SK24597A3 - Surface-active formulations - Google Patents

Abstract

The invention relates to surface-active soap formulations, comprising (a) 0.01 to 0.2 % by weight of a microbicidal active substance, (b) 0.1 to 7.5 % by weight of one or more than one hydrotropic agent, (c) 0 to 2 % by weight of one or more than one synthetic surface-active substance or of a soap or of combinations of the cited substances and/or of a salt of a saturated and/or unsaturated C8-C22fatty acid, (d) 0 to 10 % by weight of a dihydric alcohol, (e) 0 to 70 % by weight of a monohydric alcohol, and (f) mains water or deionised water to make up 100 %. The formulation is used for the disinfection and cleansing of the human skin and hands and of hard objects.

Description

Field of the invention

The invention relates to surfactant compositions as well as to their use for disinfecting and cleaning human skin, hands and resistant articles.

BACKGROUND OF THE INVENTION

Special hygiene requirements exist not only in hospitals, restaurants or the food sector, but also in the private sector, such as private households or when traveling, and in these sectors the requirements for the use of disinfectants are less stringent than in the above group. However, these disinfectants should act as quickly as possible and their purchase should pay off, as they are well-tolerated and environmentally safe.

SUMMARY OF THE INVENTION

It has now surprisingly been found that a formulation containing an extremely low concentration of microbicidally active substance as well as other components, usually surfactant components, has these properties.

The present invention provides a surfactant comprising (a) from 0.01% to 0.2% by weight of a microbicidal active ingredient, (b) from 0.1% to 7.5% by weight of one or more hydrotropes, (c) 0 to 2% by weight of one or more than one synthetic surfactant or soap or a combination of said substances and / or a saturated salt and / or an unsaturated fatty acid of 8 to 22 carbon atoms; (e) 0 to 70% by weight of a monohydric alcohol; and (f) as a major component water or deionized water up to 100%.

By soap formulations are meant aqueous soap solutions which can be obtained as soaps or as so-called syndet solutions (synthetic detergent).

The antimicrobial activity of the novel formulations has an effect on gram-positive and gram-negative bacteria as well as on yeast, dermatophytes and the like.

Suitable components (a) are preferably 2-hydroxydiphenyl ethers, 2-hydroxy-diphenylmethanes and 2-hydroxydiphenylthioethers in general of formula I Y r- -Λ Λ-A Λ / si ( ¹ ) ^<H ° C = (\ = A (OH) _n OH

where

X is O, S or -CH-,

Y is a chlorine or bromine atom,

Z is SO 4 H, NO _a or alkyl having 1 and 4 carbon atoms, r is 0 to 3, o is 0 to 3, p is 0 or 1, m is 0 or 1, and n is 0 or 1.

Of particular interest are compounds of formula I wherein

X is oxygen, sulfur or -CH-, and

Y is chlorine or bromine, m is 0, n is 0 or 1, o is 1 or 2, r is 1 or 2 and p is 0.

s

Even more important are compounds of formula I wherein X is an oxygen atom, and

Y is chlorine, m is 0, n is 0, o is 1, r is 2 and p is 0.

Most preferred is a compound of formula II

(II)

Component (a) is preferably present in the novel formulation in an amount of 0.02 to 0.2% by weight.

The following components are preferably used as component (b):

(b _x ): sulfonates, preferably salts of terpenoids or aromatic compounds with one or two nuclei, for example sulfonates of camphor, toulene, xylene, cumene or naphthene, (b ₂ ): saturated or unsaturated di- or polycarboxylic acids with 3 to 12 atoms carbon such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid and malic acid as well as citric acid and acid aconitic, (b ₃ ): -aliphatic saturated or unsaturated monocarboxylic acids having 1 to 11 carbon atoms, for example acetic acid, propionic acid, hexanoic acid, capric acid or undecylenic acid,

saturated or unsaturated di- or polycarboxylic acids malonic, adipic, azelaic with 3 to C acid, succinic, pimelic acid, for example glutaric acid, suberic acid, sebacic acid, undecanecarboxylic acid and dodecanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid and malic acid, as well as citric acid and aconitic acid,

- aminocarboxylic acids, for example ethylenediaminetetraacetic acid, hydroxyethylenediaminetetraacetic acid and nitrilotriacetic acid,

