EP0948393A1 - Detergent compositions containing low concentration levels of gemini surfactants - Google Patents

Abstract

Aqueous surfactant compositions containing low concentrations of surfactant actives are provided comprising a surfactant mixture with one or more gemini surfactants. The aqueous composition containing a total amount of surfactant based on active weight equal to or less than 0.01 % by weight based on the total weight of the composition. The gemini surfactants comprise from about 10 % to about 100 % by weight of the total surfactant active weight in aqueous composition.

Description

DETERGENT COMPOSIΗONS CONTAINING LOW CONCENTRAΗON LEVELS OF GEMINI SURFACTANTS

This invention relates to improved surfactant systems useful as emulsifiers and in detergents at very low concentration.

Emulsification is an extremely important technology and it is a process which is used in detergencN . emulsion polymerization, cosmetics, food, agrochemicals. paints, paper, transportation of crude oil. etc Emulsifiers function as essential ingredients in personal care and household products, industrial and institutional cleaners including shampoo, car washes, carpet shampoo, hand dishwashing liquids, latex foaming and oil recovery compositions: and the like In order to form a relatively stable emulsion, an emulsifier is required to adsorb at an oil-water interface to prevent emulsion αroplet coalescence The maioπn of emulsifiers are synthetic surfactants or natural products with amphiphiiic character Presently, usage levels of surfactants for effective emulsification are usually above 0.1% active based on the total weight of the detergent solution which is used in the final use composition. For a given emulsifier system, it would be advantageous to use a lower amount of surfactant to reduce the cost and amount of surfactant waste discharged into the environment: and to improve the performance of final products (e.g.. the film forming and water resistance will be improved in latex paints and skin irritation will be reduced for cosmetic proαucts with less surfactants ) While conventional surfactants generally have one hydrophilic group and one hydrophobic group, recently a class of compounds having at least two hydrophobic groups and at least two hydrophilic groups have been introduced. These have become known as "gemini surfactants" in the literature (Chemtech. March 1993, pp 30 - 33), and J. American Chemical Soc. 1 5. 10083-10090. (1993) and the references cited therein). Other gemini surfactant compounds, that is. compounds having at least two hydrophilic groups and at least two hydrophobic groups are also disclosed in literature but often are not referred to expressly as gemini surfactants.

An intensive study of gemini surfactants as emulsifiers has been made. From these studies, it has been found that gemini surfactants are unexpectedly effective emulsifiers when used at very low concentrations in comparison to conventional surfactants. This finding is reflected in superior detergencv at very low concentrations. Other performance properties related to emulsification as mentioned above can be also improved using low concentrations of gemini surfactants.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has been discovered that gemini surfactants of the type described and claimed herein can be extremely effective emulsifiers for oil-in-water emulsions at lower concentrations than that needed

utilizing corresponding conventional surfactants. Furthermore, the detergencv is also improved over that provided by conventional surfactants at these low concentration levels. BRIEF DESCRIPTION OF THE DRAWINGS

Figures 1 and 2 are bar graphs representing the comparison of detergencv of polyoxyethylene (13) methylene bis (octylphenol) (MBOP) versus a control of polyoxyethylene (7.5) octylphenol (OP) on different fabrics at 0.005% & 0.01 % by weight respectively.

Figures 3 and 4 are bar graphs representing the comparison of detergencv of polyoxyethylene(13) methylene bis (octylphenol) (MBOP) in a 1 : 1 blend with sodium

dodecylbenzene sulfonate versus a control of polyoxyethylene (7.5) octylphenol (OP)in a 1 :1 blend with the same sulfonate on various fabrics at 0.001% & 0.005% by weight

respectively.

DETAILED DESCRIPTION OF THE INVENTION

The surfactant solutions of the invention are based on certain gemini surfactants. As used herein, the term "gemini surfactants^" is intended to mean surfactants having at least 2 hydrophobic groups and at least 2 hydrophilic groups per molecule.

A number of the gemini surfactants are reported in the literature, see for example. Okahara et al. J. Japan Oil Chem. Soc. 746 (Yukagaku) (1989); Zhu et al..

67 JAOCS 7.459 (July 1990); Zhu et al. 68 JAOCS 7.539 (1991); Menger et al.. J. Am. Chemical Soc. 1 13. 1451 ( 1991): Masuyama et al.. 41 J. Japan Chem. Soc. 4.301

( 1992): Zhu et al. 69 JAOCS 1.30 (Jan. 1992); Zhu et al.. 69 JAOCS 7.62^~6 July 1992 ):

Menger et al.. 1 15 J. Am. Chem. Soc. 2. 10083 (1993): Rosen. Chemtech 30 (March

1993): and Gao et al.. 71 JAOCS 7.771 (July 1994). all of this literature incorporated

herein bv reference. Also, gemini surfactants are disclosed by U.S. Patent Nos. 2,374.354. Kaplan; 2.524.218, Bersworth; 2.530.147 Bersworth (two hydrophobic tails and three hydrophilic heads); 3.244.724. Guπmann; 5,160,450. Okahara. et al., all of which are incorporated herein by reference.

The gemini surfactants may be anionic. nonionic. cationic or amphoteric. The hydrophilic and hydrophobic groups of each surfactant moiety (A,A^!) may be any of those known to be used in conventional surfactants having one hydrophilic group and one hydrophobic group.

For example, a typical nonionic gemini surfactant, e.g.. a bis-polyoxyethylene alkyl ether, would contain two polyoxyethylene alkyl ether moieties.

Each moiety would contain a hydrophilic group, e.g., polyoxyethylene. and a hydrophobic group, e.g., an alkyl chain.

Anionic and nonionic gemini surfactants which are. useful in the present invention include those of the formula: R,

I

I. R - A - (R₂)_t - Z

I R₃ I

R - A - (R₂), - Z

I R.

wherein R is independently C, to C ₂ alkyl. R₄C(0) -. or R -B-R₅-

wherein R4 is C, to C alkyl. R is C, to C₁₂ alkyl. and B is an amide group. [ -C(0)N(R₆)- ]. an amino group [ -N(R₆)- ]. a carboxyl group [ -C(0)-0- ]. a carbonyl group, and a polyether group [ -0(EO)_aPO)_h- ] wherein EO represents ethyleneoxy radicals. PO represents propyleneoxv radicals, a and b are numbers of from 0 to 100, a is preferably from about 0 to about 30 and b is preferably from about 0 to 10. wherein a plus b is at least one, and the EO and PO radicals can be randomly mixed or in discrete blocks, and R^ is hydrogen or C_{ to C₆

alkyl;

Rι is independently hydrogen or C, to C₂₂ alkyl;

R₂ is independently a C_rC_j0 alkyl. -0-. an amide group [ -C(0)N(R₆)- ]. a polyether group [ -0(EO)_a(PO)_b- ]. -R₇-D-R₇- or

-D-R₇-D wherein R₇ is independently a C, -C₆ alkyl and D is -0-. -S-. an amide group [ -C(0)N(R₆)- ], or an amino group [ -N^Rg)- ], wherein ^, , a and b are as defined above, and t is independently 0 or 1.

Z is independently hydrogen. -S0₃Y, -P(0)(OY)₂. -COOY, -CH₂COOY, -CH₂-CH(OH)CH₂S0₃Y and when R₂ is not a polyether. Z is also -OS0₃Y. and - OP(0)(OY)₂: wherein Y is hydrogen, alkali metal such as sodium and potassium; alkaline earth metal such as magnesium and calcium: ammonium: or organic base salt such as monoethanolamine. diethanolamine. triethanolamine. triethylamine, trimethylamine. N-hydroxyethyl morpholine. and the like.

A is independently a straight chain or branched C, to C₆ alkyl. such as

-CH-CH,-. -CH-CH,-. or -C-CH,-

CH, CH, an O-R₅-O- group or aryl; preferably phenyl; R₃ is a bond, an aryl group such as a

phenyl or diphenyl group, a C, to C_I0 alkyl group, preferably a C, to C₄ alkyl group, most preferably methylene. -0-. -S-, -S-S-. -N(R₆)-. -R₅-0-. -R₅[0(EO)_a(PO)_b-]. -D,- R₈-D_r or -R_g-D,-R₈- wherein R₈ is independently a C_rCι₀ alkyl group. -C(O)-, -R₅[0(EO)_a(PO)_b]-, -0-R₅-0-. or aryl, e.g. phenyl. and D, is independently -0-. -S-, -

S-S-. -S0₂-. -C(O) -. a polyether group [ -0(EO)_a(PO)_b- ], an amide group [- C(0)N(R₆)-]. an amino group [ -N^)-], -O-R₅-O-. or aryl wherein R₅. R₆. a and b are as defined above.

