CA2196774A1

CA2196774A1 - Surface-active formulations

Info

Publication number: CA2196774A1
Application number: CA002196774A
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: BG101306A; JPH10504591A; CZ55597A3; FI970741A0; HUT77706A; EP0777716A2; BR9508767A; SK24597A3; MX9701417A; FI970741A; AU3345195A; WO1996006152A3; WO1996006152A2

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

~wo 96/0615, ~ ?1n Surface-active r..,.".,l-~;.... 2 1 q 6 7 7 4 The present invention relates to surface-active r ~ as well as to their use for the r~., ;.... and cleansing of the human skin and hands and of hard objects.

Special demands of hygiene are not only in hospitals, restaurants or in the food sector, but also in the private sector, as for example in private hmlc~hrllrlc or when travelling whereby the demands made upon the .1:~., F, . ~-.,t~ employed are ...,.1r...: t~.11y less stringent in these sectors than in the frrst 1 group. Nun.,~L~,lc~ ~ these .1;~;, . rr~ should act within as short a time as possible, and they should preferably be worth the money, have good skin romr~ hility and be ecologically safe.

Surprisingly, it has now been found that a fr~rrnrh~ ir~n cnmrricing an extremely low of a ~ 1~ ~ul - 1,1~1 active substance as well as further CO..I~ ', typically surface-active ~ . has these properties.

The surFace-active r. ., . , ~ comprise (a) 0.01 to 0.2r~, by weight of a ll~;WU~ l active substance, (b) 0.1 to 7.5~o by weight of one or more than one Ly~hullu~ agent, (c) 0 to 2% by weight of one or more than one synthetic surface-active substance or of a soap or of rr~mhi~ ir nC of the cited substances and/or of a salt of a saturated and/or t~ d Cs-C??fatty acid, (d) û to 109~o by weight of a dihydric alcohol, (e) 0 to 70% by weight of a Illu~lohy~i~. alcohol, and (f) mains water or deionised water to make up 100%.

Soap ~o, ., ,1 ~l ;....~ will be understood as meaning aqueous soap solutions which may be obtained as soap or so-called syndet solutions (synthetic detergents).

The ~LI~Lil--;-,lUIJh~l activity of the novel formulation reaches gram-positive and gram-negative bacteria as well as yeasts, d~ a~u~hyi~, . and the like.

Suitable cr~ - ..,r ~ (a) are preferably 2-hydlu~ydi~ ,l.yl ethers, 2-hydlu~ylliphe~lyl methanes and 2-Ly~u~yL~ ,.lyl thioethers of the general formula ~V0 96/û6152 r~

-2- 2 ~ 96774 (OH)~ X ~ (OH) n OH

wherein X is oxygen, sulfur or -CH2-, Y is chloro or bromo, Z is SO2H, NO2 or Cl-C4alkyl, r isOto3, o isOto3, p isOorl, m isOorl,and n isOorl.

Of particular interest are e~ of formula (1), wherein X is oxygen, sulfur or -~2-, and Y is chloro or bromo, m is O, n isOorl, o is 1 or 2, r 1 is or 2, and p isO.

Of very particular interest are ~ of formula (1), wherein X is oxygen, and Y is chloro, m isO, n isO, o is 1, r is 2, and p isO.

The compound of formula ~ WO 96/06152 ~ 0 2 ~ 96774 (2) C

Cl HO

is very ~ LuuLuly preferred here.

t'nmrcmf nr (a) in the novel r. " " . "~ ", is preferably used in amounts of 0.02 to 0.2'io by weight.

The following cn.,.l,u~,.k are suitable for use as component (h):
(b1): sulfonates, preferably the salts thereof of terpenoids, or mono- or binuclear aromatic co,..l~u ,rl~ typically sulfonates of camphor, toluene, xylene, cumene or naphthene;
(b2): saturated or I ' C3-CI2di- or pulyu~ubu~yLu acids, typically malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, unde-. ~ d,~ ~ ylh, acid and fln~ yL, acid, fumaric, maleic, tartaricand malic acid as well as citric and aconitic acid;
(b3): - aliphatic saturated or ' Cl-CI jl~lull~bu~ylic acids, typically acetic, propionic, hexamoic, capric or ulldf ~"~L,.,v;c acid;
- saturated or I ' C3-CI2di- or polyu~ul,u,.yLu acids, typically malonic, succmic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, I,u,.~ and ~' ' ' ' yL, acid, fumalic, maleic, tartaric and malic acid as well as citric and aconitic acid;
- - ~; . nc ~ ylic acids, typicaLy f;Llly~ l..;... r~ l"" I ;r acid, h~Lw~
oLllyl. .1;"...;,.. ~ n ,.. m;r acid and nimlrltri~rr~ir acid;
- cyf In~lirh~if carboxylic acids such as camphoric acid;
- aromatic carboxylic acids, typically benzyl, ~JL~,..JL~ c, ~L ~ u~y~ ic and cinnamic acid, 2-, 3- and ~hy~hw~l),,.l~u;c acid, anilinic acid as well as o-, m-and p- ~ ""~ yldc~lic acid and o-, m- and p-~Llolu~L~,llu~y~l~,clic acid;
- allcali metal salts and amine salts of inorganic acids, typically the sodium or potassium salts and amine(RlR2R3) salts of hydrochloric, sulfuric, rhn~rhnrif Cl-ClOaL~y~ acid and boric acid, in which amine salts Rl, R2 and R3 have the meaning inclicated above;
- isethionic acid;
- tannic acid;

