CA2092561C - Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and a critically selected suds enhancing agent - Google Patents
Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and a critically selected suds enhancing agentInfo
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- CA2092561C CA2092561C CA 2092561 CA2092561A CA2092561C CA 2092561 C CA2092561 C CA 2092561C CA 2092561 CA2092561 CA 2092561 CA 2092561 A CA2092561 A CA 2092561A CA 2092561 C CA2092561 C CA 2092561C
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Abstract
The present invention provides detergent compositions comprising one or more anionic sulfate or sulfonate surfactants:
one or more polyhydroxy fatty acid amides having formula (I), wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and a critically selected suds enhancing agent. The present invention also provides for a method for cleaning soiled dishes by treating said dishes with the detergent compositions disclosed herein.
one or more polyhydroxy fatty acid amides having formula (I), wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and a critically selected suds enhancing agent. The present invention also provides for a method for cleaning soiled dishes by treating said dishes with the detergent compositions disclosed herein.
Description
WO 92/1)6161 PCr/US91/06981
2 ~ ~ S~
DETERGENT COMPOSITIONS CONTAINING POLYHYDROXY FATTY
ACID AMIDES AND SUDS ENHANCING AGENT
TECHNICAL FIELD
lile pr~s2nt invention relates to detergent compositions com-pri;ing i - or mor2 anionic ;ul5ate or sulfonate surfactants, one or more polyhydroxy fatty acid amides and a critically selected suds 2nhano ,.~ ~el.. !n particular, it relates to detergent composi-tions ~hich poss2ss enhanced cleaning and sudsing properties, are-,ild ~ e hand, and are especially suitable for use in dishwashing a~p~ ;"~.
BACKGROUND OF ~HE INVENTION
The use of anionic sulfated or sulfonated surfactants in detergent compositions is known. However, it would be desirable to incorporate such surfactants into detergent compositions which exhibit improved cleaning and sudsing performance across varying temperature and humidity conditions.
it has now been found that detergent compositions containing one or more anionic sulfated or sulfonated detergent surfactants, one or more polyhydroxy fatty acid amides and a suds enhancing agent selected from the group consisting of amine oxides, betaines, sult2ines, and certain nonionics, and mixtures thereof, exhibit sudsing and cleaning performance superior to the performance of
DETERGENT COMPOSITIONS CONTAINING POLYHYDROXY FATTY
ACID AMIDES AND SUDS ENHANCING AGENT
TECHNICAL FIELD
lile pr~s2nt invention relates to detergent compositions com-pri;ing i - or mor2 anionic ;ul5ate or sulfonate surfactants, one or more polyhydroxy fatty acid amides and a critically selected suds 2nhano ,.~ ~el.. !n particular, it relates to detergent composi-tions ~hich poss2ss enhanced cleaning and sudsing properties, are-,ild ~ e hand, and are especially suitable for use in dishwashing a~p~ ;"~.
BACKGROUND OF ~HE INVENTION
The use of anionic sulfated or sulfonated surfactants in detergent compositions is known. However, it would be desirable to incorporate such surfactants into detergent compositions which exhibit improved cleaning and sudsing performance across varying temperature and humidity conditions.
it has now been found that detergent compositions containing one or more anionic sulfated or sulfonated detergent surfactants, one or more polyhydroxy fatty acid amides and a suds enhancing agent selected from the group consisting of amine oxides, betaines, sult2ines, and certain nonionics, and mixtures thereof, exhibit sudsing and cleaning performance superior to the performance of
3~ anionic sulfated or sulfonated surfactants alone. In addition to these performance benefits, such compositions are, when compared to anionic sulfated or sulfonated surfactants, milder to the hand, have improv~d rinsability, are not as slippery to the touch, and are easier tO formulate due to a reduced need for process additives such as solvents and hydrotropes.
~ ~urther ber,efit associated with such compositions is that their ;ud;ir,~ p~rformance is unexpectedly uniform across varying tem~erature and humidity conditions.
w o 92/06161 PCT/~Sgl/069 ? ~ 9 2 ~ ~ ~ BACKGROUND ART
The use of anionic sulfate or sulfonate surfactants in deter-gent compositions is known in the art, U.S. Patent 4,~3~,317 (Gerritson et al., March 6, 1984), discloses liquid detergont compositions which contain alkyl sulfato, alkyl et~er su'~~ n~
alkylbenzene sulfonate surfactants. U.K. Pat~nt Specif,cat on 809,060, assigned to Hedley & Co. Ltd., published February 1~, discloses detergent compositions containing a sul,ate or a sul,ona.
surfactant with a particular polyhydro~y -ratty acid a~ide.
The polyhydroxy fatty acid amidP component contained .i ...... e comDosition of the present invention is also known in .he â~~~, ,._ are several of its uses.
',-acvl, N-methyl gluc~mides, f~r ~-xlm~le, are disc'os~d ~v 1, W. Goodby, i1. A. ;~arcus, .. Ch-,n, and ~. L. ,-inn in "T;12 i;ic~~mv~
tropic Liquid-Crystalline Properties OT Some Straight Chain Carbohy-drate Amphiphiles," Liquid Crystals, 1988, Yolume 3, No. 11, pp1569-1~81, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R.
Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Deter-gent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Com-pounds, a New Class of Non-Ionic Detergents For Membrane Bio-chemistry," Biochem. J. (1982), Vol. 2C7, pp 363-366, by J. E. K.
Hildreth.
The use of N-alkyl glucamides In detergent compositions has also been discussed. U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.K. Patent Specification 809,060, already discussed herein, relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally WO 92/05161 PCr/US~1/06981 ~a32~
indicated that additional constituents to impart desirable proper-ties to the composition can also be included in the compositions, ~uch as ,luorescent dye;, bleaching agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz, r~l~-~s ~uoous detergent compositions containing the condensa-tion r-aaction product of N-alkyl glucamine and an aliphatic ester of a .~at~j cid. The p,cduc~ of this reaction is said to be useable in aquacus ~at7rSPnt compositions ~ithout further purification. It is a~so ~n~Jn o ~;~e?ar~ a sulfuric ester of acylated glucamine as ~~ disc~ ~d n U.S. Pate,n~ ;',717,894, issued September 13, 1955, to A.
~ U~I in,erna,ional ~pplication WO 83/04412, published December 2'', 1.aQ3, h'~ ildreth, relates to amphiphilic compounds contain~
ir.s ;~ Jh,d oxyl - "~"at,c g,oups said to be useful for a ~J2riety of l~i purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing liposomes.
Included in this disclosure are compounds of the formula R'CON(R)CH2R" and RnCON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.
'uropean Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a - C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g (prefer-ably C1-C~) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl haYing four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide. The thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic ac;d half ester salts, 3~ and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alconol polygl~co1 ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/N-methyl coconut fatty acid w o 92/06161 PCT/~'S91/069Xl ~ ~J ') ~ ~ ~ i 4 glucamide/nonionic surfactant shampoo formulations are exemplified In addition to thickening attributes, the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attribut~s.
