CA2196771A1

CA2196771A1 - Surface-active formulations

Info

Publication number: CA2196771A1
Application number: CA002196771A
Authority: CA
Inventors: Laszlo Moldovanyi
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1994-08-25
Filing date: 1995-08-14
Publication date: 1996-02-29
Also published as: EP0777717A2; FI970742A0; CZ55697A3; FI970742A; WO1996006153A3; JPH10504592A; HUT76688A; AU3345295A; SK24497A3; BR9508775A; MX9701416A; WO1996006153A2; BG101308A

Abstract

The invention relates to surface-active soap formulations, comprising: (a) 0.01 to 5 % by weight of a microbicidal active substance selected from the group consisting of (a1) phenol derivatives (a2) diphenyl compounds (a3) benzyl alcohols (a4) chlorohexidine (a5) C12-C14alkylbetaines and C8-C18fatty acid amidoalkylbetaines (a6) amphoteric surfactants and (a7) trihalocarbanilides; (b) 0.1 to 25 % by weight of one or more than one hydrotropic agent; (c) 0 to 10 % by weight of one or more than one synthetic surface-active substance or of a soap or of combinations of the cited substances; (d) 0 to 8 % by weight of a salt of a saturated and/or unsaturated C8-C22fatty acid; (e) 0 to 50 % by weight of a dihydric alcohol; (f) 0 to 70 %
by weight of a monohydric alcohol or of a mixture of several monohydric alcohols; and (g) mains water or deionised water to make up 100 %, with the proviso that the formulations contain at least one of components (c) and (d).
The formulations are used for the disinfection and cleansing of the human skin and hands and of hard objects.

Description

~ wos6/06ls3 21 96 7 7 1 r~.",~ 711 Surface-active ft~rnnIAAtiomc It is commonly knowledge that the ~ 5Jh -V~ ,1ub;l,idal properties of activesubstances in aqueous solutions of soaps or surfactants are strongly influenced by micell systems and may even be almo5t totally blocked.

Surprisingly, it has now been found that certain hy~huLIu~J;c suppress the ~ uI .;. ;IIA
inhibiting acivity of the micells of soap and surfactant systems (so-callcd "deblocked surfactant systems"). Accordingly, the A . . l; l l l ;l ~ ul ~ luLlicid~l activity of different active ingredients can be cienifirAn-ly enhanced in many surfactant systems.

The novel surface-aciive surfactant r.. ~ c comprise (a) 0.01 to 5~o by weight of a . " ;. . ub; ;. IA1 active substance selectcd from the group consisting of (al) phenol derivatives, (a2) diphenyl~
(a3) benzyl alcohols, (a4) ~.IllUlU~ Ai~l;llC, (a5) Cl2-CI4alkylb~ .sandC8-Cl8fattyacid ' " y~L c, (a6) amphoteric 5nrfA~rAArrc (a7) Ll;l1AluwlLI_1ilides, and (a8) quaternaryA.,. ~ , salts;
(b) 0.1 to 259~o by weight of one or more than one Lydluilu~ , agent;
(c) 0 to lO~o by weight of one or more than one synthetic surface-active substance or of a soap or of c~." '.; I.Al;l .,.~ of the cited c.~hc.An~l-c (d) 0 to 8% by weight of a salt of a saturated and/or . ~ I C8-C2~fatty acid;
(e) 0 to 50% by weight of a dihydric alcohol;
(f) 0 to 70% by weight of a 111w1ol1y~ic alcohol or of a mixture of several 1lu~lwll r~i~, alcohols; and (g) mains water or deioniscd water to make up 100%, with the proviso that the ' ' contain at least one of c~ - (c) and (d).

Soap r .. . ~ .IIC will be understood as meaning aqueous soap solutions which may be obtained as soap or so-called syndet solutions (= synthetic detergents).

The .. .: ;, ..1~, oI.: I activity of the deblocked surfactant systems reaches upon gram-positive wo 96/06153 2 ! 9 6 7 7 1 and gr un-negative bacteria as well as yeasts, ~ ' , ' y ;~ and the lilce.

The: . ' of component (a1) preferably correspond to the general formula OH
Rs ~ R
(I) R4 ~R2 wherein Rl is hydrogen, hydroxy, Cl-C4allcyl, chloro, nitro, phenyl oder benzyl, R2 is hydrogen, hydroxy, Cl-C6allcyl or halogen, R3 is hydrogen, Cl-C6allcyl, hydroxy, chloro, nitro or a sulfo group in the form of the alkali metal salts or ~ salts thereof, R4 is hydrogen or methyl, R5 is hydrogen or nitro.

