonium can be encapsulated in cyclodextrin, calixarenes (for example 4-tert-butyl group cup [4] aromatic hydrocarbons), liposome, catezone or the both sexes betain polymer.

The polymeric quaternary biocide

The polymeric quaternary biocide that is suitable for includes but not limited to the polymeric quaternary borate, for example United States Patent (USP) the 4th, 970,201 and 5,304, polymeric quaternary borate of describing in No. 237 (above patent is incorporated this paper by reference into) and poly-[oxygen ethene (dimethylimino)-ethene (dimethylimino) (can be available from the Buckman Laboratories of tennessee,USA Memphis, the trade mark is BuckmanWSCP).

Ketone acid

Ketone acid can be ring-type or acyclic ketone acid.The term of Shi Yonging " cyclic ketones acid " comprises the compound of the ring with carbonyl group-containing groups herein.

The cyclic ketones acid that is suitable for includes but not limited to have the compound of following structural formula

And salt, wherein R ⁷, R ⁸And R ⁹Should be C independently of each other ₁-C ₁₀Alkyl, C ₁-C ₁₀Thiazolinyl, C ₁-C ₁₀Aryl or (C that thiazolinyl, aryl, halogen replace ₁-C ₁₀Alkyl) aryl.R ⁷, R ⁸And R ⁹Should be C independently of each other ₁-C ₄Alkyl; Or R ⁷And R ⁸Form 5-12 unit ring.Preferred cyclic ketones acid includes but not limited to have the compound of following structural formula

And salt.Preferred cyclic ketones acid is dehydroactic acid and salt (comprising its hydrate) thereof, for example dehydro sodium acetate (for example a hydration dehydro sodium acetate and a hydration dehydro sodium acetate).

Can (but not must) acid encapsulates to increase its solvability in desirable solvent or preparaton to cyclic ketones to use any method known in this field.For example, the cyclic ketones acid seal can be contained in cyclodextrin, calixarenes (for example 4-tert-butyl group cup [4] aromatic hydrocarbons), liposome, catezone or the both sexes betain polymer.Acid encapsulates to cyclic ketones can to use known any method in this field.

The combination of preferred cyclic ketones acid and ammonium is dehydroactic acid or its salt and benzethonium chloride.Preferred combination is dehydro sodium acetate and benzethonium chloride.

Aromatic carboxylic acids

The aromatic carboxylic acids that is suitable for includes but not limited to benzoic acid, its derivative and salt thereof.According to an implementation, aromatic carboxylic acids has following structural formula

R wherein ¹⁰And R ¹¹Be independently H ,-OH or-OC (O) CH ₃And R ¹²Be H, Na, K, Ca or Mg.Work as R ¹²During for Ca or Mg, aromatic carboxylic acids can be 1: 1 or 2: 1 with the ratio of Ca or Mg.

For example, aromatic carboxylic acids can be hydroxybenzoic acid, its derivative or its salt.Preferred hydroxybenzoic acid is salicylic acid and salt thereof.The salicylic salt that is suitable for includes but not limited to sodium salicylate.

The combination of preferred aromatic carboxylic acids or its salt and ammonium is sodium salicylate and benzethonium chloride.

Said composition can comprise solvent, for example water and the solvent miscible with water include but not limited to alcohol, dihydroxylic alcohols (for example glycerine, diglycerol, butanediol, butoxy diglycol, propane diols and dipropylene glycol), ester, ether, polyethers and any combination of above material arbitrarily.For example, solvent can comprise water and a kind of alcohol, for example Phenoxyethanol and/or phenmethylol.

In composition, can comprise other additive known to the personnel of general knowledge in this field.Useful additives includes but not limited to preservative, solubilizer, chelating agent (for example ethylenediamine tetra-acetic acid (EDTA) and salt thereof) and zeolite, surfactant (cation for example, anion, nonionic and amphoteric surfactant), antioxidant (for example butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT)), amine oxide, tertiary amine, zinc compound, hydrotropic agent, fluoride, magnesium salts, calcium salt, carboxylic acid, phosphate (phosphate), phosphonate (phosphonate), formaldehyde donor, glycereth-7, nutmeg acid myristin, glutaraldehyde, biguanides, natural products (geranoil for example, lichenic acid and tea oil) and any combination of above material arbitrarily.