- cycloaliphatic carboxylic acids such as camphoric acid,

aromatic carboxylic acids, for example benzoic acid, phenylacetic acid, phenoxyacetic acid and cinnamic acid, 2-, 3- and 4-hydroxybenzoic acid, anilic acid, as well as o-, m- and p-chlorophenylacetic acid and o-, m - and p-chlorophenoxyacetic acid,

- alkali metal and amine salts of inorganic acids, for example sodium or potassium salts and ammonium (NR ^X R ² R ³ ) salts of hydrochloric, sulfuric, phosphoric, alkylphosphoric, where the alkyl group has 1 to 10 carbon atoms, and boronous, where the ammonium salts of R ^1, R ² and R ³ are as defined above,

- 2-hydroxyethanesulfonic acid,

- tannic acid,

- acid amides of the general formula III

R ²

FROM

R ^{X -} CO - N (III)

R ³ where

R ^x is hydrogen or C 1 -C 12 alkyl, and R ² and R ³ are independently hydrogen, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 1 hydroxyalkyl C 12 -C 12 hydroxyalkenyl or a C 1 -C 30 polyglycol ether chain or -CHY _x -CHY ₂ -O groups wherein one of Y ^x or Y ² is hydrogen and the other is methyl, for example N-methylacetamide,

- urea derivatives of the general formula IV

N-CO-N

R ² R ⁴ where

R ¹ , R ² , R ³ and R ³ are independently hydrogen, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 1 -C 8 hydroxyalkyl, or C 2 -C 8 hydroxyalkenyl 8 carbon atoms,

- monohydric aliphatic alcohols having 4 to 18 carbon atoms and monocyclic alcohols, for example alkanols with 2 to 18 carbon atoms, alkenols with 2 to 18 carbon atoms and terpenic alcohols, for example ethanol, propanol, isopropanol, hexanol, cis-3-hexene-1 -ol, trans-2-hexen-1-ol, 1-octen-3-ol, heptanol, octanol, trans-2-cis-6-nonadien-1-ol, decanol, linalol, geraniol, dihydroterpineol, myrcenol, nopol and terpineol,

aromatic alcohols of the general formula

(V) where

X is - (CH), -CH = CH-CH-, or -O- (CH), and

R ^{@ 1} , R ^{@ 2} and R ^{@ 3} are each independently hydrogen, hydroxy, halogen or C1 -C6 alkoxy, for example benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenoxyethanol, 1-phenoxy-2-propanol (phenoxyisopropanol) and cinnamyl,

- polyhydric alcohols and polyhydric alkoxylated, in particular ethoxylated and / or propoxylated alcohols, as well as their ethers and esters of general formula VI

R ^x -OXOR ² (VI) wherein

R ^x and R ² are each independently hydrogen, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 1 -C 8 alkanoyl, C 3 -C 18 alkenoyl, of the general formula

R ³ - (O-CH -) ---- '2'X-SO. . I

R ⁴ where

R ³ is hydrogen, alkyl of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms, and R ⁴ is hydrogen or -CH _a , and

X is C 2 -C 10 alkylene or C 2 -C 10 alkenylene, - (CH CHO) -CH -CH- or -22

- (CH-CH-Oj ----- CH-CH '2 | * X — SO 2 |

CHCH

All organic acids mentioned under (b) can also be used in the form of their water-soluble salts, such as alkali metal salts, preferably sodium and potassium salts or ammonium salts (NR ^X R ² R ³ ), where

R ¹ , R ² and R ³ are independently hydrogen, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 1 -C 8 hydroxyalkyl, C 5 -C 8 cycloalkyl or a C 1 -C 18 polyalkenyleneoxyalkyl group, or R ¹ , R ² and R ³ together with the nitrogen atom to which they are attached form an unsubstituted or C 1 -C 4 alkyl group substituted by morpholino.

Component (b) may consist of only one compound of subclass (b) or else a mixture of one or more than one compound of subclass (b ^), also together with components of other subclasses.

Preferably, a combination of one or more than one compound of subclass (b _x ) and one or more than one compound of subclass (b ₂ ) is used. Particularly preferred is a combination of cumene sulfonate and citric acid monohydrate.

Suitable components (c) are anionic, non-ionic or zwitterionic and amphoteric synthetic surfactants.