wo 96/06152 4 2~ ~6774 - acid amides of formula (3) Rl-co-N

wherein Rl is hydrogen or C~-C12alkyl, and R2 and R3 are each ' r 1 ~/ of the other hydrogen, Cl-CI2aikyl, C2-Cl2aikenyl, C1-CI2hyl1~u~y~ yl, C2-CI2hydroxyaikyl, or a polyglycol ether chain containing 1 to 30 -CH2-CH2-O- or -CHY1-CHY2-O- groups, wherein one of the radicais of Yl or Y2 is hydrogen and the other is methyl, e.g.
N-~I..,L~
- urea derivatives of formula Rl\ / R3 N-CO N
R2 \ R4 wherein Rl, R2, R3 and R4 are each ;~L ~ y of one another hydrogen, Cl-CsaL~cyl, C2-C8alkenyl, Cl-Csl-y~llu~JdL~ I or C2-CshydroxyaLIcenyl;
- I.lu..Jh.~dl;., C4-C18aliphatic and mono~,y.,li-. aicohois, typicaily C2-CI8alkanols, C2-CI8aL~enols and terpene alcohol8 e.g. ethanol, propanol, ;~ul~ u~ 1 hexanol, cis-3-hexene-1-ol, trans-2-hexene-1-ol, 1-octen-3-ol, heptanol, octanol, trans-~-cis-~nonadien-l-ol, decanol, iinaiol, geraniol, Li.. ~ f~l.
myrcenol, nopol and terpineol;
- aromatic aicohols of formula (5) ~ X--OH
R2~=/

wherein X is -(CH2)l 6, -CH=CH-CH2-, or -O-(CH2)2 6, and Rl, R2 and R3 are each i~ L lly of one another hydrogen, hydroxy, halogen ~Wo 96/06152 . ~l/~ _. û

or Cl-C6alkoxy, typically benzyl alcohol, 2,~d;~ 1ulub~ yl alcohol, y~ ol, 1-phenoxy-2-propanol (I)L~IIU~ U~ )I) and cinnamyl alcohol;
- polyhydric alcohols and polyhydric aLlcoxylated, preferably ctllu~yl~.~,d andlor l~u~u~ y' ' alcohols as well as the ethers and esters thereof of the general formula (6) Rl-O-X-O-R2, wherein Rl and R2 are each; L l,.. 1.. ;ly of the other hydrogen, Cl-CI2aLkyl, C2-CI2alkenyl, Cl-Csalkanoyl~ C3-Cl8alken~Y
R3-(OCH-CH2t~, wherein R3 is hydrogen, Cl-CI2alkyl or C2-CI2alkenyl, and R4 is hydrogen or -CH3, and X is C2-CIOalkylene or C2-CIOalkenylene, -(CH2CH2O~ CHrcH2- or -(CH2-CH-O ~ CH2-CH-.

All organic acids mentioned under (b) may also be obtained in the form of their water-soluble salts, such as the aL~ali metal salts, preferably the sodium or potassium salts or the amine(NRlR2R3) salts, wherein Rl, R2 and R3 are each ~ , of one another hydrogen, Cl-C8alkyl, C2-Csalkenyl, Cl-Cshydroxyalkyl, C5-Cscycloalkyl or polyalh~ yl~,uo~y-Cl-CIsalkyl, or Rl, R2 and R3, together witb the linking nitrogen atom, are . . . l or Cl-C4aL~cyl-substiwted ~ /u~

Con~p~ nt (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 .... "I~.u ~ ~ of further subclasses.