The preservative that is suitable for includes but not limited to the chlorination quaternary ammonium, quaternary ammonium carbonate, benzalkonium, contain iodine compound (for example butyl carbamic acid-3-iodo-2-propynyl ester (IPBC)), glycolylurea (for example dimethyl hydantion and halogenated hydantoin), isothiazolinone (isothiazolinone), P-hydroxybenzoic acid (methyl P-hydroxybenzoic acid for example, ethyl P-hydroxybenzoic acid and propyl group P-hydroxybenzoic acid), chloroxylenol, chlorhexidine, Phenoxyethanol, phenmethylol, benzyl carbinol, benzoic acid and salt thereof, methaform, sorbic acid and salt thereof, triclosan, neko or any combination of above material arbitrarily

Typically, said composition is water or oil based system, is not emulsion.In oil based system, should and not that hydrate is advisable with ketone acid ammonium is not encapsulated as.The solvent that is applicable to oil based system is Phenoxyethanol and/or phenmethylol.

Said composition can be a liquid or solid.

Generally speaking, (1) weight ratio of ketone acid, aromatic carboxylic acids or its salt or its mixture and (2) ammonium, polymeric quaternary biocide or its mixture at about 0.00056: 1 to about 1990: 1 scope, preferably between about 0.0056: 1 to about 1400: 1.

In order to prepare the preparaton that contains composition of the present invention, generally at first prepare concentrate.Table A illustrated in typical concentrate each component and, based on 100% gross weight of concentrate, the scope that each component exists.

Table A

Scope	Ammonium, polymeric quaternary biocide or its mixture	Ketone acid, aromatic carboxylic acids, its salt or its mixture
			Generally	About 0.05 to about 90%	About 0.05 to about 99.5%
Preferably	About 0.5 to about 40%	About 0.50 to about 70%
			More preferably	About 1 to about 20%	About 5 to about 40%

With the concentrate dilution, the preferred use solvent identical with the solvent that is used for concentrate dilutes before using.Typically, the application dilution of composition contains killing biology, antifungal or sterilization effectively (1) ammonium and/or polymeric quaternary biocide (being component (a)) and/or (2) component (a) and the mixture (b) (wherein component (b) is ketone acid, aromatic carboxylic acids or its salt or its mixture) of amount.Typically, use dilution and also contain ketone acid or its salt, aromatic carboxylic acids or its salt or its mixture (being component (b)) of raising (or enhancing) being killed the effective amount of biology, antifungal or bactericidal effect.Generally speaking, use dilution and contain about 0.0001 weight % or 0.01 weight % concentrate to about 2 weight %.According to a preferred implementation, use dilution and contain about 0.1 concentrate to about 1 weight %.Table B illustrated in using dilution each component and, based on 100% gross weight of using dilution, the general range that each component exists.

Table B

Scope	Ammonium, polymeric quaternary biocide or its mixture	Ketone acid, aromatic carboxylic acids, its salt or its mixture
			Generally	About 0.00005 to about 0.45%	About 0.00005 to about 0.5%
Preferably	About 0.0005 to about 0.2%	About 0.0005 to about 0.35%
			More preferably	About 0.001 to about 0.1%	About 0.005 to about 0.2%

Another preferred implementation is the preservative preparaton of leaveing no choice but composition benzoic acid, Phenoxyethanol and phenmethylol that comprises dehydroactic acid, benzethonium chloride, salicylic acid and can contain or not contain again.100% gross weight based on the preservative preparaton, the preparaton of conc forms can contain 5 dehydroactic acids to about 40 weight % of having an appointment, about 1 benzethonium chloride to about 20 weight %, about 2.5 salicylic acids to about 20 weight %, and, what can contain or not contain leaves no choice but composition, about 2.5 benzoic acid to about 20 weight %, about 20 to about 50 weight % Phenoxyethanol and about 5 phenmethylols to about 50 weight %.100% gross weight based on the preservative preparaton, the implementation of preferred preservative preparaton contain the benzethonium chloride of the dehydroactic acid of the 10 weight % that have an appointment, about 5 weight % and about 10 weight % salicylic acid and, what can contain or not contain leaves no choice but composition, the Phenoxyethanol of the benzoic acid of about 10 weight %, about 35 weight % and the phenmethylol of about 30 weight %.