On the formulae of this disclosure, the term "alkali^*" includes substituted alkali, especially the hydroxy substituted derivatives thereof and straight as well as branched chains. When Z is hydrogen, the gemini surfactants are nonionic.

The compounds of Formula I are more fully described in copending application U.S.S.N. 08/292,907 filed 08/19/94, the entire disclosure of which is incorporated herein by reference. Other gemini surfactants specifically useful in the present invention include gemini anionic or nonionic surfactants of the formulae:

I

R₄-R_c-0(EO)_a(PO)_b-Z I

II. R₃ and

I R₄-R_c-0(EO)_a(PO)_b-Z

I R, I R₄-C-CH,-0(EO)_a (PO)_b-Z III. I

R₃

R₄-C-CH,-0 (E0)_a (PO)_b-Z

I R,

wherein R_c represents aryl, preferably phenyl.

R|. R₃. R₄. Y. Z. a and b are as defined above. More specifically, these compounds comprise:

R, R₄ ^~fc) -0(EO)_a(PO)_b-Z IV. R₅

R,

R₄ C) -0(EO)_a(PO)_b-Z

I

C(O)

I

V. R<

C(O)

R₄ ^. , -0(EO)_a(PO)_b-Z

R, R,

R₄ ^"rc) -0(EO)_a(PO)_b-Z O

VI. I R₅ o

R_A -(£) - 0(EO)_a(PO)_b-Z

wherein R₎. R₄, R₅, Z. a. and b are as defined hereinbefore.

The primary hydroxyl group of these surfactants can be readih phosphated. sulfated or carboxylated by standard techniques.

The compounds included in Formula II can be prepared by a variety of synthetic routes. For instance, the compounds of Formula IV can be prepared by condensing a monoalkyl phenol with paraformaldehyde in the presence of an acid catalyst such as acetic acid. The compounds of Formula V can be synthesized by a Lewis acid catalyzed reaction of an alkylphenol with a dicarboxylic acid, e.g., terephthalic acid.

The compounds of Formula II are more fulh described in copending

application U.S.S.N. 60/009.075 filed 12/21/95. the entire disclosure of which is incorporated herein by .reference.

A class of gemini surfactants that can be used in providing the improved emulsions which are operable at lower concentrations as disclosed in the present invention include a group of amphoteπc, and cationic quaternan surfactants comprising compounds of the formula VII.

(R.), wherein R. t, and Z are as defined hereinbefore. R, is as defined before and includes the [ -(EO)_a(PO)_bO- ]H moiety. R₂ is as defined before, however, D includes the

following moieties: -N(R₆)-C(0)-R₅-CH₂0- and -N(R₆)-C(0)-R₅-N(R₆)-R₄-. When t is zero, the compounds are amphoteric and when t is 1 , the compounds are cationic quaternary compounds. R₃ is selected from the group consisting of a bond. C _|-C₁₀ alkyl. and -R₈-D,-R₈- wherein D,, R₅, R^. a. b. and R₈ are as defined above (except R₈

is not -OR₅0-).

Preferably, the compounds of Formula VII comprise:

R - C(O) - N(H) - R₅ - N - R₂ - Z I

VIII. (CH₂)_n

R - C(O) - N(H) - R; - N - R₂ - Z wherein R. R₂. R₅ and Z are as defined above and n equals a number from about 2 to about 10. More particularly, the compounds of Formula VII comprise:

R - C(O) - N(H) - (CH₂)_m - N - R, - Z

I

IX. (CH₂)_n i

R - C(O) - N(H) - (CH₂)_m - N - R₂ - Z

wherein R. R₂. R . Z. and n are as defined hereinbefore: and m independently equals a number between about 2 and about 10. Representative compounds of Formula VII include.

R - C(O) - N(H) - CH, - CH, - N - CH,CO,Na

I CH,

X I CH,

I

R - C(O) - N(H) - CH, - CH, - N - CH,CO,Na

R - C(O) - N(H) - CH, - CH, - N - CH,CH,CO,Na

I

XI CH,

I CH,

I R - C(O) - N(H) - CH, - CH, - N - CH,CH,CO,Na

R - C(O) - N(H) - CH, - CH, - N - CH, - CH(OH) - CH, - S0₃ - Na

I

CH,

XII I CH,

R - C(O) - N(H) - CH, - CH, - N - CH, - CH(OH) - CH, - SO, - Na

While the compounds of Formulae VII - XII can be prepared by a variety of synthetic routes, it has been found that they can be produced particularly effectively by a process which utilizes a polyamme reactant having at least four amino groups of which two are terminal primary amines such as methylene tetramine These processes are more fully set forth in copending application ^"Amphoteπc Surfactants Havins Multiple Hydrophobic and Hydrophilic Groups^*'. U.S.S N 08/292.993 filed 08/19/94. the entire disclosure of which is incorporated herein by reference Another group of gemini surfactants which have been found to provide the low concentration emulsions of this invention are the cyclic cationic quaternary surfactants of the

wherein R and R are as identified hereinbefore in formula VII: R₉ is independently a C _| - C_|0 alkyl or alkylaryl; and X represents a counterion such as an anion illustrated by halogen (Cl . Br. and I), alkylsulfate such as methyl or ethylsulfate. alkylphosphate such as methylphosphate. and the like.

Preferably, the compounds used in the present invention comprise those of

Formula XIII in which R₃ is a C, - C₄ alkyl. most preferably ethyl. Ro is a lower alkyl of from 1 to about 4 carbon atoms, most preferably methyl: and X is halogen or methylsulfate.

The compounds of Formula XIII can be prepared by a variety of snythetic

routes though it has been found that they can be produced particularly effectively by quaternizing a bisimidazoline prepared by a process disclosed and claimed in copending application "Amphoteric Surfactants having Multiple Hydrophobic and

Hydrophilic Groups^"". U.S.S.N. 08/292.993 filed 08/19/94 wherein a polyamme reactant having at least four amino groups, of which two are terminal primary amine groups, is reacted with an acylating agent such as a carboxylic acid, ester, and the naturally occurrins trislvceride esters thereof or acid chlorides thereof in an amount sufficient to provide at least about 1.8 fatty acid groups [R,C(0)-] per polyamine to provide the bisimidazoline.

Also included in the gemini surfactants useful in this invention are those of the formula: R₁₃-(CH,)_p-N-R₁₄

XIV. R₃

R₁₃-(CH₂)_p N-R₁₄

wherein R,₃ is a sugar moiety, e.g.. a monosaccharide. desaccharide, or polvsaccharide such as glucose: or a polyhydroxy compound such as glycerol; p is independently 0 to 4: R₃ is as defined above in formula VII; and R_M is a C_rC,₂ alkyl or -C(0)R₄ wherein R₄ is as described above.

Some σf the compounds such as those described above are set forth more fully in U.S. Patent 5.534,197 which description is incorporated herein by reference.

In the compounds used in the invention, many of the moieties can be derived from natural sources which will generally contain mixtures of different saturated and unsaturated carbon chain lengths. The natural sources can be illustrated by coconut oil or similar natural oil sources such as palm kernel oil. palm oil. osya oil. rapeseed oil.

castor oil or animal fat sources such as herring oil and beef tallow. Generally, the fatty acids from natural sources in the form of the fatty acid or the triglyceride oil can be a mixture of alkyl radicals containing from about 5 to about 22 carbon atoms. Illustrative of the natural fatty acids are caprylic (C₈). capric (C₁₀). lauric (C,,). myristic (C,₄). palmitic (C,₆). stearic (C₁₈). oleic (C₁₈. monounsaturated). linoleic (C,_g, diunsaturated). linolenic (C,₈. triunsaturated). ricinoleic (C₁₈. monounsaturated)

arachidic (C₂₀). gadolic (C₂₀. monounsaturated). behenic (C,,) and erucic (C₂₂). These fatty acids can be used per se. as concentrated cuts or as fractionations of natural source acids. The fatty acids with even numbered carbon chain lengths are given as illustrative though the odd numbered fatty acids can also be used. In addition, single

carboxylic acids.e.g.. lauric acid, or other cuts, as suited for the particular application, may be used.