Halogen is bromo or, preferably, chloro.

Such cr~ u~ are typically ~ ~ ,, ~ 1 (o-, m-, p-~,Llulu~
2,~rlirhlr~Fh.-n~l, p- I ' 1, picric acid, xylenol, p-chloro-m-xylenol, cresols (o-, m-, p-cresols), p-chloro-m-cresol, p~ ' resorcinol, orcinol, ~n-L.,AyL~so..,;,,ol, pyrogallol, 1~ ugl-- ;,-, carvacrol, thymol, p-~,LIUlU~ llUI, O-~ h~llOl, o-l,~ yl~h~,l..,l,p-chloro-o-l,c..~ L.,..uland4pl ...,1-..Ir~...;~ acid.

The c ~ u ~ of component (a2) preferably correspond to the general formula R'~ R 2 R~ R2 (2) R 3 ~ X ~ R3 wherein X is sulfur or the methylene group, ~ WO 96/06153 2 1 9 6 7 7 1 r~

Rl and R'l are hydrnxy, and R2, R'2, R3, R'3, R4, R'4, R5 and R'5 are each; l ~ I. ly of one another hydrogen or halogen.

Typical examples of c~ ,v.. l~ of foimula (2) are 1.. ,.. ~ h , ~ U
h. . 2,3-dihydinxy-5,5'- li~,hlu~ b~.lrld~"
2,2'-dihydroxy-3,3',5,5' ~..I~. I,l~,,~lil,l,, .~yl~lllrld~"
2,2'-dihydroxy-3,3',5,5',6,6'-h~Y~rhh.,~ lrldc and 3~3~-dibromo-s~5~-dic~hioro-2~2~-dill~llu~y~

The r ' of component (a3) preferably correspond to the general formula Rs (3) R4 ~ R2 wherein Rl, R2, R3, R4 and R5 are each ;.. 1. ~ ly of one another hydrngen or chloro.

Illustrative examples Of - - r ~ of formula (3) are benzyl alcohol, 2,4-, 3,5- or 2,6-1;. hl- ~ vl .. ~ ~1 alcohol and 1 R. I.L ~1 ub ~ alcohol.

~' A (a4) is ~ and salts thereof together with organic and inorganic acids, which type of compound may preferably be ill~ ' into syndet systems.
Cl , (a5) is typically C8-CI8c~ - ,.;.I.l u~y ~

Amphoteric surfactants ~. .. ,r~ ,...i;.lg to component (a6) are suitably Cl~al~ yli~, and C~ ' yli~. acids such as aL~y' or alhyLullil~v~ u~

The ~ r ~ of component (a7) preferably correspond to the general formula Hal n Hal m (4) ~ NH-CO-NH~

wherein Hal is chlorv or bromo, n and m are I or 2, and n+m are3.

The quaternsry ~-mm~nillm salts of component (a8) preferably correspond to formula Rf, (5) R6--N+--R8 wherein R6, R7, R8 and Rg are each "..1 l~r 'A~ y of one another Cl-CI8aL~cyl, Cl-C~8alkoxy or phenyl-lower aLlcyl, and Hal is cbloro or bromo.

Among these salts, the compound of formula CH3 ~

(6) H3C-(CH2) --N+--CH2~ cr wherein n is an integer from 7 to 17, is very ~L;uul~ly preferred.