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an ~-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
Oth~r glucamide surfactants are disclosed, for example, i~ DT
lC 2,226,3~2, published December 20, 1973, H. ~. Ec~ert, e~ al., ~nich relates to washing compositions comprising one or more surfactanls and build~r salts selected from polymeric phosphat2s, s2questerins agents~ and washing alkalis, improved by the addition of an N-acyl-?olyhydrox~ ylamine of the ormula RlC(O~I(R2)CH~tCHO~)~C~
1~ wher~in R1 is a C1-C3 alkyl, R2 is a C10-c22 al~yl, and n is 3 or ~.
The N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxyalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is a C10-c22 alkyl, R2 is a C7-C21 alkyl, R1 and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CHOH)m-CH20H where m is 3 or 4.
U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, etal., relates to skin treating cosmetic compositions containing N-polyhydroxyalkyl-amines which include compounds of the formula R1N(R)CH(CHOH)mR2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R1 but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabil-ized against polymerization with the addition of amides of the 3~ formula RC(O)N(R1)G wherein R is a carboxylic acid functionality naving at least seven carbon ato~,s, R1 is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
w o 92/06161 PCT/US91/06981 - 5 -~23~1 German Patent 1,261,861, February 29, 1968, A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of th2 -roi~mul ~ 2) ~h2r~in R is a sugar residue of glucamine, Rl is 2 Cl~-C20 al~yl radical, and R2 is a Cl-Cs acyl radical.
~ +~n+ ~4~,036, ?ublishod February 15, 1956, assigned to Atl~s C~ or rO~ nV, relat~s to heterocyclic amides and carboxylic eâ~2~~S ~;,c~; ;.01- tha; ;,e ~aid to be useful -~s chemical intermediates, 2muls-. ',~-,-s, .~etting and dispersing agents, detergents, textile so~ c. ,~e co",~oun~s ar~ ~pressed by the formula lG N(~,(?~ norein ,l i; '~e r sicue of an anhydrized hexane ~r~ r ~ e~r~o~ylic -~c d ostQr theroof, R1 is a monovalent hydror~nbon ~~dical, ~nd -C(0)2~ is the acyl radical of a carboxylic ~cid ~ . $r~m ~ to ~5 car~on ~toms.
v.i. "~ ,31 ,6 " ,;,~ed '~r,l -" '367 t~ D. T. ~.ooker, disclos~s solid ~oilet bars that are substantially free of anionic detergents and al~aline builder materials, and which contair. lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NRl(R2) wherein RC(0) contains from about 10 to about 14 carbon atoms, and Rl and R2 each are H or Cl-C6 al~yl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
The use of amine oxides, betaines, sultaines, and the nonionics of the present invention are also known in the art. U.S. Patent
~ ~urther ber,efit associated with such compositions is that their ;ud;ir,~ p~rformance is unexpectedly uniform across varying tem~erature and humidity conditions.
w o 92/06161 PCT/~Sgl/069 ? ~ 9 2 ~ ~ ~ BACKGROUND ART
The use of anionic sulfate or sulfonate surfactants in deter-gent compositions is known in the art, U.S. Patent 4,~3~,317 (Gerritson et al., March 6, 1984), discloses liquid detergont compositions which contain alkyl sulfato, alkyl et~er su'~~ n~
alkylbenzene sulfonate surfactants. U.K. Pat~nt Specif,cat on 809,060, assigned to Hedley & Co. Ltd., published February 1~, discloses detergent compositions containing a sul,ate or a sul,ona.
surfactant with a particular polyhydro~y -ratty acid a~ide.
The polyhydroxy fatty acid amidP component contained .i ...... e comDosition of the present invention is also known in .he â~~~, ,._ are several of its uses.
',-acvl, N-methyl gluc~mides, f~r ~-xlm~le, are disc'os~d ~v 1, W. Goodby, i1. A. ;~arcus, .. Ch-,n, and ~. L. ,-inn in "T;12 i;ic~~mv~
tropic Liquid-Crystalline Properties OT Some Straight Chain Carbohy-drate Amphiphiles," Liquid Crystals, 1988, Yolume 3, No. 11, pp1569-1~81, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R.
Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Deter-gent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Com-pounds, a New Class of Non-Ionic Detergents For Membrane Bio-chemistry," Biochem. J. (1982), Vol. 2C7, pp 363-366, by J. E. K.
Hildreth.
The use of N-alkyl glucamides In detergent compositions has also been discussed. U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.K. Patent Specification 809,060, already discussed herein, relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally WO 92/05161 PCr/US~1/06981 ~a32~
indicated that additional constituents to impart desirable proper-ties to the composition can also be included in the compositions, ~uch as ,luorescent dye;, bleaching agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz, r~l~-~s ~uoous detergent compositions containing the condensa-tion r-aaction product of N-alkyl glucamine and an aliphatic ester of a .~at~j cid. The p,cduc~ of this reaction is said to be useable in aquacus ~at7rSPnt compositions ~ithout further purification. It is a~so ~n~Jn o ~;~e?ar~ a sulfuric ester of acylated glucamine as ~~ disc~ ~d n U.S. Pate,n~ ;',717,894, issued September 13, 1955, to A.
~ U~I in,erna,ional ~pplication WO 83/04412, published December 2'', 1.aQ3, h'~ ildreth, relates to amphiphilic compounds contain~
ir.s ;~ Jh,d oxyl - "~"at,c g,oups said to be useful for a ~J2riety of l~i purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing liposomes.
Included in this disclosure are compounds of the formula R'CON(R)CH2R" and RnCON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.
'uropean Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a - C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g (prefer-ably C1-C~) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl haYing four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide. The thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic ac;d half ester salts, 3~ and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alconol polygl~co1 ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/N-methyl coconut fatty acid w o 92/06161 PCT/~'S91/069Xl ~ ~J ') ~ ~ ~ i 4 glucamide/nonionic surfactant shampoo formulations are exemplified In addition to thickening attributes, the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attribut~s.
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an ~-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
Oth~r glucamide surfactants are disclosed, for example, i~ DT
lC 2,226,3~2, published December 20, 1973, H. ~. Ec~ert, e~ al., ~nich relates to washing compositions comprising one or more surfactanls and build~r salts selected from polymeric phosphat2s, s2questerins agents~ and washing alkalis, improved by the addition of an N-acyl-?olyhydrox~ ylamine of the ormula RlC(O~I(R2)CH~tCHO~)~C~
1~ wher~in R1 is a C1-C3 alkyl, R2 is a C10-c22 al~yl, and n is 3 or ~.
The N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxyalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is a C10-c22 alkyl, R2 is a C7-C21 alkyl, R1 and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CHOH)m-CH20H where m is 3 or 4.
