JPS6345217A - Fungicidal composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to disinfectant compositions and their use for the disinfection and disinfection of skin and hands and of hard surfaces.

As bactericidal active substances, for example, hexachlorophene,
p-chloro-O-benzylphenol, O-phenyl-
Phenol, p-chloro-m-xylenol, 2.4-
Dichlorobenzyl alcohol, polyvinylpyrrolidone
Hand disinfectant disinfectants containing iodo complex salts, betaine, quaternary ammonium compounds, chlorhexidine salts, zinc pyridinethione, etc. are known. However, these known hand disinfectants generally have unnecessarily high active substance concentrations and/or have a narrow spectrum of action and/or have an unsatisfactory tolerance to skin la and/or
Or, it has drawbacks such as low skin affinity.

According to Ullmann 10.31, the average pH value of normal skin is 5.2, and the average pH value of hand skin is 4.5. During washing and washing, this pH value increases to some extent, depending on the type of detergent. H. Tony (H.

Tonnier), Gee Schuster (G,, 5c
Hu-ster), and H, Mod
Arch, klin, exptl, Derm,
) As reported in 221.232 (1985), a certain degree of alkalinity is currently allowed even if eradication is limited, taking into account the rapid recovery of monovalent skin. . However, this is for normal skin and is only acceptable for detergents that are used only 2.3 times a day. This is because alkaline conditions cause maceration symptoms, which strongly promote bacterial growth. This is because most pathogens prefer alkaline media [E.K.
Eining's paper, Aerztliche Praxis.

21, No. 103.5788-5794 (198
9)].

Even worse, in the case of skin cleansers that contain antiseptic additives and contain soaps or synthetic cleansers and are used 20 to 50 times a day, these undesirable effects can be compounded. It becomes even stronger. Additionally, the cleanser may contain alcohol such as ethyl alcohol, n-
When propyl alcohol, isopropyl alcohol, or a mixture thereof is contained, these effects are further enhanced. This is because the use of this alcohol substantially extends the neutralization time [W.
der ) paper, Theravivo 7, (Thera
Piewoche), pp. 18.875-879 (
1988)].

In the past, skin-friendly pH levels below 7 were often used without precipitation of the active substance and concomitant reduction in the level of action.
In order to keep the active substance in solution, it was not possible at first to produce liquid disinfectants containing halogenated hydroxydiphenyl ethers with a large amount of monohydric or dihydric alcohol, e.g. Ethyl alcohol,
This required the use of n-propyl alcohol, isopropyl alcohol, propylene glycol, very high surfactant concentrations, or the use of expensive amphoteric surfactants or betaine.

Furthermore, for example, skin cleansers or disinfectants containing halogenated hydroxydiphenyl ethers are effective against Durum-positive and Durum-negative bacteria at pH 7.2 to 7.8, but at pH 5.5, they are effective against Durum-positive bacteria and Durham-negative bacteria. At least some Durham-negative bacteria such as Escherichia coli (Esch
erichia coli) or Pseudomonas spp.
It has been found that this method is ineffective against bacteria such as Domonas aeruginosa.

There is therefore hereby provided according to the invention a disinfectant composition which can be used for skin and hand disinfection and sterilization, which does not have the above-mentioned disadvantages and which has a branch-friendly pH value of 5.0 to 5.5. It has been developed.

That is, the present invention relates to a fungicidal composition, and the features of the fungicidal composition of the present invention are as follows: a) 0.1 to 2.5% by weight of a fungicidal compound; b) Aryl- or aryloxy-C? -C4-alkanol 0 to 10% by weight, C) anionic surfactant O to 20% by weight, d) amphoteric (P?) surfactant O to 10% by weight, e) nonionic surfactant O to 10% by weight 3% by weight, f) dihydric alcohol 0-1531Q%, g) Cs-Cl2-fatty acid O-10% by weight, h) solubilizer 1-25% by weight, i) deionized water 4.5-98.9%. % by weight.

The 'f2 fungicide compositions of the invention can have a pH value in the range from 3.0 to 9.0 and can additionally contain conventional thickeners and opacifiers.