The following ~ ,. .,. N are suitable for use as component (b):
(bl): sulfonates, preferably the salts thereof of terpenoids, or mono- or binuclear aromatic c r~ l.v~ ..1 c typically sulfonates of camphor, toluene, xylene, cumene or naphthene;
(b2): saturated or ' C3-CI~di- or poly~ul,v~ylh. acids, typically malonic,succinic, gluLaric, adipic, pimelic, suberic, azelaic and sebacic acid, unde-b~yli~, acid and ~I~NL ~ vv~yli~, acid, fumaric, maleic, tartaric ~ wo 96106153 2 1 9 6 7 7 1 ~ 1 , and malic acid as well as citric and aconit*c acid;
(b3): - aliphatic saturated or ~ 1 cl-cll~U~ llJUAylic acids, typically acetic, propionic, hexanoic, capric or, ~ y L.loic acid;
- saturated or I ' C3-CI2di- orl,uly~bv~yli~ acids, typically malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, I ~ ' ylic and ~ r .li. - bu~.yli., acid, fumaric, maleic, t_rtaric and malic acid as well as citric and aconitic acid;
h~ ylic acids, typically ~ yl~ acid, hyLu~y~lh ~ihy!~ ; t~ U ~ acid and r~: -ilf~1Tiare~ir acid;
- cyrk~alirh~*f carhoxylic acids such as camphoric acid;
- aromatic carboxylic acids, typically benzyl, yhC~Iy;~.Li~., ph~..w~y~ , and cinnarnic acid, 2-, 3- and ~hyLw~yb~,~l~iu acid, anilinic acid as well as o-, m-and p-chlu~ulJh~ yla~lic acid and o-, m- and p-l,l.l-..,; ' yf~.e,~ic acid;
- alkali metal salts and amine salts of inorganic acids, typically the sodium orpotassium salts and arnine(RIR2R3) salts of l.ydll ' ' , sulfuric, ph~~srhf)rif Cl-CIOalky~ " ' ~ acid snd boric acid, in which amine salts Rl, R2 and R3 have the meaning indicated above;
- isethionic acid;
- tannic acid;
- acid arnides of forrnula (7) R1-CO-N

wherein Rl is hydrogen or Cl-CI2aL~yl, and R2 and R3 are each h~l 'IJ' I lly of the other hydrogen, Cl-CI2aLkyl, C2-CI2allcenyl, Cl-CI2hydroxyallcenyl, C2-CI2Ly~u-~y~l~yl~ or a polyglycol etherchain containing I to 30 -CH2-CH2-O- or -CHYI-CHY2-O- groups, wherein Yl or Y2 is a hydrogen radical and the other is methyl, e.g.N .II.,LI,yl - . I A . .. if ll~, - urea derivatives of formula Rl / R3 (8) N-CO-N
R2 \ R4 . .

WO96/06153 2 1 967~ O

wherein Rl, R2, R3 and R4 are each '~. ' 'y of one another hydrogen, Cl-C8allcyl, C2-C8allcenyl, Cl-C8Ly~w-y~16yl or C2-Cb' ~LW~Y~ .IIJI~
- ' y~Lh, C4-CI8aliphatic and l~-u--~y~.LI, alcohols, typically C2-Cl8aLcanols, C2-CI8allcenols and terpene alcohols e.g. ethanol, propanol, i~ 1, hexanol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 1-octen-3-ol, heptanol, octanol, trans-2-cis-6-nonadien-1-ol, decanol, linalol, geraniol, dihy~llvt I~ hh myrcenol, nopol and terpineol;
- aromatic alcohols of formula (g) ~ X--OH
R2~l=' wherein X i8 -(CH2)l 6, -CH=CH-CH2-, or -O-(CH2)2 6, and Rl, R2 and R3 are each ~I ' 'y of one another hydrogen, hydroxy, halogen or Cl-C6a~1coxy, typically benzyl alcohoL 2,~dichlorobenzyl alcohol, ~L~u~.y~ ' -1, 1-phenoxy-2-propanol (l~h~ w~ u~ 1 ') and cinnamyl alcohol;
- polyhydric alcohols and polyhydric allcoxylated, preferably ~,llw~yL.:~ andlor~IIUIJUA~' ' alcohols as well as the ethers and esters thereof of the general formula (10) Rl-O-X-O-R2, wherein Rl and R2 are each h ~ L ~ly of the other hydrogen, Cl-CI2allcyl, C2-CI2allcenyl~ Cl-Csallcanoyl, C3-CIgallcenoyl, R3-(OCH-CH2)l So, wherein R3 is hydrogen, Cl-CI2allcyl or C2-CI2allcenyl, and R4 is hydrogen or -CH3, and X is C2-CIOallcylene or C2-CIOallcenylene, -(CH2CH20~CH2-CH2- or 21 9677l WO96/061S3 .~ Ll~b. I

~_T I
-(CH2-CH-Oh~ 2-CH-.

All organic acids mentioned under ~b) may also be obtained in the form of their wa~er-soluble salts, such as the allcali metal salts, preferably the sodium or potassium salts or the amine(NRIR2R3) salts, wherein Rl, R2 and R3 are each i,..l IJ' ~ Iy of one another hydrogen, Cl-C8alkyl, C2-C8allcenyl, Cl-C8hydroxyallcyl, C5-C8cycloaLlcyl or poly~l.yL~ y-Cl-CI8allcyl, or Rl, R2 and R3, together with the linlcing nitrogen atom, are . h~ d or Cl-C4allcyl ' ' ' 1....,l.1.~.1;"~.