Thereby another implementation of the present invention be by with antimicrobial, sterilization or antifungal effectively the composition of the present invention of amount impose on and suppress microorganism, bacterium (staphylococcus aureus (S.aureus for example on the matrix, ATCC#6538), Pseudomonas aeruginosa (P.aeruginosa, ATCC#9027) and Escherichia coli (E.coli, ATCC#8739)) and/or fungi (for example candida albicans (Candidaalbicans) and aspergillus niger (Aspergillus the niger)) method of on matrix, growing.Composition can impose on the matrix with the known any method in this field, and said method includes but not limited to brush, floods, soaks, vacuum impregnation and pressure treatment.

Can be by ketone acid or its salt and/or aromatic carboxylic acids or its salt, ammonium, polymeric quaternary biocide, solvent and additive be mixed with composition of the present invention.Can or stir this mixture heating to quicken mixing.

The description of preferred implementation

Following examples have been illustrated the present invention and it have not been limited.Except as otherwise noted, all umbers and percentage are all by weight.

Embodiment 1

As follows to each anionic shampoo sample test in the following table 1.According to following program preparation standard mixed cell solution.3 agar stab cultures of staphylococcus aureus (ATCC#6538), Pseudomonas aeruginosa (ATCC#9027) and Escherichia coli (ATCC#8739) were cultivated about 24 hours down at about 35 ℃ respectively.Subsequently each acupuncture culture is washed with aseptic 0.85% salting liquid of 3mL.Thereby the cleaning solution of 3 acupuncture cultures is merged together formation organism mixture.By adding salting liquid the organism mixture is adjusted to about 1.00. salting liquid blank sample calibration spectroscope in the absorbance of 530nm.Thereby the organism mixture that 5mL measures consumption mixed obtain standardization mixed cell solution.Subsequently, each shampoo sample of 40g is inoculated and mixing with 0.2mL standardization mixed cell solution.The 1g mixture is added aseptic 20 * 150mm spiral cover test tube.

The aseptic D/E neutralizer of 9mL meat soup is added test tube also to be mixed to form 10 ^-1Dilution.Water with phosphate-buffered prepares until 10 ^-6Dilution serial dilution thing.The serial dilution thing is coated on the tryptic soy agar and at about 35 ℃ to descend to cultivate 2 days.Carry out count of bacteria after 0 and 14 day.The result is presented in the table 1.

Anionic protein shampoo Compositions comprise 35 weight % sodium lauryl tri(oxyethyl) sulfates, 25 weight % triethanolamine laurilsulfates, 3 weight % coconut oil diethanol amides (cocamideDEA), 1 weight % Hydrolyzed Collagen (can be available from Minn. Austin's HormelFoods, the trade mark is Polypro 5000 ^TM) and 36 weight % deionized waters.

Be mixed with a hydration dehydro sodium acetate, sodium salicylate and Hyamine by preservative and above-mentioned Anionic Protein matter shampoo Compositions with appropriate amount

1622 shampoo samples, and with mixture be heated to about 50 ℃ about 15 minutes.

Table 1

All percentages are the percetage by weight based on 100 weight % of total shampoo in the table 1.

¹One hydration dehydro sodium acetate can be available from the Lonza Inc. of N.J. Fair Lawn

²Hyamine

1622 is that chlorination diisobutylphenoxy ethoxyethyl dimethyl benzene ammonium methyl (benzethonium chloride) can be available from the Lonza Inc. of N.J. Fair Lawn

³Sodium salicylate can be available from the Sigma Chemical Co. of St. Louis

^*-being lower than the concentration of the preservative of appointment, shampoo contains 〉=10cfu/g after 14 days.