The disinfectant composition of the present invention is effective against both Gram-positive and Gram-negative bacteria, and can also be used against other microorganisms such as yeast, fungi, viruses, and algae.

Another object of the invention is the use of the water composition for the disinfection and sterilization of skin 1a and hands and for the disinfection and sterilization of hard surfaces.

As component (a), the following bactericidal substances can be used: (A) Compound of formula (1) below? H Table 3 where R1 is hydrogen, hydroxyl, c, -Ca-alkyl, chlorine, nitro, phenyl or benzyl, R2 is hydrogen, hydroxyl, Cl-Cb-alkyl or chlorine, R3 is hydrogen, C1-C6-alkyl , hydroxyl, chlorine, nitro or a sulfo group in the form of an alkali metal or ammonium salt, R4 means hydrogen or methyl, R5 means hydrogen or nitro.

Examples of compounds in this group are phenol, chlorophenol (o-, m-, p-), 2,4-dichlorophenol, p-nitrophenol, picric acid, xylenol, p-chlorom-xylenol, cresol (o -, m-, p-), p-chloro-m-cresol, pyrocatechol, resolnol, orcinol, 4-n-hexylresorcinol, pyrogallol, phloroglycitur, carvuacrool, thymol, p
-chlorothymol, O-phenylphenol, 0-benzylphenol, p-chloro-0-benzylphenol, 4-phenolsulfonic acid, and the like.

CB) Following - Compound of formula (2) In the formula, X is sulfur or methylene group, R1 and R1 are hydroxyl, R2, R;, R3, R3, R4, R'4, R5, Rζ are means hydrogen or chlorine.

For example, the compound of formula (2) is hexachlorophene,
Tetrachlorophene, dichlorophene, 2,3-dihydroxy-5,5'-dichlorodiphenyl sulfide,
2.2′-dihydroxy-3,3′,5.5′-tetrachlorodiphenyl sulfide, 2.2′-dihydroxy-3,3′,5.5°,6.6′-hexachlorodiphenyl sulfide, and 3,3′-dibromo-5,
5'-dichloro-2,2''-dihydroxydiphenylmethane and the like.

(c) Compound A3 of the following formula (3) In the formula, R1, R2, R3, R4, and R5 each independently represent hydrogen or chlorine.

Examples of compounds of formula (3) are benzyl alcohol, 2.4
−． 3.5- or 2.6-cyclobenzyl alcohol or trichlorobenzyl alcohol.

(D) Chlorhexidine and its salts with free or organic acids, (E) Cl2-Cl4-alkylbetaine and as
C'16 = fatty acid amidoalkyl betaine, for example coconut fatty acid amidopropyl betaine, (F) Cl2-C+a-alkylaminocarboxylic acid,
c. -c3-furcanecarboxylic acid, an amphoteric surfactant such as alkylaminoacetic acid or alkylaminopropionic acid, (G) zinc pyridinethione, (H) preferably a hydroxydiphenol ether of the following formula (4), R' 1 is hydrogen or hydroxyl, R2, R
2', R3, R4, Ra, and R5 independently represent hydrogen or chlorine, preferably R'2 and R'3 are chlorine, and R2, R. , R'4 and R5 mean hydrogen.

Particularly preferred compounds of formula (4) are 2, 4, and 4.
'-Trichloro-2'-hydroxydiphenyl ether.

The fungicidal active substances, alone or in the form of mixtures with each other,
In other words, it is also possible to use a mixture of fungicidal agents of the same or different classes. The same is true for components (c) and (d
) and (e).

Aryl- or aryloxy-C2-ca-alkanolkas having unsubstituted aryl groups and straight-chain alkylene groups are preferably considered as component (b). 2-phenylethanol, 2-phenoxyethanol, 3-phenokidibrobanol, and 4-phenoxybutanol are preferred, and 2-phenoxyethanol is particularly preferred.

Component (c) of the agent according to the invention is sarcosinate;
Sulfurizing surfactants, such as alkyl sulfate,
Alkyl ether sulfates, alkylamides sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates or monoglyceride sulfates, sulfonates such as alkyl sulfonates, alkylamides sulfonates, alkylaryl sulfonates, α-olefin sulfonates; or sulfosuccinic acid derivatives such as alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl ether sulfosuccinates, or alkyl sulfosuccinamide derivatives, and also fatty acid methyltaurides, alkyl isosuccinates; Thionates, fatty acid polypeptide condensation products and fatty alcohol phosphate esters are considered. Preferably, the alkyl group present in these compounds has 8 to 24 carbon atoms.