Suitable anionic surfactants are: sulfates, for example, fatty alcohol sulfates containing from 8 to 18 carbon atoms in the alkyl chain, for example sulfated lauryl alcohol, fatty alcohol ester sulfates, for example acid esters or polyadduct salts 2 to 30 moles of ethylene oxide per mole of fatty alcohol of 8 to 22 carbon atoms,

- alkali metal salts, ammonium salts or salts with amines of C8-C20 fatty acids, referred to as soaps, for example coconut oil fatty acids,

- alkyl amide sulphates,

- alkylamine sulphates, for example monoethanolamine lauryl sulphate,

- alkyl amide ether sulfates,

- sulphates of alkyl aryl polyethers,

- sulphates of monoglycerides,

- alkanesulfonates containing 8 to 20 carbon atoms in the alkyl chain, for example dodecylsulfonate

- alkyl amide sulfonates,

- alkylarylsulfonates,

- α-olefin sulfonates,

- sulphosuccinic acid derivatives, for example alkylsulphosuccinates, alkylsulphosuccinates or alkylsulphosuccinates derivatives,

-N- [alkylamidoalkyl] amino acids of formula VII

CH (CH) - CO - N

2 n

CH-Z-COO 'M where

X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or COO-M *,

Y is a hydrogen atom or a (C1-C4) alkyl group Z is - (CH) '2' ml-1 'm _i is 1 to 5, n is an integer between 6 and 18, and

M is an alkali metal or amine ion,

-alkyl ether carboxylates and alkylaryl ether carboxylates of formula VIII

CH - X - Y - A (VIII) wherein

X is the remainder of the formulas

-TCHi ^ O-, - (CH

or

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms

Y is - (CHCHO) -, 1-50 '

A is - (CH ₂ ) m ₂ - _x - COO ^- M * or

0 "M *

0M * m _a is 1 to 6, a

M is an alkali metal cation or an amine cation.

Furthermore, fatty acid methyltaurides, alkylisothionates, fatty acid and polypeptide condensates, and phosphoric acid esters of fatty alcohols can be used as anionic surfactants. The alkyl radicals in these compounds preferably contain 8 to 24 carbon atoms.

The anionic surfactants are usually obtained in the form of their water-soluble salts, such as alkali metal salts, ammonium salts and amine salts. Typical examples of such salts are lithium, sodium, potassium, ammonium and triethylamine, ethanolamine, diethanolamine or triethanolamine salts. Preferably, the use of sodium or potassium salts, or ammonium (NR ^X R ² R ³⁾ salts thereof, wherein R ^x, R ² and R ³ are independently H, alkyl of 1 to 4 carbon atoms or hydroxyalkyl groups of 1 to 4 carbon atoms.

Particularly preferred anionic surfactants in the novel formulation are monoethanolamine lauryl sulfate or alkali metal fatty alcohol sulfate salts, preferably sodium lauryl sulfate and the reaction product of 2 to 4 moles of ethylene oxide and sodium lauryl ether sulfate.

Suitable zwitterionic and amphoteric surfactants are C 8 -C 18 betaines, C 8 -C 18 sulfobetains, C 8 -C 24 alkylamidoalkylene betaines, C 1 -C 4 alkylamide moiety, imidazinecarboxylates, alkylamphocarboxylates, for example, lauroamphoglycinate) and N-alkyl-β-amino-propionates or N-alkyl-β-iminodipropionates. It is preferred to use C 10 -C 20 alkylamidoalkylene betaines having an C 1 -C 4 alkylamide moiety, and in particular cocoamidopropyl betaine.

Nonionic surfactants are propylene oxide / ethylene oxide adduct derivatives having molecular weights of 1000 to 15000, fatty alcohol ethoxylates (1 to 50 EO), alkylphenol polyglycol ethers (1 to 50 EO), ethoxylated carbohydrates, partially fatty acid esters of glycol, e.g. fatty acid dialkanolamides, ethoxylated fatty acid alkanolamides and fatty acid amine oxides.

In addition, salts of saturated and unsaturated fatty acids having 8 to 22 carbon atoms can be used as component (c), either alone in admixture with each other or in admixture with the other surfactants mentioned for component (c). Examples of such fatty acids are, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, dodecenic acid, tetradecenic acid, octadecenic acid, oleic acid, eicosanoic acid and erucic acid, as well as technical mixtures of these acids, for example coconut fatty acids. These acids can be obtained in the form of a salt, suitable cations being alkali metal cations such as sodium and potassium cations, metal atoms such as zinc and aluminum atoms, or nitrogen-containing organic compounds with sufficient basicity, for example amines or ethoxylated amines. Such a salt may also be prepared in situ.