Where desired, the surfactants used in the present invention can be oxyalkylated by reacting the product with an alkylene oxide according to known methods, preferably in the presence of an alkaline catalyst. The free hydroxyl groups of the alkoxylated derivative can then be sulfated. phosphated or acylated using normal methods such as sulfation with sulfamic acid or sulfur trioxide-pyridine complex, or acylation with an acylating agent such as a carboxylic acid, ester, and the naturally occurring triglyceride esters thereof.

For alkylation conditions and commonly used alkylating agents, see

Amphoteric Surfactants Vol. 12, Ed. B. R. Bluestein and C. L. Hilton, Surfactant Science Series 1982, pg. 17 and references cited therein, the disclosures of which are incorporated herein by reference.

For sulfation and phosphation. see Surfactant Science Series. Vol. 7, Part 1. S. Shore & D. Berger, page 135. the disclosure of which is incorporated herein by reference. For phosphating review, see Surfactant Science Series. Vol. 7. Part II. E. Jungermarm & H. Silbertman, page 495. the disclosure of which is incorporated herein by reference.

The surfactant compositions of the invention are extremely effective in aqueous solution at low concentrations as defined herein. The surfactants of the invention can be used in any amount needed for a particular application which can be easily determined by a skilled artisan without undue experimentation.

W ile the gemini surfactants of the invention can be used alone, it has been unexpectedly found that blends of the compounds of the invention with certain other conventional well known anionic, nonionic. cationic and amphoteric surfactants provide synergistic effects in relation to critical micelle concentration (cmc) and surface tension reducing ability, and hence improved detergencv.

A. Nonionic Surfactants

Nonionic surfactants, including those having an HLB of from 5 to 17. are well known in the detergency art. Examples of such surfactants are listed in U.S. Patent No.

3,717.630. Booth, issued February 20. 1973, and U. S. Patent No. 3.332.880. Kessler et al., issued July 25, 1967, each of which is incorporated herein by reference.

Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows:

(1 ) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example. from polymerized propylene. diisobutylene. and the like. Examples of

compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol: dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol: dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630. marketed by Rhone-Poulenc Inc. and Triton X-45, X-1 14, X- 100, and X-102, all marketed by Union Carbide.

(2) The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9

moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitol 15-S- 9. marketed by Union Carbide Corporation. Neodol 45-9. Neodol 23-6.5. Neodol 45-7. and Neodol 45-4. marketed by Shell Chemical Company.

(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds typically has a molecular weight of from about 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50%) of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketed by Wyandotte Chemical Corporation.

(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and e hylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80%) by weight of polyoxyethylene and has a molecular weight of from about 5.000 to about 1 1 ,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetroniα compounds, marketed by Wyandotte Chemical Corporation.

(5) Semi-polar nonionic detergent surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2

moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms: water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbons atoms: and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms. Preferred semi-polar nonionic detergent surfactants are the amine oxide

detergent surfactants having the formula:

O t R'(OR²)_xNR₂ ³

wherein R¹ is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms. R is an alkylene or hydroxy alkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to about 3 and each R is an alkyl or hydroxy alkyl group containing from 1 to about 3 carbon atoms or a_polyethylene oxide group containing from one to about 3 ethylene oxide groups and said R groups can be attached to each other, e.g.. through an oxygen or nitrogen atom to form a ring structure.

Preferred amine oxide detergent surfactants are C_{] 0}-Cj₈ alkyl dimethyl amine oxide. C₈-C_{I 8} alkyl dihydroxy ethyl amine oxide, and C₈.₁₂ alkoxy ethyl dihydroxy ethyl amine oxide.

Nonionic detergent surfactants ( l )-(4) are conventional ethoxylated nonionic detergent surfactants and mixtures thereof can be used.

Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the liquid, powder, and gel applications are biodegradable and have the formula R(OC,H₄)_nOH wherein R is a primary or secondary alkyl chain of from about 8 to about 22. preferably from about 10 to about 20 carbon atoms and n is an average of from about 2 to about 12. particularly from about 2 to about 9. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17. preferably from about 6 about 15 HLB is defined in detail in Nonionic Surfactants, by M J Schick. Marcel Dekker. Inc., 1966, pages 606-613. incorporated herein by reference In preferred

nonionic surfactants, n is from 3 to 7 Primary linear alcohol ethoxvlates (e.g , alcohol ethoxylates produced from organic alcohols which contain about 20%_> 2-methyl branched isomers, commercially available from Shell Chemical Company under the trademark Neodol) are preferred from a performance standpoint

Particularly preferred nonionic surfactants for use in liquid, powder, and gel applications include the condensation product of C_{) 0} alcohol with 3 moles of ethylene oxide, the condensation product of tallow alcohol with 9 moles of ethylene oxide, the

condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of C_!2 alcohol with 5 moles of ethylene oxide; the condensation product of C_{12 I3} alcohol with 6 5 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions, the condensation product of C_{12 13} alcohol with 2 3 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylated and nonethoxylated fractions, the condensation product of C₁₂.₁₃ alcohol with 9 moles of ethylene oxide, the condensation product of C_]4. alcohol with 2.25 moles of ethylene oxide, the condensation product of C_|4.^ alcohol with 4 moles of ethylene oxide: the condensation product of C,₄ ,, alcohol with 7 moles of ethylene oxide, and the condensation product of C,₄ ,_< alcohol with 9 moles of ethvlene oxide For bar soap applications, nonionic surfactants are preferably solids at room temperature with a melting point above about 25° C , preferabh above about 30° C Bar compositions of the present invention made with lower melting nonionic surfactants are generally too soft, not meeting the bar firmness requirements of the present invention.

Also, as the level of nonionic surfactant increases, i.e.. above about 20% by weight of the surfactant, the bar can generally become oily. Examples of nonionic surfactants usable herein, but not limited to bar applications, include fatty acid glycerine and polyglycerine esters, sorbitan sucrose fatty acid esters, polyoxyethylene alkyl and alkyl allyl ethers, polyoxyethylene lanolin alcohol, glycerine and polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol and sorbitol fatty acid esters, polyoxyethylene lanolin, castor oil or hardened castor oil derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidone, glucamides, alkylpolyglucosides. and mono- and dialkanol amides.

Typical fatty acid glycerine and polyglycerine esters, as well as typical sorbitan sucrose fatty acid esters, fatty acid amides, and polyethylene oxide/polypropylene oxide block copolvmers are disclosed by U.S. Patent No. 5.510.042. Hartman et al. incorporated herein by reference.

The castor oil derivatives are typically ethoxylated castor oil. It is noted that other ethoxylated natural fats, oils or waxes are also suitable.

Polyoxyethylene fatty acid amides are made by ethoxylation of fatty acid amides with one or two moles of ethylene oxide or by condensing mono-or diethanol amines with fatty acid.

Polyoxyethylene alkyl amines include those of formula: RNH-(CH,CH,0)_n-H. wherein R is C₆ to C,, alkyl and n is from 1 to about 100. Monoalkanol amides include those of formula: RCONHR'OH. wherein R is C₆-C₂ alkyl and R is C, to C₆ alkylene. Dialkanol amides are typically mixtures of: diethanolamide: RCON(CH,CH,OH)₂; amide ester: RCON(CH,CH,OH)-CH,CH,OOCR; amine ester: RCOOCH,CH,NHCH,CH,OH; and amine soap: RCOOH,N(CH,CH,OH)₂, wherein R in the above formulas is an alkyl of from 6 to 22 carbon atoms.