U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, etal., relates to skin treating cosmetic compositions containing N-polyhydroxyalkyl-amines which include compounds of the formula R1N(R)CH(CHOH)mR2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R1 but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabil-ized against polymerization with the addition of amides of the 3~ formula RC(O)N(R1)G wherein R is a carboxylic acid functionality naving at least seven carbon ato~,s, R1 is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
w o 92/06161 PCT/US91/06981 - 5 -~23~1 German Patent 1,261,861, February 29, 1968, A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of th2 -roi~mul ~ 2) ~h2r~in R is a sugar residue of glucamine, Rl is 2 Cl~-C20 al~yl radical, and R2 is a Cl-Cs acyl radical.
~ +~n+ ~4~,036, ?ublishod February 15, 1956, assigned to Atl~s C~ or rO~ nV, relat~s to heterocyclic amides and carboxylic eâ~2~~S ~;,c~; ;.01- tha; ;,e ~aid to be useful -~s chemical intermediates, 2muls-. ',~-,-s, .~etting and dispersing agents, detergents, textile so~ c. ,~e co",~oun~s ar~ ~pressed by the formula lG N(~,(?~ norein ,l i; '~e r sicue of an anhydrized hexane ~r~ r ~ e~r~o~ylic -~c d ostQr theroof, R1 is a monovalent hydror~nbon ~~dical, ~nd -C(0)2~ is the acyl radical of a carboxylic ~cid ~ . $r~m ~ to ~5 car~on ~toms.
v.i. "~ ,31 ,6 " ,;,~ed '~r,l -" '367 t~ D. T. ~.ooker, disclos~s solid ~oilet bars that are substantially free of anionic detergents and al~aline builder materials, and which contair. lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NRl(R2) wherein RC(0) contains from about 10 to about 14 carbon atoms, and Rl and R2 each are H or Cl-C6 al~yl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
The use of amine oxides, betaines, sultaines, and the nonionics of the present invention are also known in the art. U.S. Patent
4,555,360, issued November 26, 1985 to Bissett et al., discloses detergent compositions comprising certain sulfated and sulfonated surfactants, a betaine surfactant, and an amine oxide. These compositions may also optionally contain certain nonionic detergent surfactants. U.S. Patent 3,351,557, issued November 7, 1967 to 3~' Almstead et al., discloses built lio,uid detergent compositions containing a nonionic detergent, 2 builder, an emulsion stabilizer, water, and a detergent selected from a group of detergents which include sultaines.
w o 92/06161 PCT/~S91/06981 ~ a ~ 6 -However, there is nothing in the art which teaches the unex-pected cleaning and sudsing performance, lack of "slippery" feel, mildnes, to the handt and ease of rinsing associated with the detergent compositions of the present invention which contain anionic s~llf~ted or sulfonated anionic surfactants, certain polyhy-droxy fatty acid amides and a critically selected suds enhancing agent.
Additionally, nothing in the art teaches that such compositions provi'~ su~stantially uniform improved sudsing performance across l3 varyi,~ a"perature and humidity c~nditions.
Tt is 'herefore an object of the present invention to provide sucin Ge-~argent compositions which exhibit such properties.
It is still another object of the present invention to provide a ~ ,h~d T~J'~ n~ j~y soilod diihPs by tr~tl~g ;~id dish~s with th~
partic~,a~~ det2rgent compositions described herein.
These objects are realized by the present invention.
SUMMARY OF THE INVENTION
The present i m ention is directed to detergent compositions comprising from about 5% to about 65% by weight of a surfactant mixture comprising:
(a) from about 5% to about 95% by weight of one or more anionic sulfate or sulfonate surfactants;
(b) from about 5% to about 95% by weight of one or more polyhydroxy fatty acid amides having the formula o R1 R2 - C - N - z wherein Rl is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a Cs-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative i;hereof; and ~c) from about 1% to about 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyeihylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene WO 92/06161 PCJ/US91/06~81 2 ~
oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene ox,de ~ ,rop~13ne 31~col, th2 condensation product of ethylene oxide ~.Yi th ~he product resulting from the --?.~ . ~?~l ?nD O:~i dD ~nd othyl enedi ami ne, alkylpol~saccharides, ~nd f~tty acid amides; and mixtures ;;'~ci cv, .
Th~ ?r 2s2nt ,n~/en-~ion .s also ~irected to~ard a method for cleani"g ~ sl n ~ ;-O~~ Oalm'-JI i;i,s v.eating said disnes w i t ~ ~ ~ P ~ r ~ ' " ~
' S ~ ? T ? T '' '! !~ r ~ ?IT T ON
~ he .a~er ~er.t rr.mr~o~,j"; ons or (,I!e oresen~ invent ion comorise I rG~ '0'!1 ''~;'/'! r~ro-s~r~hl ~ om ~u~out 10~~ to about 50%, mos ~ ~'c ~ cl~a~ ' J ~ ';'J~ g~ V l a surfaclant ntixturs compri;ing one or ~ore anionic sulfated or sulfonated surfactants, one or morP polvhydrovy fatty acid amides, and a critically selected suds enhancing agent. These and other ingredients typically found in liquid detergent compositions are set forth below. The detergent compositions of the present invention are preferably in the form of a liquid or a gel, more preferably light-duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions.
Anionic Surfactant The surfactant mixture of the present invention, comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more anionic sulfate or sulfonate surfactants. The anionic sulfate or sulfonate surfactant may Se any organic sulfate or sulfonate surfactant, but is preferably selected from Cll-Cls alkyl benzene sulfonates, C10-Cl6 alkyl sulfates and their ethoxy analogues containing up to twelve moles of ethylene oxide per mole of alkyl ethoxy sulfates, Cl3-Cl2 paraffin sulfonates, C,0-Cl6 olefin sulfonatPs, C1o-C20 alkyl glyceryl ether sulfonates, Cg-C17 acyl-N-(C1-C4 alkyl3 or -N-(C2-C4 hydroxyalkyl) glucamine sulfates, 3~ and mixtures of any OT the ;orsgoing. ~ore preferably the anionic surfactant is selected from li"ear alkyl benzsne sulfonates, alkyl ethoxy sulfates, alkyl glyceryl ether sulfonates and paraffin sulfonates.
w o 92/06161 ~ PCT/~S91/06981 Alkyl benzene sulfonates useful in compositions of the present inven~ion are those in ~hich the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 10-13 carbon atoms, a ;mai;~rial 1i~h an a~crase carbon chain length of 11.2 being most pre;~rn~ci. Ih2 ?ren~l isomer distribution, i.e., the point of ~ a ~ , e;îain ~o i~h2 ~enz2ne nucleus, is not critical. ~ut alkyl b2nzenes having a high 2-phenyl isomer content ~u~ le al'~l ;ul~ates are orimary alkyl sulfates in ~hich the ; '~ ; oarbon a~oms, more pref~rably an averaige . ~ - .; ;ù~ h~ C10 r1 ~
;.S~ ,..,..._.'~.'_.. -.'.m '.i;'Jl''.i~ S) or ~ie~ r 0i2Fin build-up, or 'u~'ù ;~.'n ~-sls~ f~,m SU i~ae~a souirces ror ~he 21~yl group. ~vamples or~ s~!n~a~lC~iiJ derm/ea maleria7s include uobanol 23 ~21,~; sola oy Sh?ll ''hi~micals (~v? !td.~ .thyl 24 sold by the Ethyl Corporation, a blena or Cl3-C~s alcoilols in the ratio 67% Cl3, 33% C~s sold under the trad~ name Lutensol by BASF GmbH and Synperonic (RTM) by ICI
Ltd., and Lial 125 sold by Liquichimica Italiana. Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C~0-C~6 a kohol ~ith 2n aver~ge of up to 6 ethylene oxide groups. The C~0-C~6 alcohol itself can be obtained from any of the sources previously described for the alkyl sulfate component. C~2-C~4 alkyl ethoxy sulfates are preferred.