C'~ , (b) can consist of only one compound of subclass (bl) or also of mixtures of one or more than one compound of subclass (bl), also together with c~ of further subclasses.

A special ~ ' ' activity is achieved with a ~ h~ of one or more than onecompound of subclass (bl) and one or more than one compound of subclass b2).
Pa-Li~uLuly preferred in this connection is a c lml of cumene sulfonate and citric acid Illullull r ' Suitable ~ r ' (C) are anionic, nonionic or ~;L~I;~JIfIC and amphoteric synthetic, surface-active 5llhcrs~TIr~-c Suitable anionic surface-active substances are:
- sulfates, typically fatty alcohol sulfates, which contain 8 to 18 carbon atoms in the allcyl chain, e.g. sulfated lam yl alcohol;
- C8-C22fatty alcohol ether sulfates, typically the acid esters or the salts thereof of a polyadduct of 2 to 30 mol of ethylene oxide with 1 mol of a C8-C22fatty alcohol;- the aL~ali metal salts, ~ - . :. . salts or amine salts of C8-C20fatty acids, which are termed soaps, typically coconut fatty acid;
- alkylamide sulfates;
- allcylamide ether sulfates;
- allcylaryl polyether sulfates;
- Illollo~ly~.~,-;~ sulfates;

wo 96/06153 2 1 9 5 7 ? 1 - aLlcane sulfonates, containing 8 to 20 carbon atoms in the aL~cyl chain, e.g. dodecyl sulfonate;
- alkylamide sulfonates;
- aL~cylaryl sulfonates;
- ~-olefin sulfonates;
- ' ' acid derivatives, typically aLlcyl, 1 r. .~ . ,, slkyl ether . '' ' oraLlcyl 1r.-~ lr d~,,;v~
- N-[aL~' ' " yl]amino acids of formula CH3(CH2)n-CO-N
(11) \CH-Z-COO-M+
I
X

wherein X is hydrogen, Cl-C4alkyl or -COO-M+, Y is hydrogen or Cl-C4aLicyl, Z is -(CH2) m 1 ~
ml is 1 to 5, n is an mteger from 6 to 18, and M is an allcali metal ion or an amine ion;
aL~cyl ether COLI~UA~ and aL~cylaryl ether ~ u~' of formula (12) CH3-X-Y-A, wherein X is a radical tCH2)s l9 ~~, tCH~ ~--or -(CH~3:;~N

R is hydrogen or Cl-C4alkyl, Y is -(CHCHO~I 50, 2~ 96771 ~ wo s6/06ls3 r~

11~ O-M+
A is-(CH2~ COO~M or p \ O-M+
m2 is 1 to 6, and M is an alkali metal cation or amine cation.

The anionic surfactants used may f U~ ..J.C be fatty acid methyl taurides, alky1;~ fatty acid polypeptide: ' and fatty alcohol phosphoric acid esters. The allcyl radicals in these . , ' preferably contain 8 to 24 carbon atoms.

The fatty alcohols which may be present in the above-mentioned surfactants are those containing 8 to 22, preferably 8 to 18 carbon atoms, typically octyl, decyl, lauryl, tridecyl, miristyl, cetyl, stealyl, oleyl, arachidyl or behenyl alcohol.

The anionic surfactants are usually obtained in the form of their water-soluble salts, such as the aikali metal, ~, .";, .. or amine salts. Typical examples of such salts are lithium, sodium,potassium, Il;~,lhyl~llulc;,!' I e,.~ -h1~ ;-.or , ;. 11. - ,~,1~ ..;,~ salts. It is preferred to use the sodium orpotassium salts or the (NRIR2R3) salts, wherein Rl, R2 and R3 are each ~ r ~ ly of one another hydrogen, Cl-C4aLIcyl or Cl-C4hydroxyaikyl.

The anionic surfactants preferably used in the r.. 1 ;.. of this invention are C8-C22fatty acid alcohol ether sulfates, more particularly the alkali metal salts of laut ether sulfate.

Very IJG~ ,ulolly preferred anionic surfactants in the novel r. ." ", 1 l ;"" are ' ' lauryl sulfate or the aikali metal salts of fatty alcohol sulfates, preferably the sodium lauryl suifate and the reaction product of 2 to 4 mol of ethylene oxide and sodium lauryl ether sulfate.