Examples of preferred but not limiting surfactants for detergent bar products are the following:

Straight-Chain Primary Alcohol Alkoxylates

The deca-, undeca-. dodeca-, tetradeca-. and pentadeca-ethoxylates of n- hexadecanol. and n-hexadecanol. and n-octadecanol having an HLB within the range recited herein are useful nonionics in the context of this -invention. Exemplary ethoxylated primary alcohols useful herein as the conventional nonionic surfactants of the compositions are n-C₁₈EO(10): n-C₁₄EO(13): and n-C₁₀EO( l 1 ). The ethoxvlates of mixed natural or synthetic alcohols in the "tallow^** chain length range are also useful herein. - Specific examples of such materials include tallow-alcohol-EO(l 1 ). tallow- alcohol-EO(18). and tallow-alcohol-EO(25). Straight-Chain Secondary Alcohol Alkoxylates

The deca-, undeca-. dodeca-, tetradeca-. pentadeca-. octadeca-. and nonadeca- ethoxylates of 3-hexadecanol. 2-octadecanol. 4-eicosanol. and 5-eicosanol having an HLB within the range recited herein are useful conventional nonionics in the context of this invention. Exemplary ethoxylated secondary alcohols useful herein are 2- C_l EO(l 1); 2-C₂₀EO(l 1 ): and 2-C₁₆EOf 14). Alkyl Phenol Alkoxylates

As in the case of the alcohol alkoxylates, the hexa- through octadeca- ethoxylates of alkylated phenols, particularly monohydπc alkylphenols. having an HLB within the range recited herein are useful as conventional nonionic surfactants in the instant compositions The hexa- through octadeca-ethoxylates of p-tπdecylphenol,

m-pentadecylphenol, and the like, are useful herein Exemplary ethoxylated alkylphenols useful in the mixtures herein are p-tπdec> Iphenol EO(l l ) and p- pentadecylphenol EO(18) Especially preferred is Nonyl Nonoxynol-49 known as Igepal* DM-880 from Rhone-Poulenc Inc As used herein and as generally recognized in the art a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms For present purposes, nonionics containing a phenylene group are considered to contain an equivalent number of carbon atoms calculated as the sum of the carbon atoms in the alkyl group plus about 3 3 carbon atoms for each phenvlene group Olefinic Alkoxylates

The alkenyl alcohols, both pπman and secondaπ and alkenvl phenols corresponding to those disclosed immediately hereιnabo\ e can be ethoxylated to an HLB within the range recited herein and used as the conventional nonionic surfactants of the instant compositions

Branched Chain Alkoxylates

Branched chain primary and seconda alcohols which are available can be ethoxylated and employed as conventional nonionic surfactants in compositions herein The above ethoxylated nonionic surfactants are useful in the present compositions alone or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surface active agents. Alkylpolysaccharides

Still further suitable nonionic surfactants of this invention include alkylpolysaccharides, preferably alkylpolyglucosides of the formula:

R O(C_nH,_πO)_t(Z)_x wherein

Z is derived from glucose:

R is a hydrophobic group selected from the group consisting of a C_{| 0}-C_{l 8}. preferably a C,,-C|₄, alkyl group, alkyl phenyl group, hydroxyalkyl group, hydroxyalkylphenyl group, and mixtures thereof: n is 2 or 3: preferably 2; t is from 0 to 10; preferably 0; and x is from 1.5 to 8; preferably 1.5 to 4: more preferably from 1.6 to 2.7.

These surfactants are disclosed in U.S. Patent Nos. 4.565.647. Llenado. issued Januan- 21. 1986; 4.536.318. Cook et al.. issued August 20. 1985: 4.536.317. Llenado

et al.. issued August 20, 1985: 4.599.188 Llenado. issued July 8. 1986; and 4.536.319. Payne, issued August 20. 1985: all of which are incorporated herein by reference. The compositions of the present invention can also comprise mixtures of the above nonionic surfactants.

A thorough discussion of nonionic surfactants for detergent bar and liquid products is presented by U.S. Patent Nos. 5.510.042. Hartman et al.. and 4.483.779. Llenado. et al.. incorporated herein by reference. B Anionic Surfactants Anionic surfactants include any of the known hydrophobes attached to a carboxylate. sulfonate. sulfate or phosphate polar, solubihzing group including salts Salts may be the sodium, potassium, ammonium and amine salts of such surfactants Useful anionic surfactants can be organic sulfunc reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfomc acid or sulfunc acid ester group, or mixtures thereof (Included in the

term "alkyl" is the alkyl portion of acyl groups ) Examples of this group of synthetic detersive surfactants which can be used in the present invention are the alkyl sulfates. especially those obtained by sulfating the higher alcohols (C₈-C_{l g} carbon atoms) produced from the glyceπdes of tallow or coconut oil. and alkyl benzene sulfonates

Other useful anionic surfactants herein include the esters of alpha-sulfonated fatty acids preferably containing from about 6 to 20 carbon atoms in the ester group, 2- acvloxvalkane-1 -sulfomc acids preferably containing from about 2 to 9 carbon atoms in the ac\ l group and from about 9 to about 23 carbon atoms in the alkane moiety,

alkyl ether sulfates preferably containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide, olefin sulfonates preferabh containing from about 12 to 24 carbon atoms, and beta-alkvloxv alkane sulfonates preferably containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety

Anionic surfactants based on the higher fatty acids, l e ' soaps^"" are useful anionic surfactants herein Higher fatn acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms and the coconut and tallow soaps can also be used herein as corrosion inhibitors Preferred water-soluble anionic organic surfactants herein include linear alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; branched alkyl benzene sulfonates containing from about 10 to about 18 carbon

atoms in the alkyl group; the tallow range alkyl sulfates; the coconut range alkyl glyceryl sulfonates; alkyl ether (ethoxylated) sulfates wherein the alkyl moiety contains from about 12 to 18 carbon atoms and wherein the average degree of ethoxylation varies between^" 1 and 12. especially 3 to 9; the sulfated condensation products of tallow alcohol with from about 3 to 12, especially 6 to 9. moles of ethylene oxide: and olefin sulfonates containing from about 14 to 16 carbon atoms. Specific preferred anionics for use herein include: the linear C_{! 0}-C_M alkvl benzene sulfonates (LAS); the branched C_]0-C_]4 alkyl benzene sulfonates (ABS) the tallow alkyl ^"sulfates, the coconut alkyl glyceryl ether sulfonates; the sulfated condensation products of mixed C,₀-C_!8 tallow alcohols with from about 1 to about 14 moles of ethylene oxide: and the mixtures of higher fatty acids containing from 10 to

18 carbon atoms.

It is to be recognized that any of the foregoing anionic surfactants can be used

separately herein or as mixtures. Moreover, commercial grades of the surfactants can contain non-interfering components which are processing by-products. For example, commercial alkaryl sulfonates, preferably C₁₀-C₁₄, can comprise alkyl benzene sulfonates. alkyl toluene sulfonates. alkyl naphthalene sulfonates and alkyl poly- benzenoid sulfonates. Such materials and mixtures thereof are fully contemplated for

use herein.

Other examples of the anionic surfactants used herein include fatty acid soaps,

ether carboxylic acids and salts thereof, alkane sulfonate salts, α-olefin sulfonate salts. sulfonate salts of higher fatty acid esters, higher alcohol sulfate ester or ether ester

salts, alkyl, preferably higher alcohol phosphate ester and ether ester salts, and condensates of higher fatty acids and amino acids.

Fatty acid soaps include those having the formula: R-C(0)OM, wherein R is C₆ to C₂₂ alkyl and M is preferably sodium.

Salts of ether carboxylic acids and salts thereof include those having the formula: R-(OR')_n-OCH,C(0)OM. wherein R is C₆ to C,, alkyl. R¹ is C, to C,₀, preferably C, alkyl. and M is preferably sodium.

Alkane sulfonate salts and α-olefin sulfonate salts have the formula: R- S0₃M. wherein R is C₆ to C ₂ alkyl or α-olefin. respectively, and M is preferably

sodium.

Sulfonate salts of higher fatty acid esters include those having the formula:

RC(0)0-R'-S0₃M,

wherein R is C_I2 to C₂₂ alkyl, R is C_{ to C ₁₈ alkyl and M is preferably sodium. Higher alcohol sulfate ester salts include those having the formula:

RC(0)0-R'-OS0₃M.

wherein R is C,,-C,, alkyl. R is C,-C₁₈ hydroxyalkyl. M is preferably sodium. Higher alcohol sulfate ether ester salts include those having the formula: RC(0)(OCH,CH,)_X-R' -OS0₃M. wherein R is C₁₂-C,₂ alkyl. R is C_rC₁₈ hydroxyalkyl. M is preferably sodium and x is

an integer from 5 to 25.

Higher alcohol phosphate ester and ether ester salts include compounds of the

formulas: R-(OR')_n-OPO(OH)(OM);

(R-(OR')_n-0),PO(OM): and

(R-(OR^l)_n-0)₃-PO. wherein R is alkyl or hydroxyalkyl of 12 to 22 carbon atoms, R¹ is C₂H₄, n is an integer from 5 to 25. and M is preferably sodium.