~ o m2r.t.ûnal base-catalyzed ethoxylation processes to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 eihoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. 81ends can be made of material having different degrees of ethoxy,a~idn and/or di " er2nt ethoxylate distributions arising from the specific ethoxylation te~hniques employed and subsequent proceC ing st3~s such 3S distillation. For example, it has been fourd that sudsing and ~rease r-moval performance equivalent to that gi1en oJ a olend G-- 21kyl sulrate and alkyl triethoxy sulfate can be obtained by reducing the level of alkyl sulfate and using an alkyl WO 92/06161 PC'r/l~S91/06981 ethoxy sulfate with an average of approximately two ethoxy groups per mole of alcohol. In preferred composition; in accordance with the present invention an al~l ethox~ sulfatA is usod which h2s an average degree of ethoxylation of from 0.~ to 5, more preferably from 0.4 to 3Ø
Paraffin sulfonates useful in the presen~ invention nave rrom 13 to 18 carbon atoms pr~r ",ol 5OU1~ m~O~A 'AeSj--b1_/ 13 'o !5 ca,bon atoms per molecule. These sulfonates ar? pr?;arabiy prepared oy subjecting a cut of para,~,in, ~-r~s~ S :~ ~h~ ~ aln len~'h specified above, to the -,0 a~ 0~' 5~ A O j~X'de ' n~ OXtSal1 j 1 accordanc~ with the well-kr.c~.Jr. - '.-3~idar.3n ~rOA?SS. Ih? pro~uct of this reaction is a seconGarJ iui;onic aci~ ~riiC~l i; '~nein neutralized with a s~litablD base to provide a water-soluble secondary al~yl ;u~ ,a~ J~
be obtained by other methods, e.g., D~ the sul,~ochlorinaLion me.hod in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates. Whatever technique is employed, it is normally desirable to produce the sulfonate as the monosulfonate, having no unreacted starting hydrocarbon or having only a limited proportion thereof present and with little or no inorganic salt by-product.
Similarly, the proportions of disulfonate or higher sulfonated material will be minimized, although some may be present. The monosulfonate may be terminally sulfonated or the sulfonate group may be joined on the 2-carbon or other carbon of the linear chain.
Similarly, any accompanying disulfonate, usually produced when an excess of sulfonating a~ent is present, may have the sulfonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the monosulfonates and disulfonates may be present.
Mixtures of monoalkane sulfonates wherein the alkanes are of 14 and 15 carbon atoms are particularly preferred wherein the sulfonates are present in the weight ratio of Cl~-Cls paraffins in the range from 1:3 to 3:1.
Olefin sulfonates useful ir the pre;ent inventton are mixtures of alkene-l-sulfonates, alkene r,ydrox~sulfonates, alkene disulfon-ates and hydroxydisulfonates, and are described in the commonly ~O 92/06161 ~ PCI/~S91/06981 jj;J.~b~ lo- , assigned U.S. Patent 3,332,880, issued to P. F. Pflauner and A.
Kessler on ~uly 25, 1957.
Suitable alkyl glycer,~l ether sulfonates are those deriYed from ethers 3f C'aaJ"~_ ;il iniJi ';'ll-'i u~ ?. ~ S~ C ,2,1~ lCl udi~ L;l~ g-Ci7 acyl-N-(cl-c4 al~. ; .''? ~ S, iYI ~fi~rz31y those in :lhich ~he C~-Cl~ ac~l ciloup is d~rived from coconut or palm ? ' ... .: .?. _ .~-' ?-' ' ' ' - ? ? ~-- -i-' ' ? ~ hgd idisc'osed in U S ~ert ~717 ~ issu~?d ~eDt?mber 13, lg55 to Schwartz.
0 ~ ' -!,1 ? ' ' ~ n ' '~ ar '~ n ~ com,~onent is ~- ,;; " ~ 5 i~lV;;
pr~ r e, ,'"!~ .
~n ~re'~ -.ra~s ---Icn, ilc~rqorai:-ng ~ -Cls alkyl eilloxy sulfa-e ~ e anionic surr1c~ant~ ;rhe ~olar amount of magnesium ion in the co~pos ,vns is cont~ollav to corraspc,d to 0.3~-0.v5X ~here X is the number of moles of C1~-C~s alkyl sulfate present. Most preferably the magnesium ion content is adjusted to provide the stoichiometric equivalent, i.e., half the molar amount of the alkyl sulfate present. In such positions the magnesium ion will be present at a level of from about 0.15% to about 3.0% by weight, preferably from 0.25% to 1.5% by weight of the composition.
PolYhvdrox~ Fa'tv Acid A,,ide ComDonent Th~ ~urfactant mixture orr the pr sent invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more polyhydroxy faLty acid amides haiins :he structural formula:
(I) R2 - C - N - Z
wherein: ~1 is H, Cl-C4 hydrocarb;l, 2-hydroxy ethyt, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C~ alkyl, most Drererably C1 alkyl (i.e., methyl);
and R2 is a C~-C31 h~drocarb~', ure'erably ,traight-chain C7-C1g alkyl or alkenyl, more ~referably straight-chain Cg-C17 alkyl or alkenyl~ ~oSr ~reFzr~o~y str~i~ -o"ain ~ 17 alkyl or alkenyl, or mixture thereof; and ~ is a pvl/h~dr~xvh~drocarbyl having a linear hydrocar~yl chain ~ith ~t leas ~ h~drsxyls directly connected to the chain, or an alkoxylated derivatiYe (preferably ethoxylated or w o 92/06161 ~ J ~ pcT/~s9l/o69xl propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, tructose, maltose, lactose, galactose, mannose, and xylo;e. ~s r~ llal,, high dextrose corn syrup, high fructose corn s/rup ~nd 'n~ alt~se corn syrup can be utili~ed 3S '~211 ~:5 '~
above. These corn syrups may yield a mi~ o,~ a'~al O~ v"~..'; ,~0. 7.
It should be understood that it is oy no ,ne~ il7L ~îd=d ~v ~c~dc other suitable raw materials. Z preferably iill oe ielcc~ ,r.,", the group consisting of -C~2-(C~OH
CH2O~., -CH~-(CHOH)2(CHOR')(CHOH)-C~2~n! .ln~ a, ,,;
to 5, inrlusl~/o, and R' iS H or a cvclil o; ;;;~i; r ide, ~nd ~lkoxylat~d deri~atl/as t~r~-o~. ;- ~. r~
glycit,7i ~r,~rein n is " ?art c l3i~'y -C! -'r. o~; r~
In Formula (1), Ri can oe, ror e~c,l~ .lc;n~ ",;"
N-propyl, N-isopropyl, N-but~l, N-2-hydroxy ~thyl, or ~ -nydroxy propyl.