Suitable components (d) are dihydric alcohols, preferably those containing 2 to 6 carbon atoms in the alkylene chain, for example ethylene glycol, 1,2- or 1,3-propanediol,

1,3-, 1,4- or 2,3-butanediol, 1,5-pentanediol and 1,6-hexanediol. 1,2-Propanediol (propylene glycol) is preferred.

Component (e) is preferably ethanol, n-propanol and isopropanol or a mixture of these alcohols.

Components (d) and (e) can also be obtained in admixture with each other.

The pH of the novel formulation is 3 to 10, preferably 3.5 to 5.5.

The novel preparations obtained as soaps or as so-called "syndet solutions" may further contain conventional additives such as masking agents, coloring agents, perfume oils, thickeners or reinforcing agents (consistency regulators), emollients, UV absorbers, skin protection agents, antioxidants, additives that improve mechanical properties such as dicarboxylic acids and / or salts of fatty acids having 14 to 22 carbon atoms with aluminum, zinc, calcium or magnesium, and optionally stabilizing agents.

The soap compositions of the invention can be prepared by mixing components (a) and (b) and optionally (c), (d) and (e) in any order with the necessary amount of water and mixing the mixture until homogeneous. The mixture is made up to 100% with water or deionized water. This is a purely physical process. Thus, there is no reaction between the components.

For the disinfection and cleaning of human skin, hands and resistant articles, new soap formulations can be applied either in diluted or undiluted form, suitably in an amount of at least 2 ml, for disinfecting hands, preferably in undiluted form.

The present invention is illustrated by the following examples. Parts and percentages are parts and percentages by weight.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

0,075% 0.5% 0.25% 0.4% 0.5% 2,4,4'-trichloro-2'-hydroxydiphenyl ether, monoethanolamine lauryl sulfate, sodium cumene sulphonate powder, citric acid monohydrate and propylene glycol

is mixed to homogeneity and then about 90% of the water required is added. The pH was adjusted to 4.0 with monoethanolamine. Deionized water was then added to the solution to make a total of 100 parts. The pH is checked again and, if necessary, adjusted to pH 4.0 with monoethanolamine.

Example 2

0.25% 2,4,4'-trichloro-2'-hydroxydiphenyl ether

1,0% monoethanolamine lauryl sulphate,

2.5% sodium cumene sulphonate powder,

1.5% citric acid monohydrate a

1.5% propylene glycol is mixed to homogeneity and then about 90% of the necessary water is added. The pH was adjusted to 4.0 with monoethanolamine. Deionized water is then added to this solution to adjust to

total 100 parts. The pH is checked again and, if necessary, adjusted to pH 4.0 with monoethanolamine. Example 3 0.15% 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 1.0% monoethanolamine 0.5% sodium cumene sulphonate powder, 0.8% citric acid monohydrate; and 5.0% propylene glycol is stirred to homogeneity and then about 90% needed water. The pH was adjusted to 4.0 with monoethanolamine. Then to

deionized water is added to this solution to make a total of 100 parts. The pH is checked again and, if necessary, adjusted to pH 4.0 with monoethanolamine.

Example 4

0,1% 2,4,4'-trichloro-2'-hydroxydiphenyl ether,

4,0% monoethanolamine lauryl sulphate,

0,5% sodium cumene sulphonate powder; and

The 0.019% NaOH is mixed to homogeneity and then about 90% of the necessary water is added. The pH is adjusted to 9.1 with monoethanolamine. Deionized water was then added to the solution to make a total of 100 parts. The pH is checked again and, if necessary, adjusted to pH 9.1 with monoethanolamine.

Example 5

Microbicidal activity test of new formulations

The microbicidal activity (in decimal logarithm) of the novel formulations of Examples 1 to 4 is determined by the suspension test. This test is used to evaluate the bactericidal efficacy of water-soluble antiseptics, disinfectants and liquid soaps. The test consists in seeding the test product in selected dilutions with the test bacilli. After a period of contact, aliquots are taken and the number of surviving bacilli is determined. The difference between the number of added bacilli and the number of surviving bacilli is expressed as the reduction of bacilli in decimal logarithm. Concentration is 90%, contact time is 30 seconds.