=

Preferably a c~rAhinA~iem of one or more than one compound of subclass (bl) and one or more than one compound of subclass (b2) is used.
P,~ ' 'y preferred in this connection is a e.~ ;. . . of cumene sulfonate and citric acid IllulloLyd Suitable ~ v -- n ~ (c) are anionic, nonionic or ~w;L~iu,.i., and amphoteric synthetic, surface-active 5nh~orrl c Suitable anionic surface-active substances are:
- sulfates, typically fatty alcohol sulfates, which contain 8 to 18 carbon atoms in the aL~cyl chain, e.g. sulfated lauryl alcohol;
- fatty alcohol ether sulfates, typically the acid esLers or the salts thereof of a polyadduct of 2 to 30 mol of ethylene oxide v.~ith 1 mol of a C8-C22fatty alcohol;
- the aLcali metal salts, ~r salts or amine salts of C8-C20fatty acids, which are termed soaps, typically coconut fatty acid;
- alkylamide sulfates;
- aLlcylamine sulfates, typically, ' ' lauryl sulfate;
- allcylamide etber sulfates;
- alkylaryl polyether sulfates;
- I~.ollo~ ~.idc sulfates;
- aLtcane sulfonates, containing 8 to 20 carbon atoms in the aLl~yl chain, e.g. dodecyl sulfonate;
- alkylamide sulfonates;
- allcylaryl sulfonates;
- cc-olefin sulfonates;
1r~I~'-'~'' ;~ acidderivatives,typicallyalkyl ''( - aLI~ylether ,~,l r~ A S ~ or aLIcyl ~, ,1 r ~ lr ~li~_Li~
- N-[alkylamidoalkyl]amino acids of formula CH3(CH2)n-CO-N
\ CH-~COO-M+

~Wo 96106152 . ~ 'C

wherein X is hydrogen, Cl-C4alkyl or -COO-M+, Y is hydrogen or Cl-C4alkyl, Z is -(CH2) m~
ml is 1 to 5, nl is an integer from 6 to 18, and M is an aL~cali metal ion or an amine ion;
- allcyl cther ~ w~y' and aLlcylaryl ether ~,r~l~uA~yh..~," of formula (8) CH3-X-Y-A, wherein X is a radical tCH21~ ~-, ~CH~ ~--or -(CH2)s 19 N

R is hydrogen or Cl-C4alkyl, Y is -(CHCHO}~

Il O-M+
A is-(CH~ COO~M+ or p O-M+
m2 is I to 6, and M is an aL~ali metal cation or an amme cation.

The anionic surfactants used may fu~Lh~ .o c be fatty acid mcthyl taurides, yl;~u~ , fatty acid ~July~ rl. ..,~.~t. .~ and fatty alcohol phosphoric acid esters. The aL"yl radicals in these; . ' prcferably contain 8 to 24 carbon atoms.

The anionic surfactants are usually obtaincd in the form of their water-soluble salts, such as the allcali metal, or amine salts. Typical examples of such salts are lithium, sodium, potassium, A~ y~ r~ . or - - - i, salts. It is preferred to use the sodium or potassium salts or the (NRIR2R3) salts, wherein Rl, R2 and R3 are each ~r ~ '~y of one another hydrogen, Cl-C4alkyl or Cl-C4hydroxyaL'cyl.

Very particularly preferred anionic surfactants in the novel r.",., l~li. ,., are wos6/06ls2 l~,~/~l9' ~ ---8- 2~96774 ~ Iauryl sulfate or the aLcali metal salts of fatty alcohol sulfates, preferably the sodium lauryl sulfate and the reaction product of 2 to 4 mol of ethylene oxide and sodium lautyl ether sulfate.

Suitable L,W;Ii~,liUlli~, and amphoteric surfactants are C8-CI8betaines, C8-C~8~ Iruh ~
C8-C24aLkylamido-CI-C4all~yl. b~ l - c, ' ' ' '' ~albu~y- , aL~ylCl..~JIIU~GlbUAy carboxylic acids, aLI~y' .1 ~ yli~, acids (e.g l "~ h~;IY~ ) and N-aLlcyl-~-~UII;IIUIJ1~ l or N-alkyl-~-;,..; n~ , v~;n; t ~ It is preferred to use the CIO-C20aIICYIamidO-CI-C4aIIf Y~ r b~ .. C and, more ~ .ul~ly~
~uCr.- -;~ ulJylbetaine~

Nonionic surfactants ate typically derivatives of the adducts of propylene wd~/u~ll.yl~.ll~.
oxide having a molecular weight of 1000 to 15000, fatty alcohol G~hu~.y' tl-50 EO), rL~yl~ lol polyglycol ethers (1-50 EO), ethoxylated wlbuLyl' fatty acid glycol partial esters, typically diethylene glycol - , fatty acid ~'11 ' ' ' and fatty acid ~i~lL ~-,..;.l . fatty acid -~ll A .h~ . ethoxylates and fatty acid amine oxides.