R2-C0-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be l-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, l-deoxylactityl, l-deoxygalactityl, l-deoxymannityl, 1-deoxymalto-triotityl, etc.
The most preferred polyhydroxy fatty acid amide has the general formula R2 - C - N - CH2 - (CHOH)4CH20H
wherein R2 is a C11-C17 straight-chain al~l or al~enyl group.
Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl Polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. ?rocesses Eor making compositions containing polyhydroxy ratt~ acid amid2s are disclosed, for exa~ple, in G.B. Patent Specitication 809,060, published ~ebruary 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. ~ilson, and U.S. Patent w o 92/0616~ r~j i PCT/~S91/06981 2,703,798, Anthony M. Sch~artz, issued March 8, 1955, and U.S.
Patent 1,985,~24, j.SUeA u~cqm-~r 75, 1~3~1 io ~',3Sott, e2ch of which is incorporated heroin by r~,-?r-n.c2.
In one procef~sl-~ns ~ ai'~-~ or ~-nydrcxyal~yl, N-deox~g~c1t~l ,a~t~ c-.~her~in ~.e ~yeityl co~onent is deri~d ~~o~ .~Jc~ v.~Gl,ty is N-meth~ -eth~ re~I-m~ . N-h~!droxye'~yl, or N-hydroxypr~ J ~ a '~yl- or methyl ;~ a;l~
preS2nC~ O; a ~ C~ i n~~~ 0;
tetrasodium pyropiios;i~a~e, ue..~;~oLassiu,;l 'r~ unospi;d.e, li~inium hydroxid~ ,~d;~ ~ - ,~,- s.,~ d-~x ~.-. ~-lci~.~ n ~r3xid~~
lithiu~ c~h~ nn-~ r~sod~um tartrate, dipotassium LarLnaL~, sodium po~assium tartra-ce, trisodium citrate, tripotassium citrate, sodium basic silicat2s, potassium bas;c s;licates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about lO mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 13~'C to about 170'C 'or typically from about 20 to abûut 90 mi~utes. Wnen triglycertdes are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agen~, cal.ulat2c on a weisht p=rcent basis of total reaction mixture, selecte~ fr~~ saturaied falty alcoho7 polyethoxy7-ates, alkylpolyglucosides, line~r glucamide surfactant, and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty -;ter to about i38~C to about 170~C;
(b) addins t.,e 'J-al'~;l v~ ,.-hydr~xya'~jl glucamiil to the heated fatty acid es'-r and mixing t~ khe extent needed to rorm a two-.,hase lig;i-.'li,:.~id mixture;
(c) mixing the catal~st ~ th~ reactiun mixture ?.nJ
(d) stirring f5r th- ;pec :-,e'' r_dCtiGn 'iine.
W o 92/06161 PCT/~S91/06981 - 13 - ~ 3 9 ~
Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide produc~
is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate. A de~ailed experimental procedure is provided below in the section entl~ed Experimental.
The polyhydroxy "fatty acid" amide materials used herein also offer the advantages to the detergent formulator 'ha~ ~h~y c--, "
prepared wholly or primarily from natural, r-n~~-ble, petrochemical feedstocks and are degradable. They a1so exn,o~ io~
toxicity to aquatic life.
~ t should be recognized that along with the polyhydroxy r~atty acid amid s of Formula (I), the proc~ss s used ~o produc~- ~.r~m ~
also typically produce quantities of nonvolatile by-product s _h a esteramides and cyclic polyhydroxy fatty acid amide. ~he level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels Gf by-products, including such cyclic amide by-product.
Suds Enhancinq Aqent The surfactant mixture of the present invention ~urther comprises from about 1% to about 20%, preferably from about 2% ~more preferably ~%) to about 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, and certain nonionics.
Amine oxides useful in the present invention include those compounds having the formula o 35R3(0R4)xN(Rs)2 wherein R3 is selected from an alkyl, hydrox~alkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R4 is an alkylene or w o 92/06161 PCT/~iS~)1/06981 2 ~3 ~ r~ 14 -hydroxyalkylene group containing from 2 to 3 carbon atoms, prefer-ably 2 carbon atoms, or mixtures ~h~reof; ~ i~, .-rû~ ~ ~o 3, ?r2,~er-ably 0; and each Rs is an al'~Jl or h,'~rOV'!?.ll'yl ~roup ~ontainin~n~
from 1 to 3, preferably from 1 to 2 carbon zt~-~, Jr ~. polyethylene oxide group containing from l ~o ', 3,~?'~ al'! ;- ?','~l.?n? o~ide groups. The Rs groups can oe a~ac;l~u ~o ~dcn ~ r. a~q. ~ Lnr~uG?
an oxygen or nitrogen atom, to ~orm a - n~ r'!~?~
These amine oxide sur,~acLan~s l~ ?ar~ n~ i'lCIUC!.? ~ C.3 alkyl dimethyl amjna OXi~ .r.
amine oxides. Examples or Sl!C.l î ' ~ ' ' l ~ ~C", ' ,: ~ l oxide, diethyldecylamine oxio~ -n~ ?C'/;~ml~
oxide, dim2thyldodecylamin~
methylethylhexadecylamine oxide, dca2cylamiaoDroDyl aim-~cnylamine oxide ~nd di~l~?th~ -h~/cl 0v~ ? ~ ;-? -?-~~ '--?
Clo ~g alkyl dimethylamine ,~,de, a"' r;' ~ ~;y~ z~
dimethylamine oxide.
The betaines useful in the pries2nt invention are those com-pounds having the formula R(R1)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group, preferably a Clo C16 alkyl group, each R1 is typically Cs-C3 alkyl, preferably methyl, and R2 is a Cl-Cs hydrocarbyl group, preferably a Cl-C3 alkylene group, more preferably a Cl-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyi dimethyl betaine; Cl2 l4 acylamidopropylbetaine; Cg l~ acylam;dohexyldiethyl betaine; 4[cl4-l6 acylmethylamidodiethylammonio]-l-carboxybutane;
C16 18 acylamidodimethylbetaine; Cl2 16 acylamidopentanediethyl-betaine; ~Cl2 16 acylmethylamidodimeth~lbetaine. Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the Cl0-l8 acylamidopro-pane (or ethane) dimethyl (or diethyl) betaines.