Suitable 4V~;It~liOll;~ and ~ surfactants are C8-CI8betaines, C8-CI~ r..l..,; ..
C8-C24aikylamido-CI-C4aiky~ b~ .JI;~ ,dlbl)~y' , aihyla~ l-o-..ui,w~y carboxylic acids, aihylal..~l.~lul,~".~li., acids (e.g. I-.~ p1.~s~;1y~ ) and N-aikyl-~-all~;fiv~ r or N-aikyl-~: I .1;1,.~,,,.;. ., ." ~, c It is preferred to use the C10-C20alkylamido-Cl-C4aih~ and, more ~ ul~ly, WO 96/06153 2 1 9 ~ 7 7 1 r~

Nonionic surfactants are typically derivatives of Khe adducts of propylene u.~i~/ul~jL,~
oxide having a molecular weight of 1000 to 15000, fatty alcohol ethoxylates (1-50 EO), allcylphenol polyglycol eKhers (1-50 EO), ~.llw~y' ' ~,olbul..~,' faKy acid glycol partial esters, typically diethylene glycol , faKy acid Al' ' ' and faKy acid fli~ ;fir C, faKy acid ~ - ethoxylates and faKy acid amime oxides.
The fatty acid A lL A ~ ~1l ' ; ri~ C and faKy acid rliA l L ~ and, preferably, f~U. .h -- ~ are to be l~ ul~lly l~ighlighr~rl Suitable ~ u~ r)~ (d) are the salts of saturated and I ' Ci2-C22fatty acids, typically lauric, myristic, palmitic, stearic, arachic, behenic, fir)rl, ~ hA.l.. ";, u~ oleic, eicosanic and erucic acid, as well as the technical mixtures of such acids, typically coconut faKy acid which is preferably used in the novel r... ..1 I;.. These acids may be obtained in the form of salts, suitable cations being aLcali metal cations such as sodium and potassium cations, metal atoms such as zinc atoms and aluminium atoms or nitrogen-containing organic ~ u- l~ of sufficient aLcalinity, typically amines or clLw~yL:~ amines. These salt can also be prepared in situ. ('rimrf~n~n~ (d) can also be a mixture of the indicated salts.

Suitable ~ (e) are dihydric alcohols, preferably those containing 2 to 6 carbon atoms in the aL~ylene radical, typically ethylene glycol, 1,2- or 1,3-~ u~ - ~1 1,3-, 1,~
or 2,3-butanediol, 1,5-1 ' ' and 1,6 ' ' -' 1,2-pluJ~ lidl (propylene glycol) is preferred.

C'f I (f) is preferably ethanol, n-propanol and i~u~ ~ul~O .ol or a mixture of these alcohols.

Preferred novel ' ' - are those comprising (al) a compound of formula ~ WO 96/061S3 2 l 9 6 7 7 I P ~

OH
R5 ~R, (1) I I .
R4 ~/ ~R2 wherein Rl is hydrogen, hydroxy, Cl-C4allcyl, chloro, nitro, phenyl or benzyl, R2 is hydrogen, hydroxy, Cl-C6alkyl or chloro, R3 is hydrogen, Cl-C6allcyl, hydroxy, chloro, nitro or a sulfo group in the formof the aLkali metal salts or ~ salts thereof, R4 is hydrogen or methyl, and R5 is hydrogen or nitro, (b) 0.1 to 259to by weight of a mixture of sodium cumene sulfonate and citric acid Il~u~lullyl (c) 1 to lO~o by weight of a C8-C22fatty acid alcohol ether sulfate, (e) 0 to 50% by weight of a dihydric alcohol;
(f) 0 to 70% by weight of a ' Jl~i~, alcohol or of a mixture of several Illu~lohydli~, alcohols; and (g) mains water or deionised water to malce up 100%.

The pH of the novel r. ." . ~ .. . is 3 to 10, preferably 4.5 to 6.

The novel r..,.,.. ~ obtained as soap or syndet solutions may additionally comprise customary additives, typically I dyes, perfume oils, thickeners or solidifiers (consistency regulators), emollients, UV absorbers, skin-protection agents, ' .adclitives which improve the ' I properties, such as di~,~ubu7.yli~. acids andlor Al, Zn, Ca, Mg salts of Cl4-C22fatty acids and, if desired, 1~ Vd~ ,s.

The novel soap bars can be fabricated in per se known manner, typically by mixing the novel co~ (a) and (b) and, optionally, (c), (d), (e) and (f), as well as any additives in a jerk mixer at 18-25~C After the ~ ." obtained has been processed, it is extruded at 40 to 60~, preferably from 45 to 50~C, and then cut and stamped in moulds.