Other anionic surfactants herein are sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms. C. Cationic Surfactants Preferred cationic surfactants of the present invention are the reaction products of higher fatty acids with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof.

A preferred component is a nitrogenous compound selected from the group consisting of:

(i) the reaction product mixtures of higher fatty acids with hydroxyalkylalkylenediamines in a molecular ratio of about 2: 1. said reaction product containing a composition having a compound of the formula:

2 S wherein R, is an acyclic aliphatic C_{! 5}-C₂₁ hydrocarbon group and R, and R₃ are divalent C|-C alkylene groups, commercially available as

Mazamide 6 from PPG, (n) the reaction product of higher fatty acids with dialkylenetπamines in a molecular ratio of about 2.1 , said reaction product containing a composition having a compound of the formula

O O

II II

R,-C-NH-R,-NH-R₃-NH-C-R, wherein R,, R, and R₃ are as defined above; and mixtures thereof Another preferred component is a cationic nitrogenous salt containing one long chain acyclic aliphatic C^-C,, hydrocarbon group selected from the group consisting of

(l) acyclic quaternary ammonium salts having the formula

R<

R₄-N-R, A [-]

I R* wherein R is an acyclic aliphatic C^-C,, Hydrocarbon group. R_< and R^ are C_rC₄ saturated alky l or hydroxyalkyl groups, and A [-] is an anion. especially as described in more detail hereinafter, examples of these surfactants are sold by Witco Chemical Company under the Adogen trademarks; (ii) substituted imidazolinium salts having the formula:

N-CH, + //

R.-C A [-]

\ N-CH₂

/\ R₇ H wherein R, is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group, R₇ is a hydrogen or a C C₄ saturated alkyl or hydroxyalkyl group, and A [-] is an anion

(iii) substituted imidazolinium salts having the formula:

N-CH, +

// R.-C I A [-]

\ _

N-CH,

/\ HO-R, R, wherein R, is a C_rC₃ alkyl group and R,. R and A [-] are as defined above; an example of which is commercially available under the Monaquat ISIES trademark from Mona Industries. Inc.: (iv) alkylpyridihium salts having the formula:

wherein R is an acyclic aliphatic C_{I 6}-C₂₂ hydrocarbon group and A [-] is an anion; and (v) alkanamide alkylene pyridinium salts having the formula: wherein R, is an acyclic aliphatic C^-C,, hydrocarbon group, R, is a divalent C,-C₃ alkylene group, and A [-] is an ion group; and mixtures thereof.

Another class of preferred cationic nitrogenous salts having two or more long chain acyclic aliphatic C|₅-C₂, hydrocarbon groups or one said group and an arylalkyl group are selected from the group consisting of:

(i) acyclic quaternary ammonium salts having the formula:

wherein each R₄ is an acyclic aliphatic C,₅-C,, hydrocarbon group. R is a C_rC₄ saturated alkyl or hydroxyalkyl group. R_g is selected from the group consisting of R₄ and R₅ groups, and A [-] is an anion defined as above; examples of which are commercially available from Witco Company under the Adogen trademarks: (ii) diamido quaternary ammonium salts having the formula: O R, O

R,-C-NH-R,-N-R,-NH-C-R, A [-]

Ro wherein each R, is an acyclic aliphatic C₁ -C₂₎ hydrocarbon group, R, is a divalent alkylene group having 1 to 3 "carbon atoms. R₅ and Rg are C,-C₄ saturated alkyl or hydroxyalkyl groups, and A [-] is an anion; examples of which are sold by Witco Chemical Company under the Varisoft trademark; (iii) diamino alkoxylated quaternary ammonium salts having the formula:

R,- A [-]

wherein n is equal to 1 to about 5. and R,. R,. R₅ and A [-] are as defined above;

(iv) quaternary ammonium compounds having the formula:

R<

R₄-N-CH,- A [-]

R<

wherein each R is an acyclic aliphatic C_{I 5}-C₂, hydrocarbon group, each R₅ is a C|-C₄ saturated alkyl or hydroxyalkyl group, and A [-] is an anion: examples of such surfactants are available from Stepan Chemical Company under the Ammonyx 490 trademark;

(v) substituted imidazolinium salts havins the formula:

wherein each Rμs an acyclic aliphatic C,^-C ₁ hydrocarbon group. R, is a divalent alkylene group having 1 to 3 carbon atoms, and R, and A [-] are as defined above, examples are commercially available from Witco Chemical Company under the Varisoft 475 and Varisoft 445 trademarks, and (vi) substituted imidazolinium salts having the formula

N-CH,

// R,-C A [-]

\

O N-CH, A

R_rC-NH-R, H wherein R,, R and A - are as defined above; and mixtures thereof

The more preferred cationic conventional surfactant is selected from the group consisting of an alkyltnmethylammonium salt, a dialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt, an alkylpyπdinium salt, an alkylisoquinohnium salt, benzethonium chloride, and an acylamino acid cationic surfactant

Anion A

In the cationic nitrogenous salts herein, the anion A [-] provides electrical neutrality Most often, the anion used to provide electrical neutrality in these salts is a hahde. such as chlonde. bromide, or iodide However, other anions can be used, such as methylsulfate. ethylsulfate. acetate, formate, sulfate. carbonate, and the like Chloride and methylsulfate are preferred herein as anion A

Cationic surfactants are commonh employed as fabric softeners in

compositions added during the rinse cycle of clothes washing Many different types of fabric conditionins asents have been used in rinse c\ cle added fabric conditionine compositions as disclosed by U.S. Patent No. 5.236,615, Trinh et al. and U.S. Patent No. 5.405,542. Trinh et al., both patents herein incorporated by reference in their entirety. The most favored type of agent has been the quaternary ammonium compounds. Many such quaternary ammonium compounds are disclosed for example. by U.S. Patent No. 5.510.042, Hartman et al. incorporated herein by reference in its entirety. These compounds may take the form of noncyclic quaternary ammonium salts having preferably two long chain alkyl groups attached to the nitrogen atoms. Additionally, imidazolinium salts have been used by themselves or in combination with other agents in the treatment of fabrics as disclosed by U.S. Patent No. 4.127.489. Pracht. et al.. incorporated herein by reference in its entirety. U.S. Patent No. 2,874.074. Johnson discloses using imidazolinium salts to condition fabrics; and U.S. Patent No.3.681,241. Rudy, and U.S. Patent No. 3,033.704, Sherrill et al. disclose

fabric conditioning compositions containing mixtures of imidazolinium salts and other fabric conditioning agents. These patents^' are incorporated herein by reference in their

entirety.

D. Amphoteric Surfactants Amphoteric surfactants have a positive or negative charge or both on the

hydrophilic part of the molecule in acidic or alkaline media.

Examples of the amphoteric surfactants which can be used herein include

amino acid, betaine. sultaine. phosphobetaines. imidazolinium derivatives, soybean phospholipids. and yolk lecithin. Examples of suitable amphoteric surfactants include the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyl amphocarboxyglycinates and alkyl amphocarboxypropionates. alkyl amphodipropionates. alkyl amphodiacetates. alkyl amphoglycinates and alkyl amphopropionates wherein alkyl represents an alkyl group having 6 to 20 carbon atoms. Other suitable amphoteric surfactants include alkyliminopropionates. alkyl iminodipropionates and alkyl amphopropylsulfonates having between 12 and 18 carbon atoms, alkylbetaines and amidopropylbetaines and alkylsultaines and alkylamidopropylhydroxy sultaines wherein alkyl represents an alkyl group having 6 to 20 carbon atoms are especially preferred.

Particularly useful amphoteric surfactants include both mono and dicarboxvlates such as those of the formulae:

O CH,CH,OH

II /

R-C-NH CH,CH,-N (I);

\ (CH₂)_xCOOM

O CH,CH,OH (CH₂) _xCOOM

R-C-NCH,CH,-N (II); and

\ (CH₂)_xCOOM

R HO-CH,CH CH,CH,COO^" (III)

wherein R is an alkyl group of 6-20 carbon atoms, x is 1 or 2 and M is hydrogen or sodium. Mixtures of the above structures are particularly preferred.