For component (c) may rul LL~llllUlCi be used the salts of saturated and C8-C2~fatty acids, either by themselves, in admixture with each other or in admixturc with the other surface-active substances cited for component (c). Illustrative examples of these fatty acids are typically capric, lauric, myristic, palmitic, stearic, arachic, behenic, AnArcl-nnir t~ .. n;~, o~ I~.l....n;~, oleic, eicosanic and erucic acid, as well as the technical mixtures of such acids, typically coconut fatty acid. These acids may be ûbtained in the form of salts, suitable cations being allcali metal cations such as sodium and potassium cations, metal atoms such as zinc atoms and aluminium atoms or nitrogen-containing organic ~ p u ,..A~ of sufficient aLcalinity, typically amines or c~l.u~y' ' amines. These salt can also be prepared in situ.

Suitable . . (d) are dihydric alcohols, preferably those containing 2 to 6 carbon atoms in the aLIcylene radical, typically etbylene glycol, 1,2- or 1,3-1,.u~ liol, 1,3-, 1,~
or 2,3-butanediol, 1,5-p. .~IAIIr~I;nI and 1,6 ~ ~ A l A;nl 1,2-1~lu~ .d;ol (propylene glycol) is preferred.

~ . (e) is preferably ethanol, n-propanol and i~u~J~u~ ol~ or a mixture of thesealcohols.

~wo 96/06152 J ~

~hmprn~ntc (d) and (e) may also be obtained in admixture with each other.
, The pH of the novel r...., .. Il -, ;..., is 3 to 10, preferably 3,5 to 5,5.

The novel r.., . ,~ obtained as soap or syndet solutions may additionally comprise customary additives, typically ~ , dyes, perfume oils, thickeners or solidifiers (~:U~ ,y regulators), emollients, UV absorbers, skin-protection agents, additives which improve the nnf rl~ ir~l properties, such as d;~ubu~.ylil, acids and!or Al, Zn, Ca, Mg salts of Cl4-C22fatty acids and, if desired, ~ \ r~

Soap r. ., . l~ of the invention can be prepared by mixing ~ lr - (a) and (b) and, optionally, (c), (d) and (e), in any order, with the requisite amount of water and stitring the mixture to hr..,.h". .;y. The mixture is bulked to 100% with mains water or deinonised water. This pt~cedure is a purely physical procedure. Accordingly, there is no chemical reaction of the individual ~

For ~ rr~ and cleamsing of the human skin and hands and of hard objects, the novel soap r ,, -l~ C 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 ~ ' ~f 1;~

The invention is illustrated by the following Examples. Parts and ~ are by weight.

Example 1:
0.075 % 2,4,4'-trichloro-2'-l.yLu,.yL~ ,.. yl ether, 0.5 % . . .r.~ ll.,. hl ; ~
0.25 % sodium cumene sulfonate powder, 0.4 % citric acid lunhl.~,' , and 0.5 % propylene glycol are stirred to I ~ ~ and about 90% of the requisite water is then added. The pH is adjusted to 4.0 with . . 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;, ""l ";"~ is added to adjust the pH to 4Ø

Example 2:
0.25 % 2,4,4'-trichlor~2'-l.~Lu~ydi~h~ l ether -lo- 279~

1.0 % ~ h " ~ Iauryl sulfate 2.5 % sodium cumene sulfonate powder, 1.5 % citric acid ' y~ , and 1.0 r;o propylene glycol are stirred to 1~ ;y and about 90~o of the requisite water is then added. The pH is adjusted to 4.0 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 4Ø

Example 3:
0.15 r~o 2,4,4'-trichloro-2'-Ly~hu~yL~ ,.lyl ether 1.0% ,,, .hll,,r,l-;,. laurylsulfate 0.5 % sodium cumene sulfonate powder, 0.8 % cittic acid ~llw~uhyd , and 5.0 % propylene glycol are stirred to 1~ y and about 90r~O of the requisite water is then added. The pH is adjusted to 4.0 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, ,.. .~,lh ~ is added to adjust the pH to 4Ø

Example 4:
0.1 % 2,4,4'-trichloro-2'-Ly~Lu~y~ l ether 4.0 % , ~nr,~ Ih- ~1 ,;, lauryl sulfate 0.5 % sodium cumene sulfonate powder, and 0.019 % NaOH
are stirred to h. ~ G~ Iy and about 9ors~r of the reo,uisite water is then added. The pH is adjusted to 9.1 with 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 9.1.