Soap r ."" ~ of the invention can be prepared by mixing ~ (a) and (b) and, optionally, (c), (d), (e) and (f), in any order, with the requisite amount of water and stirring _ _ _ _ , . . . .. .. . . . .... . .. . . . . . . . .

21 9~77.1 wo 96106153 ' - r~

the mixture to 1..~ y. The mixture is bulked to 1009~o with additional water. This procedure is a purely physical procedure. Accordingly, there is no chernical reaction of the individual e~

For ~1 ~. . u . . and cleansing of the human skin and hands and of hard objects, the novel soap r.., .. ~ , can be applied thereto in dilute or undilute form, suitably in an amount of at least 2 ml, preferably in the undilute form, for hand ~ ' The invention is illustrated by the following Examples. Parts and ~ are by weight.

ExamDle 1:
1.0 part o-pl.~,l"d~ .ol, 4.0 parts sodium lauryl ether-2-sulfate, 8.0 parts sodium cumene sulfonate powder, 8.0 parts cittic acid llw.. Jllyd~
10.0 parts propylene glycol, and water to make up 100 parts are stirred to I ~ oO. --~ ~ and abom 90% of the requisite water is then added. The pH is adjusted to 5~ with .. .~ lu , "~1 ~ ;, Deioniscd water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, is added to adjust the pH to 5.5.

Example 2:
1.0 part o-~hc.... y1, ' 1, 4.0 parts sodium lauryl ether-4-sulfate, 8.0 parts sodium cumene sulfonate powder, 8.0 parts citric acid .. onol.y.' 10.0 patts propylene glycol, and water to make up 100 parts is stitred to hl,. ~,o. ;ly and about 90~o of the requisite water is then added. The pH is adjusted to 5.5 with ' ~ ' ~. Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, ' -' is added to adjust the pH to 5.5.

~ WO961061S3 2 1 96 7 7 1 ~ . S.l Example 3:
1.0 part p-chloro-m-xylene, 4.0 parts sodium lauryl ether-2-sulfate B.0 parts sodium cumene sulfonate powder, 8.0 parts citric acid IllU~IVhyl' 10.0 parts propylene glycol, and water to make up 100 parts are mixed to h~ y and about 90% of the requisite water is then added. The pH is adjusted to 5.5 with .... ~ Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, is added to adjust the pH to 5.5.

Example 4:
1.0 part p-chloro-o-b~,.. Lyl~ .. ol, 4.0 parts sodium lauryl ether-2-sulfate 8.0 parts sodium cumene sulfonate powder, 8.0 parts citric acid Ill~ hyd 10.0 patts propylene glycol, and water to make up 100 parts are stirred to k ~ .o~ y and about 90% of the requisite water is then added. The pH is adjusted to 5.5 with ' Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, ~ ' is added to adjust the pH to 5.5.

Example 5:
2.0 parts benzyl alcohol.
4.0 parts sodium lauryl sulfate 5.0 parts sodium cumene sulfonate powder, 8.0 parts citric acid I~ lullyl 10.0 parts propylene glycol. and water to make up 100 parts are stirred to h.~ and about 90% of the requisite water is then added. The pH is adjusted to 5.5 with .. ~ Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, . .~ -- ~ Ih ~ -- 1.. is added to adjust the pH to 5.5.

, wo 96/06153 2 1 9 6 7 7 1 P~l/r 1 o Example 6: .
4.0 parts ~ Yl~
5.0 patts sodium cumene sulfonate, 10.0 parts propylene glycol, 8.0parts citricacidll~u.. uh~.' and water to makc up 100 parts arc stirred to 1.. ", r,O. ~ and about 90% of the requisite water is then added. The pH is adjusted to 5.5 with . - ...r.~ ;... Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, , . .. "., .~ :1 ,~.1- . "; - is added to adjust the pH to 4Ø

Example 7:
4.0 parts ~ q u~ Ibetaine, 12.0 parts ethanol, 8.0 parts citric acid ..,o..ol.~,' and water to make up 100 parts are stirred to 1~ y and about 909'o of the requisite water is then added. The pH is adjusted to 55 with .... ,. " . ~1,~. ,~.1 - ..;..~ Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, ........ ~ .1~ -- .~ ----;". is added to adjust the pH to 4Ø