The sultaines useful in the present invention are those com-pounds having the formula R(R1)2N+R2S03- wherein R is a C6-Clg hydrocarbyl group, preferably a Clo-cl6 alkyl group, more prefer~bly a C12-C13 alkyl group, each Rl is typically Cl-c3 alkyl, pre;eraDly methyl, and R2 is a Cl-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hycr~x~a k~l2ne ~rûup. '~zmples cf suitable sultaines include C12 lS d me-th~la~mrni~-2-hydrovypropyl sulfonate, C12 14 amido propyl am oniû-2-nyarûxypropyl sultaine, C12 14 dihydroxyethylammonio propzne sulfonate, and Cl6-l8 W O 92/06161 2 ~
dimethylammonio hexane sulfonate, with C12 14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
Suitable nonionic detergent surfactants are generally d;sclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1375, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful no~ionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene ox,~c condensates of alkyl phenols. In general, the pol~ethylene oxide concensates are preferred. These compounds include the condensa'-~.
products of alkyl phenols having an a7kyl group containi"g ,-r abou~ ~ to about 12 carbon atoms in either a straignt ch3io cr branched chain configuration with the alkylene oxide. In a pre-ferr~d e~bodiment, the ethylene oxide is present in an amount equ~l 1~ to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all marketed by the Rohm &
Haas Company.
2. The alkyl ethoxylate 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 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of 3~ alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM
24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), ~5 both ~arketed by Union Càrbide Corporation; NeodolTM 45-9 (the cond nsation product of C14-C1s linear alcohol with 9 moles of w o 92/06161 PCT/~S~?1/069Xl ~ a ~ 1 16 -ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of 2~ 12"2 D~id2), ;,co~vl i~
45-7 (the condensation product of Cll-C~ .,?~ L~,~ 7 moles of ethylene oxide), ~leodol~M ~5-~ (th~ o~d2n~~iion ?i~ 3f C14-Cls linear alcohol ~ith ~ ~oles o,~ ?tl~/' ?lî? ~ ilJj~ ?I,~r '~.V
Shell Chemical Company, and ~yro~ tU~ ? ~O~ ?ilSd~:'O.~ ~r~n~c: .Oi' C13~Cls alcohol ~ith 9 ~31'.?~ ?th~ ?~:? C''' ~~
Procter a Gamble Company.
3. Ihe conb~nsation ?ro~u 's ~ ?' n,~
phobic basa for,med by ~h~ o~i~ens propylene 91yCC?l . The hydro?hobis ?or i~ ~ ? ~ n.~
preferably has a molecular :~eig7i 0-l i ;'~m 'iL~ U
and exhibits water insolubilitv. Ihe additi3,, o, ?ol~o~v?.i7~1en~
moieties to tih;is 'nYd'~3?~ ~J~
15 solubility or the mol~cule as 3 ',l~lOle, ~U ~ ;,., oo~_, .,-,~
the product is retained up to the point ~Yher~ the polyoxyethylen~
content is about 50% of the total weight o; ~ne condensaiion prod-uct, 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 PluronicTM surfactants, marketed by BASF.
4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide ~nd ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2O00 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 11,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
w o 92/06161 PCT/~S91/06981 ~ a ~ 6 -However, there is nothing in the art which teaches the unex-pected cleaning and sudsing performance, lack of "slippery" feel, mildnes, to the handt and ease of rinsing associated with the detergent compositions of the present invention which contain anionic s~llf~ted or sulfonated anionic surfactants, certain polyhy-droxy fatty acid amides and a critically selected suds enhancing agent.
Additionally, nothing in the art teaches that such compositions provi'~ su~stantially uniform improved sudsing performance across l3 varyi,~ a"perature and humidity c~nditions.
Tt is 'herefore an object of the present invention to provide sucin Ge-~argent compositions which exhibit such properties.
It is still another object of the present invention to provide a ~ ,h~d T~J'~ n~ j~y soilod diihPs by tr~tl~g ;~id dish~s with th~
partic~,a~~ det2rgent compositions described herein.
These objects are realized by the present invention.
SUMMARY OF THE INVENTION
The present i m ention is directed to detergent compositions comprising from about 5% to about 65% by weight of a surfactant mixture comprising:
(a) from about 5% to about 95% by weight of one or more anionic sulfate or sulfonate surfactants;
(b) from about 5% to about 95% by weight of one or more polyhydroxy fatty acid amides having the formula o R1 R2 - C - N - z wherein Rl is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a Cs-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative i;hereof; and ~c) from about 1% to about 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyeihylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene WO 92/06161 PCJ/US91/06~81 2 ~
oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene ox,de ~ ,rop~13ne 31~col, th2 condensation product of ethylene oxide ~.Yi th ~he product resulting from the --?.~ . ~?~l ?nD O:~i dD ~nd othyl enedi ami ne, alkylpol~saccharides, ~nd f~tty acid amides; and mixtures ;;'~ci cv, .
Th~ ?r 2s2nt ,n~/en-~ion .s also ~irected to~ard a method for cleani"g ~ sl n ~ ;-O~~ Oalm'-JI i;i,s v.eating said disnes w i t ~ ~ ~ P ~ r ~ ' " ~
' S ~ ? T ? T '' '! !~ r ~ ?IT T ON
~ he .a~er ~er.t rr.mr~o~,j"; ons or (,I!e oresen~ invent ion comorise I rG~ '0'!1 ''~;'/'! r~ro-s~r~hl ~ om ~u~out 10~~ to about 50%, mos ~ ~'c ~ cl~a~ ' J ~ ';'J~ g~ V l a surfaclant ntixturs compri;ing one or ~ore anionic sulfated or sulfonated surfactants, one or morP polvhydrovy fatty acid amides, and a critically selected suds enhancing agent. These and other ingredients typically found in liquid detergent compositions are set forth below. The detergent compositions of the present invention are preferably in the form of a liquid or a gel, more preferably light-duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions.
Anionic Surfactant The surfactant mixture of the present invention, comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more anionic sulfate or sulfonate surfactants. The anionic sulfate or sulfonate surfactant may Se any organic sulfate or sulfonate surfactant, but is preferably selected from Cll-Cls alkyl benzene sulfonates, C10-Cl6 alkyl sulfates and their ethoxy analogues containing up to twelve moles of ethylene oxide per mole of alkyl ethoxy sulfates, Cl3-Cl2 paraffin sulfonates, C,0-Cl6 olefin sulfonatPs, C1o-C20 alkyl glyceryl ether sulfonates, Cg-C17 acyl-N-(C1-C4 alkyl3 or -N-(C2-C4 hydroxyalkyl) glucamine sulfates, 3~ and mixtures of any OT the ;orsgoing. ~ore preferably the anionic surfactant is selected from li"ear alkyl benzsne sulfonates, alkyl ethoxy sulfates, alkyl glyceryl ether sulfonates and paraffin sulfonates.