By being described in C.E.Kull etc., " as the quaternary ammonium compound of antifungal agent and the mixture of long-chain fatty acid ", Applied Microbiology, a hydration dehydro sodium acetate/Hyamine in the method computational chart 1 of 9:538-541 (1961) 1622 and sodium salicylate/Hyamine

1622 solution are at staphylococcus aureus, Pseudomonas aeruginosa and colibacillary synergy.Determined synergistic function value (synergism the value) (Q in the table 2 _A/ Q _a+ Q _B/ Q _b).Q _ABe (to have caused a hydration dehydro sodium acetate or the sodium salicylate concentration (in weight percent) of the mixture of plate count after 14 days＜10cfu/g) when having produced 100% bacterial growth retardance.Q _aBe to have produced the required independent hydration dehydro sodium acetate of 100% bacterial growth retardance or the concentration (in weight percent) of sodium salicylate.Q _BBe the Hyamine in the mixture when having produced 100% bacterial growth retardance

1622 concentration (in weight percent).Q _bBe to have produced 100% the required independent Hyamine of bacterial growth retardance

1622 concentration (in weight percent).

As (Q _A/ Q _a+ Q _B/ Q _b) value less than 1 o'clock, mixture has synergistic function.Equal 1 and greater than 1 (Q _A/ Q _a+ Q _B/ Q _b) value represented addition and reaction respectively.

The result is presented in the following table 2.

Table 2

Embodiment 2

Repeat the program of description among the embodiment 1 with the anionic shampoo in the following table 3.Carry out count of bacteria after 0 and 7 day.By with the preservative of suitable amount with anionic protein shampoo Compositions mixes and mixture is heated to about 50 ℃ about 15 minutes preparation dehydroactic acids (can available from the Lonza Inc. of N.J. Fair Lawn) and Hyamine

1622 shampoo samples.The result is presented in the following table 3.

Table 3

Dehydroactic acid/Hyamine in the table 3

1622 mixtures are determined by the program of describing among the embodiment 1 at staphylococcus aureus, Pseudomonas aeruginosa and colibacillary synergy.The result is presented in the following table 4.

Table 4

Embodiment 3

Repeat the program of description among the embodiment 1 with the anionic shampoo in the following table 5.By with the preservative of suitable amount with anionic protein shampoo Compositions mixes and mixture is heated to about 50 ℃ about 15 minutes preparation salicylic acids (can obtain from the Spectrum Chemical of N.J. New Brunswick) and Hyamine

1622 shampoo samples.The result is presented in the following table 5.

Table 5

Salicylic acid/Hyamine in the table 5

1622 solution are determined by the program of describing among the embodiment 1 at staphylococcus aureus, Pseudomonas aeruginosa and colibacillary synergistic function.The result is presented in the following table 6.

Table 6

Embodiment 4

By each composition being mixed with as following table 7 described preservative preparatons.

Table 7

Composition	％(w/w)
		Dehydroactic acid	10
Salicylic acid	10
		Benzoic acid	10
Benzethonium chloride	1
		Phenoxyethanol	37
Phenmethylol	32

Embodiment 5

By each composition being mixed with as following table 8 described preservative preparatons.

Table 8

Composition	％(w/w)
		Dehydroactic acid	10
Salicylic acid	10
		Benzoic acid	10
Benzethonium chloride	5
		Phenoxyethanol	35
Phenmethylol	30

Embodiment 6

As follows to each anionic shampoo sample test in the following table 9.According to following program preparation standard mixed cell solution.Cultivated respectively about 48 hours and 7 days under each comfortable about 25 ℃ of 2 agar slant cultures of candida albicans and 4 the agar slant cultures of aspergillus niger.Each slant culture is washed with aseptic 0.85% salting liquid of 3mL, collect also and in tissue grinder, flood.0.85% salting liquid that in each slant culture, adds q.s, thus count with the vision that the Neubauer hemacytometer obtains each candida albicans and aspergillus niger inoculum at microscopically.Thereby each candida albicans and the aspergillus niger standardization inoculum of equal volume are mixed formation standardization mixed fungus solution.

Each shampoo sample of 40g is inoculated and mixing with 0.4mL standardization mixed fungus solution.The 1g mixture is added aseptic 20 * 150mm spiral cover test tube.