Example 8:
4.0 parts sodium 1- A~
5.0 parts sodium cumene sulfonate, 10.0 parts propylene glycol, 8.0 parts citric acid .,.o.. ol.~L~.x" and water to make up 100 parts are stirrcd to h. ~ Y and about 90% of the requisite water is then added. The pH is adjusted to 5.5 with ' I Deionised water is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, .......... ll -----~ --:.. is added to adjust the pH to 4Ø

Example 9:
4.0 parts sodium I , 12.0 parts cthanol, 8.0 parts citric acid ~u~uh~l' , and 2 ~ 9677 1 ~ wo 96106153 P~

water to make up 100 parts are stirred to h~ ~'0O ~ y and about 90% of the rcquisiu water is then added. The pH is adjusted to 55 with, ' ' ~ Deionised waur is then added to thc solution to make up a total of 100 parts. The pH is checked again and, if necessary, is addcd to adjust the pH to 4Ø

Example 10:
1.0 part of the compound of formula H3C-(CH2) --N+--CH2 Q~ Cl-, wherein n is am integer from 7 to 17, 4.0 parts ~ 1 Jlb~,L~.~,, 12.0 parts ethanol, 8.0 parts citric acid IllUIIOIIyl ' ', and waur to make up 100 parts are stirred to I - u~r~, -- y and about 90% of the requisitc water is then added. The pH is adjusted to 55 with ' ' Deionised water is then added to the solution tomake up a total of 100 parts. The pH is checked again and, if necessary, h ~ .:-- is added to adjust the pH to 55.

Exam~le 11:
1.0 part 2,4~ Jb~.~yl alcohol 4.0 parts sodium 1,~
5.0 parts sodium cumene sulfonau, 1.0 patt propylene glycol, 8.0 parts citric acid Ill~ h~.' and water to make up 100 parts are stirred to h.,.. ,,. -: ~y and about 90~o of the requisitc water is then added. The pH is adjusud to S.S with - ' ~ ' Deionised waur is then added to the solution to make up a total of 100 parts. The pH is checked again and, if necessary, -' ' is added to adjust the pH to 5.5.

WO 96106153 2 1 9 6 7 7 1 P~l/~9!

Example l2: Test of the ,..i~ ,l,;.,;dal activity of the novel r~ C
The ...;. .~ activity (in decimal logarithms) of the novel r lqtjnnc according t~
Examples I to 11 is ~ t~inr~1 with a suspension test. This test is used to assess the bq~tl riri~ activity of water-soluble antiseptics~ rrJ ~ and of liquid soaps. The test consists in seeding the test product in selected dilutions with the test bacillus. After a cenain contact time, aliquots is taken and the number of surviving bacilli is ~L~t~nninrr~
The difference between the number of the bacilli added and the number of the snniving bacilli is expressed as bacilIi reduction in decimal logarithms. The . is gor~o, the contact time is 30 seconds.

The following test bacilli are used:
Example Staph. aureus Strept. faecalis E. Coli P.aeruginosa Serratia mar-ATCC 9144 ATCC 10,541 ATCC 10,536 CIP A-22 ATCC 13,880 4.6 >5.1 >53 >5.3 >5.4 2 >55 >52 >5 1 >5.3 >5.5 3 >5.5 >5.2 >5.1 >5.3 >5.5 4 >5.5 >5.2 >5.1 >5.3 >5.5 >6 >6 >6 >6 >6 6 2.0 0.2 1.4 >6 2.7 7 0 0.5 2.6 >6 1.3 8 0.1 0.3 0.7 >6 2.5 9 35 >6 >6 >6 4.2 1.0 1.7 >6 >6 4.7 1 1 3.4 >6 >6 >6 >6

Claims

What is claimed is

1. A surface-active surfactant formulation, comprising (a) 0.01 to 5% by weight of a microbicidal active substance selected from the group consisting of (a1) phenol derivatives, (a2) diphenyl compounds, (a3) benzyl alcohols, (a4) chlorohexidine, (a5) C12-C14alkylbetaines and C8-C18fatty acid amidoalkylbetaines, (a6) amphoteric surfactants, (a7) trihalocarbanilides, and (a8) quaternary ammonium salts;
(b) 0.1 to 25% by weight of one or more than one hydrotropic agent;
(c) 0 to 10% by weight of one or more than one synthetic surface-active substance or of a soap or of combinations of the cited substances;
(d) 0 to 8% by weight of a salt of a saturated and/or unsaturated C8-C22fatty acid;
(e) 0 to 50% by weight of a dihydric alcohol;
(f) 0 to 70% by weight of a monohydric alcohol or of a mixture of several monohydric alcohols; and (g) mains water or deionised water to make up 100%, with the proviso that said formulations contain at least one of components (C) and (d).