Other formulae for the above amphoteric surfactants include the following: Alkyl betaines

CH₃

R-^TN-CH,-COO^" (IV); I

CH₃

Amidopropyl betaines

O CH₃ II +|

R-C-NH-CH,CH₂CH,-N-CH,-COO^" (V)

CH₃

Alkyl sultaines

CH₃

I

R-N^T-CH,-CH-CH,-S0₃ (VI); and

I I CH₃ OH

Alkyl amidopropylhydroxy sultaines

O CH₃

I! I

R-C-NH-CH,CH,CH,-^τN-CH,CH-CH,-S0₃ ^" (VII): I I

CH, OH

where R is an alkyl group of 6-20 carbon atoms and M is hydrogen or sodium.

Of the above amphoteric surfactants, particularly preferred are the alkali salts of alkyl amphocarboxyglycinates and alkyl amphocarboxypropionates. alk> 1 amphodipropionates. alkyl amphodiacetates. alkyl amphoglycinates. alky 1 amphopropyl sulfonates and alkyl amphopropionates wherein alkyl represents an 1 group having 6 to 20 carbon atoms. Even more preferred are compounds wherein the alkyl group is derived from coconut oil or is a lauryl group, for example, cocoamphodipropionate. Such cocoamphodipropionate surfactants are commercially sold under the trademarks Miranol C2M-SF CONC. and Miranol FBS by Rhone -

Poulenc Inc. Other commercially useful amphoteric surfactants are available from Rhone-

Poulenc Inc. and include:

cocoamphoacetate (sold under the trademarks MIRANOL CM CONC. and MIRAPON FA), cocoamphopropionate (sold under the trademarks MIRANOL CM-SF CONC. and MIRAPON FAS). cocoamphodiacetate (sold under the trademarks MIRANOL C2M CONC. and MIRAPON FB), lauroamphoacetate (sold under the trademarks MIRANOL HM CONC. and MIRAPON LA), lauroamphodiacetate (sold under the trademarks MIRANOL H2M CONC. and MIRAPON LB), lauroamphodipropionate (sold under the trademarks MIRANOL H2M SF CONC. AND MIRAPON LBS). lauroamphodiacetate obtained from a mixture of lauric and myristic acids (sold under the trademark MIRANOL BM CONC). and cocoamphopropyl sulfonate (sold under the trademark MIRANOL CS CONC.)

Somewhat less preferred are:

caproamphodiacetate (sold under the trademark MIRANOL S2M CONC),

caproamphoacetate (sold under the trademark MIRANOL SM CONC).

caproamphodipropionate (sold under the trademark MIRANOL S2M-SF

CONC). and

stearoamphoacetate (sold under the trademark MIRANOL DM).

The aqueous surfactant compositions of the invention comprise a concentration of surfactant equal to or less than the cmc of corresponding conventional surfactants assuming that the gemini is represented in the conventional surfactants as a surfactant having only one hydrophobic grouping and one hydrophilic grouping corresponding to those in the gemini surfactant. Preferably, the total surfactant loading is equal to or less than 80% and more preferably equal to or-less than 60% of the cmc of the conventional surfactants in the final use area. In another embodiment, the total aqueous surfactant concentration at end-use level is less than or equal to about 0.01 % total surfactant on an active basis, preferably less than about or equal to 0.008%. more preferably from less than about or equal to 0.006%: the lower limit being an emulsifyingly effective amount. The gemini surfactant ranges from 100% to about 10%. preferably from 100% to about 20% and more preferably from 100% to about 35% of the total active surfactant in the end-use compositions. The remainder of the surfactant actives comprise other surfactants not claimed under the term "gemini surfactants^" including conventional and other

difunctional or polyfumional surfactants.

Specifically this invention relates to surfactant compositions comprising: 1 ) from about 10% to about 100% by weight of nonionic. cationic. anionic. or amphoteric gemini surfactants or a combination thereof : and

2) from about 0% to 90% conventional anionic. nonionic. cationic. or amphoteric. surfactants or mixtures thereof. The anionic. nonionic, cationic. and amphoteric conventional surfactants useful in this invention have been illustrated hereinbefore. Further description of nonionic detergents can be found in U.S. Pat. No. 4.483.780, the entire disclosure of which is incorporated herein by reference. Other ingredients and unsaturated soaps are also disclosed in U.S. Pat. No. 4.483.780. These surfactant systems of the present invention can be manufactured and used in a variety of detergent composition forms such as solids, powders, granules, pastes, and liquids.

It has been found that certain combinations of the surfactants of this invention can provide unusually good detergency at very low use levels. Detergent compositions prepared utilizing the instant surfactant compositions can be used in laundering processes by forming dilute aqueous solutions of the detergent compositions containing said surfactant compositions and agitating same with soiled fabrics. The surfactant compositions of the instant invention can be used in detergent compositions at from about 0.5% to about 80%, preferably from about 2% to about 50% by weight. based on the total weight of the detergent composition.

Any of commonly used auxiliary additives, e.g.. inorganic salts such as Glauber salt and common salt, builders, humectants. solubilizing agents. UV absorbers, pH adjusting agents, softeners, soil release polymers, soil anti-redeposition agents, conditioning polymers (cationic) for hair and fabric softening, chelating agents, and viscosity modifiers may be added to the surfactant compositions of the invention to form the detergent compositions as the ultimate end-use aqueous surfactant/composition requires.

Such detergent compositions provide excellent detergency at very low surfactant use concentrations, and can be formulated to provide different sudsing patterns by varying the amounts and types of the gemini surfactants used and the nature of the other anionic and nonionic surfactants present.

The gemini surfactants of the invention are extremely mild and non-irritating to both eyes and skin and exhibit low toxicity; enhanced wetting speed, greater surface tension reduction, low and high foaming profile depending on the gemini used, and foam stabilization properties. They also provide excellent compatibility with other surfactants. The products of the invention are stable over a wide pH range and are biodegradable. These properties make these surfactants adaptable for use in products ranging from cosmetics to industrial applications, such as for non-irritating shampoos, e.g., baby shampoos, body shampoos, bubble baths, bath gels, hair conditioning gels, lotions, skin creams, make up removal creams, detergents, fabric softeners and other washing and cosmetic products that contact the skin. The surfactants of the invention can also find use as hard surface cleaners including cars, dishes, toilets, floors, and the like; laundry detergents and soaps; metal working aids; and the like. This invention will now be described with reference to the following nonlimiting examples which are provided for purposes of convenient reference and are illustrative of the procedures by which the compositions of the invention can be prepared. All percentages, parts and ratios herein are by active weight unless otherwise

specified.

EXAMPLE 1

Since emulsifying and detergency power is related to oil-water interfacial

tension, equilibrium interfacial tension in dynes/cm between hydrocarbon (heptane) and water is determined by the spinning droplet method on compositions shown in Table 1 at 30°C The results are reported in Table 1.

Table 1

Equilibrium Interfacial Tension in Dvnes/cm

It can be seen from Table 1 that interfacial tension of the gemini surfactants of the invention is significantly lower than that of single conventional surfactants at and

below 0.01%.

EXAMPLE 2

Oil-in-water emulsions are prepared using the following formulation of 10% mineral oil. about 90% water and 0.01 % surfactant active (based on water phase). The coarse emulsions are prepared by vortex mixing each composition for 30 seconds. Each emulsion is characterized by droplet size using an optical microscope, the smaller average droplet size indicating a greater degree of emulsification. Stability is determined by the degree of separation of oil at 23°C respectively, the lower the

percent coalescence, the greater the stability. The results are reported in Table 2.

Table 2

It can be seen from Table 2 that emulsions prepared with polyoxyethylene methylene bis(octylphenol) gemini surfactants are significantly better than emulsions prepared with the conventional surfactant polyoxyethylene octylphenol.

EXAMPLE 3 The oil-in-water emulsions are prepared using a formulation of 65% mineral oil. about 35% water and 0.028% surfactant active (based on water). The emulsions are prepared by blending in a rotor-stator type mixer (2000 rpm) for 3 min. Emulsions are characterized by droplet size using an optical microscope and stability by degree of separation of oil at 23 °C respectively. The results are reported in Table 3 as follows:

Table 3

It can be seen from Table 3 that emulsions prepared with polyoxyethylene

methylene bisoctylphenol are significantly better than those prepared with the

conventional surfactant polyoxyethylene octylphenol.