w o 92/06161 ~ PCT/~S91/06981 Alkyl benzene sulfonates useful in compositions of the present inven~ion are those in ~hich the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 10-13 carbon atoms, a ;mai;~rial 1i~h an a~crase carbon chain length of 11.2 being most pre;~rn~ci. Ih2 ?ren~l isomer distribution, i.e., the point of ~ a ~ , e;îain ~o i~h2 ~enz2ne nucleus, is not critical. ~ut alkyl b2nzenes having a high 2-phenyl isomer content ~u~ le al'~l ;ul~ates are orimary alkyl sulfates in ~hich the ; '~ ; oarbon a~oms, more pref~rably an averaige . ~ - .; ;ù~ h~ C10 r1 ~
;.S~ ,..,..._.'~.'_.. -.'.m '.i;'Jl''.i~ S) or ~ie~ r 0i2Fin build-up, or 'u~'ù ;~.'n ~-sls~ f~,m SU i~ae~a souirces ror ~he 21~yl group. ~vamples or~ s~!n~a~lC~iiJ derm/ea maleria7s include uobanol 23 ~21,~; sola oy Sh?ll ''hi~micals (~v? !td.~ .thyl 24 sold by the Ethyl Corporation, a blena or Cl3-C~s alcoilols in the ratio 67% Cl3, 33% C~s sold under the trad~ name Lutensol by BASF GmbH and Synperonic (RTM) by ICI
Ltd., and Lial 125 sold by Liquichimica Italiana. Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C~0-C~6 a kohol ~ith 2n aver~ge of up to 6 ethylene oxide groups. The C~0-C~6 alcohol itself can be obtained from any of the sources previously described for the alkyl sulfate component. C~2-C~4 alkyl ethoxy sulfates are preferred.
~ o m2r.t.ûnal base-catalyzed ethoxylation processes to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 eihoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. 81ends can be made of material having different degrees of ethoxy,a~idn and/or di " er2nt ethoxylate distributions arising from the specific ethoxylation te~hniques employed and subsequent proceC ing st3~s such 3S distillation. For example, it has been fourd that sudsing and ~rease r-moval performance equivalent to that gi1en oJ a olend G-- 21kyl sulrate and alkyl triethoxy sulfate can be obtained by reducing the level of alkyl sulfate and using an alkyl WO 92/06161 PC'r/l~S91/06981 ethoxy sulfate with an average of approximately two ethoxy groups per mole of alcohol. In preferred composition; in accordance with the present invention an al~l ethox~ sulfatA is usod which h2s an average degree of ethoxylation of from 0.~ to 5, more preferably from 0.4 to 3Ø
Paraffin sulfonates useful in the presen~ invention nave rrom 13 to 18 carbon atoms pr~r ",ol 5OU1~ m~O~A 'AeSj--b1_/ 13 'o !5 ca,bon atoms per molecule. These sulfonates ar? pr?;arabiy prepared oy subjecting a cut of para,~,in, ~-r~s~ S :~ ~h~ ~ aln len~'h specified above, to the -,0 a~ 0~' 5~ A O j~X'de ' n~ OXtSal1 j 1 accordanc~ with the well-kr.c~.Jr. - '.-3~idar.3n ~rOA?SS. Ih? pro~uct of this reaction is a seconGarJ iui;onic aci~ ~riiC~l i; '~nein neutralized with a s~litablD base to provide a water-soluble secondary al~yl ;u~ ,a~ J~
be obtained by other methods, e.g., D~ the sul,~ochlorinaLion me.hod in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates. Whatever technique is employed, it is normally desirable to produce the sulfonate as the monosulfonate, having no unreacted starting hydrocarbon or having only a limited proportion thereof present and with little or no inorganic salt by-product.
Similarly, the proportions of disulfonate or higher sulfonated material will be minimized, although some may be present. The monosulfonate may be terminally sulfonated or the sulfonate group may be joined on the 2-carbon or other carbon of the linear chain.
Similarly, any accompanying disulfonate, usually produced when an excess of sulfonating a~ent is present, may have the sulfonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the monosulfonates and disulfonates may be present.
Mixtures of monoalkane sulfonates wherein the alkanes are of 14 and 15 carbon atoms are particularly preferred wherein the sulfonates are present in the weight ratio of Cl~-Cls paraffins in the range from 1:3 to 3:1.
Olefin sulfonates useful ir the pre;ent inventton are mixtures of alkene-l-sulfonates, alkene r,ydrox~sulfonates, alkene disulfon-ates and hydroxydisulfonates, and are described in the commonly ~O 92/06161 ~ PCI/~S91/06981 jj;J.~b~ lo- , assigned U.S. Patent 3,332,880, issued to P. F. Pflauner and A.
Kessler on ~uly 25, 1957.
Suitable alkyl glycer,~l ether sulfonates are those deriYed from ethers 3f C'aaJ"~_ ;il iniJi ';'ll-'i u~ ?. ~ S~ C ,2,1~ lCl udi~ L;l~ g-Ci7 acyl-N-(cl-c4 al~. ; .''? ~ S, iYI ~fi~rz31y those in :lhich ~he C~-Cl~ ac~l ciloup is d~rived from coconut or palm ? ' ... .: .?. _ .~-' ?-' ' ' ' - ? ? ~-- -i-' ' ? ~ hgd idisc'osed in U S ~ert ~717 ~ issu~?d ~eDt?mber 13, lg55 to Schwartz.
0 ~ ' -!,1 ? ' ' ~ n ' '~ ar '~ n ~ com,~onent is ~- ,;; " ~ 5 i~lV;;
pr~ r e, ,'"!~ .
~n ~re'~ -.ra~s ---Icn, ilc~rqorai:-ng ~ -Cls alkyl eilloxy sulfa-e ~ e anionic surr1c~ant~ ;rhe ~olar amount of magnesium ion in the co~pos ,vns is cont~ollav to corraspc,d to 0.3~-0.v5X ~here X is the number of moles of C1~-C~s alkyl sulfate present. Most preferably the magnesium ion content is adjusted to provide the stoichiometric equivalent, i.e., half the molar amount of the alkyl sulfate present. In such positions the magnesium ion will be present at a level of from about 0.15% to about 3.0% by weight, preferably from 0.25% to 1.5% by weight of the composition.
PolYhvdrox~ Fa'tv Acid A,,ide ComDonent Th~ ~urfactant mixture orr the pr sent invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more polyhydroxy faLty acid amides haiins :he structural formula:
(I) R2 - C - N - Z
wherein: ~1 is H, Cl-C4 hydrocarb;l, 2-hydroxy ethyt, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C~ alkyl, most Drererably C1 alkyl (i.e., methyl);
and R2 is a C~-C31 h~drocarb~', ure'erably ,traight-chain C7-C1g alkyl or alkenyl, more ~referably straight-chain Cg-C17 alkyl or alkenyl~ ~oSr ~reFzr~o~y str~i~ -o"ain ~ 17 alkyl or alkenyl, or mixture thereof; and ~ is a pvl/h~dr~xvh~drocarbyl having a linear hydrocar~yl chain ~ith ~t leas ~ h~drsxyls directly connected to the chain, or an alkoxylated derivatiYe (preferably ethoxylated or w o 92/06161 ~ J ~ pcT/~s9l/o69xl propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, tructose, maltose, lactose, galactose, mannose, and xylo;e. ~s r~ llal,, high dextrose corn syrup, high fructose corn s/rup ~nd 'n~ alt~se corn syrup can be utili~ed 3S '~211 ~:5 '~
above. These corn syrups may yield a mi~ o,~ a'~al O~ v"~..'; ,~0. 7.