These anionic surfactants are generally in the form of their water-soluble salts, e.g. alkali metal salts, especially sodium or potassium salts, or alkaline salts, where R1, R2, R3 are independently of each other hydrogen, cl-Ca-alkyl or ct
-C4-Hydroxyalkyl. Preferred anionic surfactants are c. -c24-alkyl sulfate, particularly preferably monoethanolamine-lauryl sulfate.

Zwitterionic surfactants for component (d) include CB-Cl8-betaine, C8-Cl8-sulfobetaine, ca-C24-fulkylamide-C1-C
4-alkylene betaine, imidacillin carboxylate,
N-furkyl-β-amino- or imino-propionate etc. are considered, Cl0-C20-furkylamide-
CI-C4-alkylene betaine is preferred, and coconut fatty acid amidopropylene betaine is particularly preferred.

Examples of nonionic surfactants used as component (e) are polypropylene glycol ethoxylates having a molecular weight of 1,000 to 15,000, fatty acid glycol partial esters such as diethylene glycol monostearate,
These include fatty W-furkaramides and dialkanolamides, fatty acid alkanolamide ethoxylates and fatty amine oxides. Fatty acid alkanolamides and dialkanolamides are preferred, particularly coconut fatty acid jetanolamide.

Particularly suitable as component (f) are dihydric alcohols having 2 to 6 carbon atoms in the algylene moiety. For example, l, 2- or 1,3-propanediol, 1.3
-1114- or 2,3-butanediol, 1.5-
These include pentadiol, 1,6-hexanediol, and the like. 1.2-Propanediol (propylene glycol)
These dihydric alcohols may be used alone or in admixture with one another.

Saturated and unsaturated C2-012 fatty acids, such as acetic acid, propionic acid, isovaleric acid, caproic acid, caprylic acid, capric acid, undecylenic acid, lauric acid, come into consideration as component (g). Preferred fatty acids are capric acid and undecylenic acid.