Amphoteric and cationic gemini surfactants are used as emulsifiers for mineral oil and compared to corresponding conventional surfactants. The results are shown in Table 4.

Table 4

* oil/water = 40/60 (w/w)

Systems emulsified with gemini amphoteric and cationic surfactants as disclosed herein are significantly more stable than those prepared using similar amounts of corresponding conventional surfactants.

EXAMPLE 5

The following examples illustrate the compositions and method of the present invention in detergent systems. All percentages, parts and ratios herein are by active

weight unless otherwise specified. Table 5 Composition of Detergents

Detergency for clay soil and dust-sebum on different fabnc(s) are evaluated in a Terg-O-Tometer from United States Testing under conditions of 150 ppm hard water. 37.8°C and 12 minute wash cycle The cleaning effectiveness is measured by the difference in reflectance with the Spectro Gard Color system, from Byk-gardner, before and after washing Percent reflectance correlates to detergenc} Better detergency and cleanness is evidenced by higher numbers of difference in reflectance The detergency results are reported at the corresponding surfactant concentration use levels in the final washing solution upon dilution of the compositions in Table 5 The following results (Table 6) show a slight disadvantage for the gemini surfactant over its conventional counteφart surfactant on clay soil using a relatively higher use level However, the performance is equivalent at 0 01% concentration, and greater effectiveness for the gemini surfactant is observed at

amounts below 0 01 % Table 6

Table 7 shows the detergency with dust-sebum It can be seen that gemini surfactant shows no significant advantage over the traditional surfactants at 0.02% surfactant use concentration, and especially lower performance on polyester fabric. However, gemini surfactants compositions of the invention show a significant advantage over the traditional detergent blend on dust-sebum cotton detergency at 0.01%) usage levels, and this trend is more obvious at the even lower level, 0.005%.

Table 7

The reflectance data obtained from compositions 1 and 2 at 0.01% and 0.005%

is also shown in graph form in Figures 1 and 2 EXAMPLE 6

Mixed gemini/conventional surfactant systems shows the same trend of low use level, supenor performance as illustrated in the following example.

Table 8

The following detergency performance of the compositions of Table 8 is found.

Table 9

The reflectance data obtained from compositions 3 and 4 at 0.005% and

0.001% is also shown in graph form in Figures 3 and 4 Very low use concentrations in a mixed surfactant system with gemini nonionic surfactant excels over conventional nonionic surfactant systems. Performance differences become more exaggerated at very low use concentrations.

The gemini surfactant can be also blended with conventional anionic and nonionic surfactants to enhance the detergency of the mixture. The surfactants compared are a 3/3/2 ratio blend of polyoxyethylene (7.5) octylphenol (OP), sodium dodecylbenzene sulfonate (LAS), and polyoxyethylene ( 13) methylene bis(octylphenol) (MBOP). This enhanced performance is shown in Table 10, in which the total surfactant content is kept at 0.005%. The wash condition is: 150 ppm hard water. 57 ppm triethanolamine/ monoethanolamine (1/1 ) and 37.8°C

Table 10

These reflectance results demonstrate that aqueous solutions containing blends of surfactants at low concentration levels, such surfactant containing 25% gemini surfactants provide improved washing power over a prior art blend of conventional surfactants not containing the gemini surfactants. This technology is very valuable to the detergent industry since it provides

excellent detergency to the end-user at very low surfactant concentration use levels. Hence, it reduces overall detergent composition cost, environmental impact, and use dosage at lower temperatures. Also, using low amounts of surfactant allows effective rinsing without the need of large amounts of water. Foam can be effectively monitored by working with the appropriate type and ratios of gemini to anionic and nonionic surfactants. With energy efficient washers requiring a high level of agitation and fairly low amounts of water, foam is not desirable and higher nonionic to anionic surfactant ratios are recommended. Gemini surfactants in these compositions are highly

desirable.

Claims

What is claimed is:

1. An aqueous surfactant composition comprising surfactant actives comprising one or more gemini surfactants of the formula:

I

R-A-(R,)_t -Z

I. R₃

R-A-(R,)_t -Z

R,

wherein R is independently C, to C,₂ alkyl, R₄C(0)-, or R₄-B-R₅-

wherein R₄ is C_} to C ₂ alkyl, R₅ is C| to C₁₂ alkyl. and

B is -C(0)NR₆-, -NRβ-. -C(0)0-. -C(O)-. or -0(EO)_a(PO)_b- wherein a and b each are from 0 to 100 and a plus b is at least 1. and P₆ is hydrogen or C, to C₆ alkyl; R, is independently hydrogen or C, to C₂₂ alkyl; R, is independently C, to C₁₀ alkyl. -0-. -C(0)NR₆-. -0(EO)_a(PO)_b-, -R₇-D-R-

wherein R₇ is independently C _rC alkyl. and

D is -0-. -S-. -C(0)NR₆- or -NR^- wherein R^,. a. and b are as defined above and t is. independently 0 or 1 : Z is independently selected from the group consisting of hydrogen. -S0₃ Y. - P(0)((OY)₂, -COOY, -CH,COOY. -CH,CH(OH)CH,S0₃Y. and. with the proviso that R₂ is not a polyether. -OS0₃Y or -OP(0)(OY), wherein Y is hydrogen, alkali metal, alkaline earth metal, or organic base salt;

A is independently C,-C₆ alkyl, -0-R₅-0-, or aryl;

R₃ is selected from the group consisting of a bond. aryl. C,-C|₀ alkyl, -0-. -S-. -S-S-, -NR₆-. -R₅0-. -R₅[0(EO)_a(PO)_b]-, -D_rR₈-D_r. and -R₈-D,-R₈-

wherein R₈ is independently C ,-C,₀ alkyl. -C(O)-. -R₅(0(EO)_a(PO)_b)-. -O-R₅-O-. or aryl; and

D, is independently -0-, -S-, -S-S-. -SO,-, -C(O)-. -0(EO)_a(PO)_b-. -C(0)NR₆-. -NR^-, -O-R₅-O-, or aryl wherein R . R^, a. and b are as defined above;

said composition containing a total amount of surfactant based on active weight equal

to or less than about 0.01 % by weight of the total weight of the composition and said gemini surfactant amount comprising from about 100% to about 10% by weight of the total surfactant actives in said surfactant composition.

2. An aqueous surfactant composition comprising surfactant actives comprising one or more gemini surfactants selected from the group consisting of

R. I

R₄-R_c-0(EO)_a(PO)_b-Z

11 I

R₃ and

I R₄-R_c-0(EO)_a(PO)_b-Z

I R, R.

I

R₄-C-CH, -0(EO)_a(PO)_b-Z III I

R₃

I

R₄-C-CH,-0(EO)_a(PO)_b-Z

I R, wherein R_c is aryl;

R, is independently hydrogen or C, to C,, alkyl;

R₃ is selected from the group consisting of a bond. aryl. C,-C₁₀ alkyl, -0-, -S-.

-S-S-. -NR«-, -R₅O-. -R₅[0(EO)_a(PO)_b]-. -D_rR₈-D,-. and -R₈-D,-R₈- wherein R₈ is independently C_rC,₀ alkyl. -C(O)-. -R₅(0(EO)_a(PO)_b)-, -O-R₅-O-. or aryl; and

D, is independently -0-, -S-, -S-S-. -SO,-. -C(O)-. -0(EO)_a(PO)_b-, -C(0)NR₍i-. -NRg-, -O-R₅-O-. or aryl wherein R₅ is C_rC_I2 alkyl. R₆ is hydrogen or

C,-C₆ alkyl.

R₄ is C, to C,, alkyl.

Z is independently selected from the group consisting of hydrogen. -S0₃Y, -

P(0)((OY),. -COOY, -CH,COOY. -CH,CH(OH)CH,S0₃Y. and, Y is hydrogen, alkali metal, alkaline earth metal, or organic base salt: and a and b each are from 0 to 100 and a plus b is at least 1.

said composition containing a total amount of surfactant based on active weight equal to or less than about 0.01% by weight of the total weight of the composition and said gemini surfactant amount comprising from about 100% to about 10% by weight of the total surfactant actives in said surfactant composition.

3. The aqueous surfactant composition of claim 2 wherein the gemini surfactant is selected from the group consisting of:

R,

I

R,

R,

C(O)

I ,

C(O)

R,

R₅

I o

wherein R|,.R₄. R₅ Z. a. and b are as herein defined.