The following bacilli were used:

Example 1 2 3 4 Staph.aureus ATCC 9144 > 5.0 > 5.0 > 5.0 > 5.1. Strept.faecalis ATCC 10,541 > 5.2 > 5.2 > 5.2 > 5.2 E. Coli ATCC 10,536 4.3 5.1 4 * P.aeruginosa CIP A-22 5.4 > 5.4 > 5.4 Serratia marcescens ATCC 13880 * * * > 5.4 **

* measured ** contact time 5 minutes

Values above 4 indicate good antimicrobial activity.

Claims (20)

P A T E N C L D E CLAIMS A surfactant comprising (a) 0.01 to 2.0% by weight of a microbicidal active ingredient, (b) 0.1 to 7.5% by weight of one or more than one hydrotropic agent; (c) 0 to 2% by weight of one or more than one synthetic surfactant or soap or a combination of said substances and / or salts of a saturated and / or unsaturated fatty acid having 8 to 22 carbon atoms; (e) 0 to 70% by weight of a monohydric alcohol; and (f) as a major component water or deionized water up to 100%. Composition according to claim 1, characterized in that it contains as component (a) 2-hydroxydiphenyl ether, 2-hydroxydiphenylmethane; and 2-hydroxydiphenylthioether of formula I (I) wherein X is oxygen, sulfur or -CH ₂ Y is a chlorine or bromine atom, Z is SO 4 H, NO ₌ or an alkyl group having 1 to 4 carbon atoms, r is 0 to 3, o is 0 to 3, p is 0 or 1, m is 0 or 1, and n is 0 or 1. Composition according to claim 2, characterized in that it comprises as component (a) a compound of the general formula I, wherein X is oxygen, sulfur, or -CH-, and Y is chlorine or bromine, m is 0, n is 0 or 1, o is 1 or 2, r is 1 or 2 and p is 0. A composition according to claim 2 or 3, characterized by « with and t Ý m, that as a component (A) contains compound general- him formula I, where • X is a atom oxygen, and Y is a atom chloro, m is a 0, n is 0, o is 1, r is 2 and p is 0. Composition according to claim 4, characterized in that it comprises as component (a) a compound of the formula Composition according to any one of claims 1 to 5, characterized in that it contains component (a) in an amount of 0.02 to 0.2% by weight. Composition according to any one of claims 1 to 6, characterized in that it contains as component (b ^) a sulfonate, preferably a terpenoid salt or a aromatic compound with one or two nuclei. Composition according to claim 7, characterized in that it contains, as a aromatic compound with one or two cores, a sulphonate of camphor, toluene, xylene, cumene or naphthene. Composition according to claim 7, characterized in that component (b) consists of only one compound of subclass (b ^) or also of a mixture of one or more than one compound of subclass (b ^) and also of a mixture with components of other subclasses. Composition according to any one of claims 1 to 7, characterized in that it comprises as component (b) a combination of one or more than one compound of subclass (b ₂ ). The composition of claim 9, comprising a combination of cumene sulfonate and citric acid monohydrate. Composition according to any one of claims 1 to 11, characterized in that it contains as the anionic surfactant a fatty alcohol sulphate containing 8 to 18 carbon atoms in the chain. The composition of claim 12, wherein the anionic surfactant is an alkali metal salt of sulfated lauryl alcohol or monoethanolamine lauryl sulfate. A composition according to any one of claims 1 to 11, characterized in that it comprises as component (b) an alkylamidoalkylene betain having 10 to 20 carbon atoms in the alkylamide moiety and having 1 to 4 carbon atoms in the alkylene moiety. Composition according to any one of claims 1 to 14, characterized in that it comprises, as component (c), a saturated and / or unsaturated fatty acid having 8 to 22 carbon atoms selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, dodecenoic acid, tetradecenoic acid, octadecenic acid, oleic acid, eicosanoic acid and erucic acid. A formulation according to any one of claims 1 to 15, characterized in that it comprises propylene glycol as component (d). Composition according to any one of claims 1 to 16, characterized in that it comprises as component (e) a substance selected from the group consisting of ethanol, propanol, isopropanol and mixtures of these alcohols. A composition according to claim 1, wherein the composition is used in admixture with one another. 16 or claim 17, wherein components (d) and (e) are Use of an antimicrobial soap composition according to any one of claims 1 to 18 for disinfecting and cleaning human skin, hands and resistant articles. The use of claim 19, wherein the antimicrobial soap composition is in a diluted or undiluted form.