The aseptic D/E neutralizer of 9mL meat soup is added test tube also to be mixed to form 10 ^-1Dilution.Water with phosphate-buffered prepares until 10 ^-6Dilution serial dilution thing.The serial dilution thing is coated on the sabouraud's glucose agar and at about 25 ℃ to descend to cultivate 5 days.Carry out the fungi counting after 0 and 14 day.The result is presented in the table 9.

Anionic protein shampoo Compositions has been described among the embodiment 1.By with the preservative of appropriate amount with anionic protein shampoo Compositions mixes and mixture is heated to about 50 ℃ about 15 minutes preparation shampoo samples.

Table 9

Result in the table 9 shows that benzethonium chloride does not have activity in the anionic preparaton.1.0% or 10, the 000ppm benzethonium chloride is invalid to the mixed fungus that reduces in the anionic shampoo.The shampoo sample that contains 0.6% embodiment 4 (60ppm benzethonium chloride) shows its logarithm in the fungi plate count be 2 decline.The shampoo sample that contains 0.6% embodiment 5 (300ppm benzethonium chloride) shows its logarithm in the fungi plate count be 4 decline.This demonstrates preservative blends of the present invention and has strengthened the fungicidal efficiency of benzethonium chloride in the anionic preparaton.

Embodiment 7

To the program test of each face cream sample in the following table 10 according to description among the embodiment 1.Glycerin monostearate (GMS) face cream of describing in the table 10 is prepared as follows.Polyoxyethylene glyceryl monostearate, glycerin monostearate, cetearyl alcohol, propionic acid myristin are mixed in first container and be heated to 60 ℃.In second container, glycerine and deionized water are mixed and be heated to 60 ℃.Solution in first container is poured in second container.With second container maintain 60 ℃ following 10 minutes.Solution in second container is cooled off.Thereby with sodium hydroxide the pH of solution is adjusted to pH 7 and obtains the GMS face cream.

Table 10

By with the preservative of appropriate amount with the GMS frost mixes and mixture is heated to 50 ℃ of 10-15 minute preparation 0.4% embodiment 5 samples.The result is presented in the following table 11.

Table 11

Most preservatives have effect slowly (for example need 3 or time of more days to reduce the number of microorganism), and the preservative system that shows in the table 11 works (for example typically in 1 hour) apace and keep its effect (for example at least 28 days) in long-time.

All above-mentioned patents, application, article, publication and method of testing are all incorporated this paper by reference into.

According to above detailed description, the skilled person in this field can associate many modification of the present invention.This type of tangible modification is to be included in the desired complete scope of claims.

Claims (10)

1. one kind is suppressed the method that microorganism grows in the anion preparaton, has the mixture of the following material of synergistic function comprising adding in described anion preparaton:

(a) salt of benzyl ethoxy ammonium; With

(b) following material is at least a:

(i) dehydroactic acid or its salt; With

(ii) salicylic acid or its salt.

2. according to the process of claim 1 wherein that described Synergistic mixture comprises (i) dehydroactic acid or its salt and (ii) salicylic acid or its salt.

3. according to the method for claim 2, wherein said Synergistic mixture also comprises:

(c) benzoic acid or its salt;

(d) Phenoxyethanol; With

(e) phenmethylol.

4. according to each method among the claim 1-3, wherein said anion preparaton is the personal care product.

5. according to the method for claim 4, wherein said personal care product is selected from shampoo, hair care agent, face cream, washing lotion, cosmetics and soap.

6. anion preparaton wherein comprises the mixture of the following material with synergistic function:

(a) salt of benzyl ethoxy ammonium; With

(b) following material is at least a:

(i) dehydroactic acid or its salt; With

(ii) salicylic acid or its salt.

7. according to the anion preparaton of claim 6, wherein said Synergistic mixture comprises (i) dehydroactic acid or its salt and (ii) salicylic acid or its salt.

8. according to the anion preparaton of claim 7, wherein said Synergistic mixture also comprises:

(c) benzoic acid or its salt;

(d) Phenoxyethanol; With

(e) phenmethylol.

9. according to each anion preparaton among the claim 6-8, it is the personal care product.

10. according to the anion preparaton of claim 9, wherein said personal care product is selected from shampoo, hair care agent, face cream, washing lotion, cosmetics and soap.