The following compounds come into consideration as component (h): niterpenoids or sulfonates of monocyclic or bicyclic aromatic compounds, such as the sulfonates of camphor, toluene, xylene, cumene, naphthol, these sulfonates with their water-soluble salts, e.g. , alkali metal salt,
Especially sodium or potassium salts, or amines (
N RIR2R3) salt form. Here, R1, R
2, R3 each independently represent hydrogen, C1-Ca-alkyl, C2-C8-alkenyl, C1-ca hydroxyalkyl, C,, -C,, -cycloalkyl or polyalkyleneoxy-Cl-Cps-alkyl or R1, R2, R3 together with the nitrogen atom to which they are attached mean morpholino or morpholino substituted with CI-C4-alkyl; -aliphatic saturated or unsaturated C14-C20-monocarboxylic acids, such as myristic acid, palmitic acid, stearic acid, arachidic acid, decylenic acid, dodecylenic acid, palmitoleic acid,
Oleic acid, ricinoleic acid, linoleic acid, lylunic acid, eleostearic acid, arachidonic acid, 5-eicosenoic acid, saturated or unsaturated C3-C12-di- or poly-carboxylic acids, such as malonic acid, succinic acid, geltaric acid , adipic acid, pimelic acid, succinic acid, azelaic acid, sebacic acid, undecane- and dodecane-dicarboxylic acids, fumaric acid, maleic acid, tartaric acid, malic acid, citronenic acid and aconitic acid; , hydroxyethylethylenediaminetetraacetic acid, nitrilotriacetic acid, etc.; monocyclic aliphatic carboxylic acids such as camphoric acid; monoaromatic carboxylic acids such as benzoic acid, phenylacetic acid,
Phenoxyacetic acid, cinnamic acid, salicylic acid, 3-hydroxy- and 4-hydroxy-benzoic acid, odorous acid, anisic acid and o-, m- and p-chlorophenylacetic acid, and -, m- and p-chlorophenoxyacetic acid; - Alkali metal and amine salts of inorganic acids such as a! acid, g, m
i, phosphoric acid, sodium salts, potassium salts and amines of Cl-Cl0-alkyl phosphoric acid and boric acid (N RIR
2R3) salt, where R1, R2, R3 are niisethionic acid monotannic acid acid amide of the following formula, where R1 is hydrogen, Cl-C12-alkyl, and R
2 and R3 are each independently CI -CI2-alkyl, C2-C12-alkenyl, C1-Cl2-hydroxyalkyl, C2-CI2-hydroxyalkenyl or 1 to 30 groups -CH2-CH2-O- or groups −
CHj+ -CHY2-0- (where Yl and R2 are one hydrogen and the other methyl) is meant a polyglycol ether chain. For example, N-methylacetamide; In the following formula, R1, R2, R3, and R4 are independently hydrogen,
c, -Cs-alkyl, C2-Cs-alkenyl, c,
-Cs-Hydroxyalkyl, also meaning t*c2-Cs-hydroxyalkenyl, aliphatic and monocyclic alcohols, such as C
2-C18-alkanols, C2-Cl8-artenols and terpene alcohols, such as ethanol, propatool, isopropanol, hexanol, cis
-3-hexen-1-ol, trans -2-hexen-1-ol, 1-octen-3-ol, heptatool, octatool, trans -2-cls
-6-nonadien-1-ol, decanol, linalool, geraniol, dihydroterpinol, myrcenol, nopol, terpinolny In the following aromatic alcohol formula, R1, R2, R3 are independently hydrogen, means hydroxyl, halogen or C1-C6-alkoxy. For example, benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenylethanol, phenoxyethanol, cinnamic alcohol, etc.: - free or alkoxylated, preferably ethoxylated and/or propoxylated polyhydric alcohols of the following formula; The ethers and esters R1-0-X-0-R2.

R1 and R2 each independently represent hydrogen, C1-CI2-alkyl, C2-C12-alkenyl, R3-(Offi
H-CHz) = (where ・R3 is hydrogen, C1-C12-
alkyl or C2-CI2-alkenyl, in which R4 means hydrogen or CH3-), X is C2-cto-alkylene or C2-CIO-alkylene, -(cCH2CH20)buH2 -CH2-
The compounds exemplified above may be used alone or in mixtures with each other, that is, compounds of the same or different classes may be used in admixture with each other.

The bactericidal m-acid of the present invention can be produced by a method known per se. For example, by dissolving component (a) in component (h) and adding the remaining components to the resulting solution, or alternatively by dissolving component (a) in component (f) and adding the remaining components to the resulting solution. It can be manufactured by adding ingredients.

The disinfectant composition of the invention thus obtained can be diluted for the disinfection and disinfection of the skin and hands or also for the disinfection and disinfection of hard surfaces, depending on the form of the formulation or the desired method of application. Alternatively, it can be applied to the objects to be disinfected without being diluted.

The composition of the invention preferably has the following composition: Component (a) 0.1 to 2.5% by weight Component (c)
0 to 20% by weight Component (d) 0 to 10% by weight Component (f) 0 to 15% by weight Component (g) 1 to 7% by weight Component (h) 1 to 25% by weight Deionized water
20.5 to 97.9% by weight Particularly preferred compositions according to the invention contain p-chloro-m-xylenol as component a and l-phenoxy-2-propertool as Ilb in a weight ratio of 1:2 to 1:3. Contained in ratio.

Optionally, customary additives can be added as opacifiers or pearlescent emulsifiers, such as ethylene glycol distearate, monostearate, glycerol monostearate, polystyrene latex.

Cellulose derivatives such as cellulose ethers, fatty acid alkanolamides, guar derivatives, Mg
It is also possible to use A1-silicates or glucamates.

Examples are shown below to explain the method for producing the composition of the present invention, where percentages are percent by weight and parts are parts by weight.