2. A formulation according to claim 1, wherein the compounds used for component (a1) are those of the general formula wherein R1 is hydrogen, hydroxy, C1-C4alkyl, chloro, nitro, phenyl oder benzyl, R2 is hydrogen, hydroxy, C1-C6alkyl or halogen, R3 is hydrogen, C1-C6alkyl, hydroxy, chloro, nitro or a sulfo group in the form of the alkali metal salts or ammonium salts thereof, R4 is hydrogen or methyl, R5 is hydrogen or nitro.

3. A formulation according to claim 1, wherein the compounds used for component (a2) are those of formula wherein X is sulfur or the methylene group, R1 and R'1 are hydroxy, and R2, R'2, R3, R'3, R4, R'4, R5 and R'5 are each independently of one another hydrogen or halogen.

4. A formulation according to claim 1, wherein the compounds used for component (a3) are those of formula wherein R1, R2, R3, R4 and R5 are each independently of one another hydrogen or chloro.

5. A formulation according to claim 1, wherein component (a4) is chlorohexidine or a salt thereof with an organic or inorganic acid.

6. A formulation according to claim 1, wherein component (a5) is cocamidopropylbetaine.

7. A formulation according to claim 1, wherein component (a6) is a C12alkylaminocarboxylic acid or a C1-C3 alkanecarboxylic acid.

8. A formulation according to claim 1, wherein the compounds used for component (a7) are those of the general formula wherein Hal is chloro or bromo, n and m are 1 or 2, and n+m are 3.

9. A formulation according to claim 1, wherein the compound used for component (a8) is a compound of formula wherein n is an integer from 7 to 17.

10. A formulation according to any one of claims 1 to 9, wherein component (b1) is a sulfonate, preferably a salt thereof of a terpenoid or of a mono- or binuclear aromatic compound.

11. A formulation according to claim 10, wherein the mono- or binuclear aromaticcompounds are the sulfonates of camphor, toluene, xylene, cumene or naphthene.

12. A formulation according to any one of claims 1 to 11, wherein component (b) consists of only one compound of subclass (b1) or also of a mixture of one or more than one compound of subclass (b1) together with components of further subclasses.

13. A formulation according to any one of claims 1 to 11, wherein component (b) is a combination of one or more than one compound of subclass (b1) and one or more than one compound of subclass (b2).

14. A formulation according to claim 13, wherein a combination of cumene sulfonate and citric acid monohydrate is used.

15. A formulation according to any one of claims 1 to 14, wherein component (c) is an anionic surfactant in the form of the water-soluble salt thereof.

16. A formulation according to claim 15, wherein component (c) is C8-C22fatty alcohol ether sulfate.

17. A formulation according to claim 16, wherein component (c) is an alkali metal salt of lauryl ether sulfate.

18. A formulation according to any one of claims 1 to 17, wherein component (d) is selected from the group consisting of lauric, myristic, palmitic, stearic, arachic, behenic, dodecenic, tetradecenic, octadecenic, oleic, eicosenic and erucic acid.

19. A formulation according to any one of claims 1 to 18, wherein component (e) is propylene glycol.

20. A formulation according to any one of claims 1 to 19, wherein component (f) is selected from the group consisting of ethanol, propanol, isopropanol, and mixtures of these alcohols.

21. A surface-active formulation comprising (a1) a compound of formula wherein R1 is hydrogen, hydroxy, C1-C4alkyl, chloro, nitro, phenyl oder benzyl, R2 is hydrogen, hydroxy, Cl-C6alkyl or halogen, R3 is hydrogen, C1-C6alkyl, hydroxy, chloro, nitro or a sulfo group in the form of the alkali metal salts or ammonium salts thereof, R4 is hydrogen or methyl, R5 is hydrogen or nitro, (b) 0.1 to 25% by weight of a mixture of sodium cumene sulfonate and citric acid monohydrate, (c) 0 to 10% by weight of a C8-C22fatty alcohol ether sulfate, (d) 0 to 50% by weight of a dihydric alcohol, (e) 0 to 70% by weight of a monohydric alcohol or of a mixture of several monohydric alcohols, and (f) mains water or deionised water to make up 100%.

22. Use of an antimicrobial soap formulation as claimed in any one of claims 1 to 21 for the disinfection and cleansing of the human skin and hands and of hard objects.