4. An aqueous surfactant composition comprising surfactant actives comprising one or more gemini surfactants of the formula:

(R.), I R-N-R,-Z I

R₃ I

R-N-R,-Z

I (R,),

wherein

R is independently C, to C,, alkyl. R₄C(0)- or R₄-B-R₅- wherein R₄ is C, to C₂₂ alkyl,

R₅ is C₍ to C|₂ alkyl. and

B is -C(0)NR₆-, -NRβ-, -C(0)0-. -C(O)-. or -0(EO)_a(PO)_b- wherein a and b each are from 0 to 100 and a plus b is at least 1 , and Rg is hydrogen or C, to C₆ alkyl;

R, is independently hydrogen, C_rC,, alkyl, or - (EO)_a(PO)_bO- H; R, is independently C, to C₁₀ alkyl, -0-. -C^NR^-, -0(EO)_a(PO)_b-, -R₇-D-R₇-or -D- R,-D- wherein R₇ is independently C_rC₆ alkyl. and D is -0-, -S-. -C(0)NR₆-, - NRβ-. -NR₆-C(0)-R_?-CH,0-. and -NR^-C(0)-NR₆-R₄-.

R₃ is selected from the group consisting of a bond. aryl. C,-C₁₀ alkyl. and -R₈-D,-R_g-

wherein R₈ is independently C,-Cι₀ alkyl, -C(O)-. -R₅(0(EO)_a(PO)_b)-, or aryl; and

D, is -0-. -S-. -S-S-, -S0₂-, -C(O)-. -0(EO)_a(PO)_b-. -C(0)NR₆-. -NR^, -0-R₅-0-. or aryl wherein R₅. R_$, a. and b are as defined above: t is independently 0 or 1 : and

Z is independently selected from the group consisting of hydrogen. -S0 Y. -

P(0)((OY)₂, -COOY. -CH,COOY. -CH,CH(OH)CH,S0₃Y. and. with the proviso that R, is not a polyether. -OS0₃Y or -OP(0)(OY), wherein Y is hydrogen, alkali metal, alkaline earth metal, or organic base salt;

said composition containing a total amount of surfactant based on active weight equal to or less than about 0.01% by weight of the total weight of the composition and said gemini surfactant amount comprising from about 100% to about 10% by weight of the total surfactant actives in said surfactant composition.

5. The aqueous surfactant composition of claim 4 wherein the gemini surfactant is of the formula:

VIII. R-C(0)-NH-R₅-N-R₂-Z

(CH₂)_n I

R-C(0)-NH-R₅-N-R,-Z

wherein R. R₂. R₅. and Z are as herein defined and n is from about 2 to about 10.

6. The aqueous surfactant composition of claim 5 wherein the gemini surfactant is selected from the group consisting of:

X. R-C(0)-NH-CH,-CH,-N-CH,-CO,Na

CH,

I ;

CH,

R-C(0)-NH-CH,-CH,-N-CH,-CO,Na

XI. R-C(0)-NH-CH,-CH,-N-CH₂CH,CO,Na

CH,

; and

CH,

R-C(0)-NH-CH,-CH,-N-CH,CH,CO,Na XII. R-C(0)-NH-CH,-CH,-N-CH,-CH(OH)-CH,-S0₃Na

I

CH, I

CH,

R-C(0)-NH-CH,-CH,-N-CH,-CH(OH)-CH,-S0₃Na wherein R is as herein defined.

7. An aqueous surfactant composition comprising surfactant actives comprising one or more eemini surfactants of the formula:

wherei or R₄-B-R₅- wherein R₄ is C, to C,, alkyl,

R_< is C_| to C,, alkyl. and

B is -C(0)NR₆-. -NR₆-. -C(0)0-. -C(O)-. or -0(EO)_a(PO)_b- wherein a and b each are from 0 to 100 and a plus b is at least 1. and P₆ is hydrogen or to C₆ alkyl:

R₃ is selected from the group consisting of a bond. aryl. C_rC₁₀ alkyl. and -R₈-D,-R₈- wherein R₈ is independently C,-C₁₀ alkyl. -C(O -R₅(0(EO)_a(PO)_b)-. or aryl: and D, is -0-. -S-. -S-S-, -S0₂-. -C(0)-. -0(EO)_a(PO)_b-, -C(0)NR₆-. -NP^-. -0-R₅-0-. or aryl wherein R₅, R₆, a, and b are as defined above

Rg is independently C,-C|₀ alkyl or alkylaryl: and X is a counterion;

said composition containing a total amount of surfactant based on active weight equal to or less than about 0.01% by weight of the total weight of the composition and said gemini surfactant amount comprising from about 100% to about 10% by weight of the total surfactant actives in said surfactant composition.

8. An aqueous surfactant composition comprising surfactant actives comprising one or more gemini surfactants of the formula:

XIV. R₁₃-(CH₂)_p-N-R₁₄

I r

R,

R₁₃-(CH₂)_p-N-R₁₄ wherein

R-₅ is selected from the group consisting of a bond. aryl.-C_rC|₀ alkyl, and -R_g-D,-R₈- wherein R₈ is independently C_rC_{] 0} alkyl. -C(O)-. -R<(0(EO)_a(PO)_b)-, or aryl and D, is -0-. -S-. -S-S-, -S0₂-. -C(0)-, -0(EO)_a(PO)_b-, -C(0)NPv₆-, -NR^-, -0-R₅-0-, or aryl wherein R₅ is C,-C₁₂ alkyl. R^ is hydrogen or C,-C₆ alkyl, and a and b each are from 0 to 100 and a plus b is at least 1.

R₁₃ is a sugar moiety; R,₄ is C,-C₂₂ alkyl or -C(0)R₄

wherein R₄ is C, to C₂ alkyl; and p is independently 0 to 4;

said composition containing a total amount of surfactant based on active weight equal to or less than about 0.01% by weight of the total weight of the composition and said gemini surfactant -amount comprising from about 100% to about 10% by weight of the total surfactant actives in said surfactant composition.

9. An aqueous surfactant composition as recited in claim 1 wherein the amount of total surfactant is equal to or less than 80% of the cmc of the corresponding conventional surfactant.

10. An aqueous surfactant composition as recited in Claim 2. wherein the amount of total surfactant is equal to or less than 80% of the cmc of the corresponding conventional surfactant.

1 1. An aqueous surfactant composition as recited in Claim 4 wherein the amount of total surfactant is equal to or less than 80% of the cmc of the corresponding conventional surfactant.

12. An aqueous surfactant composition as recited in Claim 7. wherein the amount of total surfactant is equal to or less than 80% of the cmc of the corresponding conventional surfactant.

13. An aqueous surfactant composition as recited in Claim 8. wherein the amount of total surfactant is equal to or less than 80% of the cmc of the corresponding conventional surfactant.

14. An aqueous surfactant composition as recited in claim 1 wherein the total amount of surfactant actives is equal to or less than about 0.008%> by weight.

15. An aqueous surfactant composition as recited in claim 2 wherein the total amount of surfactant actives is equal to or less than about 0.008%) by weight.

16. An aqueous surfactant composition as recited in claim 4 wherein the total amount of surfactant actives is equal to or less than about 0.008%) by weight.

17. An aqueous surfactant composition of claim 7. wherein the total amount of surfactant actives is equal to or less than about 0.008% by weight.

18. An aqueous surfactant composition of claim 8. wherein the total amount of surfactant actives is equal to or less than about 0.008% by weight.

19. An aqueous surfactant composition as recited in claim 1 wherein the total amount of surfactant actives is equal to or less than about 0.006% by weight.

20. An aqueous surfactant composition as recited in claim 2 wherein the total amount of surfactant actives is equal to or less than about 0.006%) by weight.

21. An aqueous surfactant composition as recited in claim 4 wherein the total amount of surfactant actives is equal to or less than about 0.006%> by weight.

22. An aqueous surfactant composition as recited in claim 7 wherein the total amount of surfactant actives is equal to or less than about 0.006% by weight.

23. An aqueous surfactant composition as recited in claim 8 wherein the total amount of surfactant actives is equal to or less than about 0.006% by weight.

24. The aqueous composition of claim 1 wherein Z is hydrogen.

25. The aqueous composition of claim 2 wherein Z is hydrogen.

26. The aqueous composition of claim 4 wherein Z is hydrogen.