Actual JL Example 5 of sodium cumene sulfonate as a 40% aqueous solution
2.0 parts of 2.4.4'-trichloro-2'-hydroxydiphenyl ether was dissolved in 1 part of the solution. The resulting clear solution was heated to 40° C. and, with constant stirring, 12.0 parts of monoethanolamine-lauryl sulfate as a 30% aqueous solution, 3.0 parts of coconut fatty acid amidopropyl betaine, and propylene were added. Add 5.0 parts of glycol, 1.0 part of capric acid and 0.3 parts of polystyrene latex as opacifying agent. After the addition is complete, stirring is continued for another 10 minutes, after which the solution is brought to 100 parts (36.2 parts of water) with deionized water, and the pH value of the resulting cloudy solution is quenched. Adjust to 5 to 5.5 with acid or sodium hydroxide.

This preparation was highly effective against both Durham-positive and Durham-negative bacteria, as well as yeast and fungi.

[Niwasara] 5 of sodium cumene sulfonate as a 40% aqueous solution
2.0 parts of 2.4.4'-trichloro-2'-hydroxydiphenyl ether was dissolved in 1 part of the solution. The resulting clear solution was warmed to 40°C and heated with constant stirring for 3
09g monoethanolamine lauryl sulfate as an aqueous solution 12.0 parts, 3.01 parts of coconut fatty acid amidopropyl betaine, 5.0 fffi of propylene glycol,
Add 2.0 ffl undecylenic acid and 0.3 parts of polystyrene-lattice. After addition, add 1 more
Continue stirring for 0 minutes and then add deionized water to the solution to bring the total to 100 parts (35.2 parts of water), which brings the pH value of the cloudy solution to 5 to 5.5. Adjusted to.

The obtained preparation is suitable for both Durham-positive and Durham-negative bacteria.
It was also very effective against yeast and fungi.

In addition, aqueous citric acid or sodium hydroxide solution can be used if necessary to adjust the pH to 7A.

The procedure was carried out as in Examples 1 and 2 above, but using the compounds listed in the following table, which were also highly effective against Durham-positive and Durham-negative bacteria, as well as against yeasts and fungi. An effective composition was obtained.

A: 2,4,4'-trichloro-2°-hydroxydiphenyl ether Boo-phenylphenol C: p-chloro-0-benzylphenol D: p-chloro-m-xylenol E: Sodium lauryl ether sulfate (2 mol (ethylene oxide) F: Sodium lauroyl sarcosinate G: Fatty acid alkylolamide sulfosuccinate [e.g. ■ Rewopol 5BL2
06] H: Sodium-5ec-alkanesulfonate [e.g. ■ Ho5tapur SAS Go] I: Fatty acid amide alkyl betaine [e.g. ■ Tego Betain (T6go-Bet-ain)
) 17) J: Sodium-cocoamphocarpoxyglycinate: Propylene oxide/ethylene oxide block polymer
Molecular weight 6800 L Nitriethanolammonium-lauryl sulfate (sodium salt) M: Sodium xylene sulfonate N: Sodium cumene sulfonate 0: Citric acid P: Acetamide MEA [e.g. ■ Shellcomide (5cherco+Ilid) AME
) Q: EDTA R: Polypropylene glycol wood The pH value was adjusted with monomethanolamine.

Example 24 One part of 24.4°-trichloro-2'-hydroxydiphenyl ether is dissolved in 10 parts of propylene glycol. Add 13.35 parts of a 30% aqueous solution of cocoamidopropyl betaine to the clear solution and stir until homogeneous. 5 parts of sodium cumene sulfonate (powdered), 50 parts of deionized water, and 8 parts of citric acid hydrate are sequentially added to this solution with constant stirring. After addition, stir until a homogeneous suspension is obtained. pH of the resulting homogeneous suspension
The titer is adjusted to 5.0 using monoethanolamine and the clear solution is made up to 100 parts with deionized water.

11 Dissolve 1 part of 2.4.4°-trichloro-2°-hydroxydiphenyl ether in 10 parts of propylene glycol. Add 6.7 parts of a 30% aqueous solution of cocoamidopropyl betaine to the clear solution and stir until homogeneous. Add 5 parts of sodium cumene sulfonate (powder), 50 parts of deionized water, and 50 parts of deionized water to this solution with constant stirring.
Add 8 parts of citric acid-hydrate. After addition, stir until a homogeneous suspension is obtained. The homogeneous suspension obtained p)1
The titer is adjusted to 5.0 using monoethanolamine and the clear solution is made up to 100 parts with deionized water.