Example 5: Test of the ~Id~,lub;c;ddl activitiv of the novel r~.. "" ~ 1;.~ -The IlI;~.lUh;~ LII activity (in decimal logarithms) of the novel ru, ~Il..l..l;l~llc according to Examples 1 to 4 is determined with a suspension test. This test is used to assess the h:~rrPrir~ zctivityofwater-solubleantiseptics~plo ~f ~'- ,l~andofliquidsoaps.T-hetest consists in seeding the test product in selected dilutions with the test bacillus. After a certain contact time, aliquots is taken and the number of surviving bacilli is ~prprmin ~Wo 96/06152 . ~

2196~7~

The difference behveen the number of the bacilli added and the number of the surviving bacilli is expressed as bacilli reduction in decimal log;~ hmc The is 90~o, the contact time is 30 seconds.

The following bacilli are used:

Example 1 2 _ _ 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 4.0 *
P. aeruginosa CIP A-22 5 4 >5 A >5.4 Serratia ~ ATCC 13,880 ~ * * >5.4**

* not measured ~* contact time 5 minutes Values above 4 indicate good --- ;...;. .~,l.:~l activi~.

Claims

What is claimed is

1. A surface-active surfactant formulation, 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%.

2. A formulation according to claim 1, wherein component (a) is 2-hydrozyphenyl ether, 2-hydroxydiphenylmethane and 2-hydroxydiphenyl thioether of the general formula wherein X is oxygen, sulfur or -CH2-, Y is chloro or bromo, Z is SO2H, N02 or C1-C4alkyl, 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.

3. A formulation according to claim 2, wherein the compounds used for component (a) are those of formula (1), wherein X is oxygen, sulfur or -CH2-, and Y is chloro or bromo, m is 0, n is 0 or 1, o is 1 or 2, r is 1 or 2, and p is 0.

4. A formulation according to claim 2 or 3, wherein the compounds used for component (a) are those of formula (1), wherein X is oxygen, and Y is chloro, m is 0, n is 0, o is 1, r is 2, and p is 0.

5. A formulation according to claim 4, wherein the compound used for component (a) is that of formula .

6. A formulation according to any one of claims 1 to 5, wherein component (a) is used in an amount of 0.02 to 0.2% by weight.

7. A formulation according to any one of claims 1 to 6, wherein component (b1) is a sulfonate, preferably a salt thereof of a terpenoid or of a mono- or binuclear aromatic compound.

8. A formulation according to claim 7, wherein the mono-or binuclear aromatic compound is a sulfonate of camphor, toluene, xylene, cumene or naphthene.

9. A formulation according to claim 7, 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), also with components of further subclasses.

10. A formulation according to any one of claims 1 to 7, 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).

11. A formulation according to claim 9, wherein a combination of cumene sulfonate and citric acid monohydrate is used.

12. A formulation of any one of claims 1 to 11, wherein the anionic surfactant is a fatty alcohol sulfate, which contains 8 to 18 carbon atoms in the chain.

13. A formulation according to claim 12, wherein the anionic surfactant is the alkali metal salt of the sulfated lauryl alcohol or of the monoethanolamine lauryl sulfate.

14. A formulation according to any one of claims 1 to 11, wherein component (b) is C10-C20 alkylamido-C1-C4alkylenebetaine.

15. A formulation according to any one of claims 1 to 14, wherein the salt of a saturated and/or unsaturated C8-C22 fatty acid corresponding to component (c) is selected from the group consisting of lauric, myristic, palmitic, stearic, arachic, behenic, dodecenoic, tetradecenoic, octadecenoic, oleic, eicosanic and erucic acid.

16. A formulation according to any one of claims 1 to 15, wherein component (d) is propylene glycol.

17. A formulation according to any one of claims 1 to 16, wherein component (e) is selected from the group consisting of ethanol, propanol, isopropanol and mixtures of these alcohols.

18. A formulation according to either claim 16 or claim 17, wherein components (d) and (e) are used in admixture with each other.

19. Use of an antimicrobial soap formulation according to any one of claims 1 to 18 for the disinfection and cleansing of the human skin and hands and of hard objects.

20. Use according to claim 19, wherein the antimicrobial soap formulation is in dilute or undilute form.