Example 26 Dissolve 1 part of 2.4.4'-trichloro-2''-hydroxydiphenyl ether in 10 i of propylene glycol. Heat this clear solution to 50°C and add cumene with constant stirring. Add 5 parts of sodium sulfonate (powder), 2 parts of propylene oxide/ethylene oxide block polymer of molecular weight 16800, 60 parts of deionized water, and 8 parts of citric acid-hydrate and stir until homogeneous. The pH number of the homogeneous suspension is adjusted to 5.0 using monoethanolamine and the clear solution is made up to 100 parts with deionized water.

Claims (1)

[Claims] 1. The following ingredients: a) 0.1 to 2.5% by weight of a bactericidal compound; b) Aryl- or aryloxy-C_2-C_4
-alkyl alkanol 0 to 10% by weight; c) anionic surfactant 0 to 20% by weight; d) amphoteric surfactant 0 to 10% by weight; e) nonionic surfactant 0 to 3% by weight. , f) 0-15% by weight of dihydric alcohol, g) 0-10% by weight of C_8-C_1_2-fatty acid, h) 1-25% by weight of solubilizer, i) 4.5-98.9% by weight of deionized water. A disinfectant composition characterized by containing. 2. Component (a) is the formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. 2. A composition according to claim 1, which is a hydroxydiphenyl ether of chlorine. 3. Component (a) is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. -C_6-alkyl or chlorine, R_3 means hydrogen, C_1-C_6-alkyl, hydroxyl, chlorine, nitro or a sulfo group in the form of alkali metal or ammonium salts, R_4 means hydrogen or methyl, R_5 means hydrogen or nitro) The composition according to claim 1, which is a compound of. 4. Component (a) has the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula,
The composition according to claim 1, wherein _5 and R_5 each independently represent hydrogen or chlorine. 5. A patent claim in which component (a) is a compound of the formula ▲There is a mathematical formula, chemical formula, table, etc.▼ (in the formula, R_1, R_2, R_3, R_4, and R_5 each independently mean hydrogen or chlorine) The composition according to item 1. 6. The composition according to claim 1, wherein component (a) is chlorhexidine. 7. The composition according to any one of claims 1 to 6, wherein component (b) is 2-phenoxyethanol. 8. The composition according to any one of claims 1 to 7, wherein component (c) is an alkanolamine fatty acid sulfate. 9. The composition according to any one of claims 1 to 8, wherein component (d) is a fatty acid amide alkylene betaine. 10. The composition according to any one of claims 1 to 9, wherein component (e) is a fatty acid dialkanolamide. 11. The composition according to any one of claims 1 to 10, wherein component (f) is C_2-C_6-alkylene glycol. 12. The composition according to any one of claims 1 to 11, wherein component (g) is a saturated fatty acid. 13. Claims 1 to 12, wherein component (h) is an alkali metal salt or ammonium salt of cumene sulfonic acid, xylene sulfonic acid, or toluene sulfonic acid.
The agent described in any of the paragraphs. 14. 0.1 to 2.5% by weight of component (a), 0 to 20% by weight of component (c), 0 to 10% by weight of component (d), 0 to 15% by weight of component (f), Claims 1 to 13 contain 1 to 7% by weight of component (g), 1 to 25% by weight of component (h), and 20.5 to 97.9% by weight of deionized water. The agent described in any of the above. 15. 0.1 to 2.5% by weight of 2,4,4'-trichloro-2'-hydroxydiphenyl ether as component (a)
, sodium monoethanolamine as component (c)
2 to 20% by weight of lauryl sulfate, component (d)
Coconut fatty acid amidopropyl betaine as 0 to 10
% by weight, 0 to 15% by weight of propylene glycol as component (f), 1% of capric acid or undecylenic acid as component (g)
15-7% by weight of sodium cumene sulfonate as component (h), and 20.5-92.9% by weight of deionized water. 16. A method of using the agent according to any one of claims 1 to 15 as a skin disinfectant and a hand disinfectant.