It should be understood that it is oy no ,ne~ il7L ~îd=d ~v ~c~dc other suitable raw materials. Z preferably iill oe ielcc~ ,r.,", the group consisting of -C~2-(C~OH
CH2O~., -CH~-(CHOH)2(CHOR')(CHOH)-C~2~n! .ln~ a, ,,;
to 5, inrlusl~/o, and R' iS H or a cvclil o; ;;;~i; r ide, ~nd ~lkoxylat~d deri~atl/as t~r~-o~. ;- ~. r~
glycit,7i ~r,~rein n is " ?art c l3i~'y -C! -'r. o~; r~
In Formula (1), Ri can oe, ror e~c,l~ .lc;n~ ",;"
N-propyl, N-isopropyl, N-but~l, N-2-hydroxy ~thyl, or ~ -nydroxy propyl.
R2-C0-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be l-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, l-deoxylactityl, l-deoxygalactityl, l-deoxymannityl, 1-deoxymalto-triotityl, etc.
The most preferred polyhydroxy fatty acid amide has the general formula R2 - C - N - CH2 - (CHOH)4CH20H
wherein R2 is a C11-C17 straight-chain al~l or al~enyl group.
Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl Polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. ?rocesses Eor making compositions containing polyhydroxy ratt~ acid amid2s are disclosed, for exa~ple, in G.B. Patent Specitication 809,060, published ~ebruary 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. ~ilson, and U.S. Patent w o 92/0616~ r~j i PCT/~S91/06981 2,703,798, Anthony M. Sch~artz, issued March 8, 1955, and U.S.
Patent 1,985,~24, j.SUeA u~cqm-~r 75, 1~3~1 io ~',3Sott, e2ch of which is incorporated heroin by r~,-?r-n.c2.
In one procef~sl-~ns ~ ai'~-~ or ~-nydrcxyal~yl, N-deox~g~c1t~l ,a~t~ c-.~her~in ~.e ~yeityl co~onent is deri~d ~~o~ .~Jc~ v.~Gl,ty is N-meth~ -eth~ re~I-m~ . N-h~!droxye'~yl, or N-hydroxypr~ J ~ a '~yl- or methyl ;~ a;l~
preS2nC~ O; a ~ C~ i n~~~ 0;
tetrasodium pyropiios;i~a~e, ue..~;~oLassiu,;l 'r~ unospi;d.e, li~inium hydroxid~ ,~d;~ ~ - ,~,- s.,~ d-~x ~.-. ~-lci~.~ n ~r3xid~~
lithiu~ c~h~ nn-~ r~sod~um tartrate, dipotassium LarLnaL~, sodium po~assium tartra-ce, trisodium citrate, tripotassium citrate, sodium basic silicat2s, potassium bas;c s;licates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about lO mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 13~'C to about 170'C 'or typically from about 20 to abûut 90 mi~utes. Wnen triglycertdes are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agen~, cal.ulat2c on a weisht p=rcent basis of total reaction mixture, selecte~ fr~~ saturaied falty alcoho7 polyethoxy7-ates, alkylpolyglucosides, line~r glucamide surfactant, and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty -;ter to about i38~C to about 170~C;
(b) addins t.,e 'J-al'~;l v~ ,.-hydr~xya'~jl glucamiil to the heated fatty acid es'-r and mixing t~ khe extent needed to rorm a two-.,hase lig;i-.'li,:.~id mixture;
(c) mixing the catal~st ~ th~ reactiun mixture ?.nJ
(d) stirring f5r th- ;pec :-,e'' r_dCtiGn 'iine.
W o 92/06161 PCT/~S91/06981 - 13 - ~ 3 9 ~
Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide produc~
is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate. A de~ailed experimental procedure is provided below in the section entl~ed Experimental.
The polyhydroxy "fatty acid" amide materials used herein also offer the advantages to the detergent formulator 'ha~ ~h~y c--, "
prepared wholly or primarily from natural, r-n~~-ble, petrochemical feedstocks and are degradable. They a1so exn,o~ io~
toxicity to aquatic life.
~ t should be recognized that along with the polyhydroxy r~atty acid amid s of Formula (I), the proc~ss s used ~o produc~- ~.r~m ~
also typically produce quantities of nonvolatile by-product s _h a esteramides and cyclic polyhydroxy fatty acid amide. ~he level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels Gf by-products, including such cyclic amide by-product.
Suds Enhancinq Aqent The surfactant mixture of the present invention ~urther comprises from about 1% to about 20%, preferably from about 2% ~more preferably ~%) to about 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, and certain nonionics.
Amine oxides useful in the present invention include those compounds having the formula o 35R3(0R4)xN(Rs)2 wherein R3 is selected from an alkyl, hydrox~alkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R4 is an alkylene or w o 92/06161 PCT/~iS~)1/06981 2 ~3 ~ r~ 14 -hydroxyalkylene group containing from 2 to 3 carbon atoms, prefer-ably 2 carbon atoms, or mixtures ~h~reof; ~ i~, .-rû~ ~ ~o 3, ?r2,~er-ably 0; and each Rs is an al'~Jl or h,'~rOV'!?.ll'yl ~roup ~ontainin~n~
from 1 to 3, preferably from 1 to 2 carbon zt~-~, Jr ~. polyethylene oxide group containing from l ~o ', 3,~?'~ al'! ;- ?','~l.?n? o~ide groups. The Rs groups can oe a~ac;l~u ~o ~dcn ~ r. a~q. ~ Lnr~uG?
an oxygen or nitrogen atom, to ~orm a - n~ r'!~?~
These amine oxide sur,~acLan~s l~ ?ar~ n~ i'lCIUC!.? ~ C.3 alkyl dimethyl amjna OXi~ .r.
amine oxides. Examples or Sl!C.l î ' ~ ' ' l ~ ~C", ' ,: ~ l oxide, diethyldecylamine oxio~ -n~ ?C'/;~ml~
oxide, dim2thyldodecylamin~
methylethylhexadecylamine oxide, dca2cylamiaoDroDyl aim-~cnylamine oxide ~nd di~l~?th~ -h~/cl 0v~ ? ~ ;-? -?-~~ '--?
Clo ~g alkyl dimethylamine ,~,de, a"' r;' ~ ~;y~ z~
dimethylamine oxide.
The betaines useful in the pries2nt invention are those com-pounds having the formula R(R1)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group, preferably a Clo C16 alkyl group, each R1 is typically Cs-C3 alkyl, preferably methyl, and R2 is a Cl-Cs hydrocarbyl group, preferably a Cl-C3 alkylene group, more preferably a Cl-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyi dimethyl betaine; Cl2 l4 acylamidopropylbetaine; Cg l~ acylam;dohexyldiethyl betaine; 4[cl4-l6 acylmethylamidodiethylammonio]-l-carboxybutane;
C16 18 acylamidodimethylbetaine; Cl2 16 acylamidopentanediethyl-betaine; ~Cl2 16 acylmethylamidodimeth~lbetaine. Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the Cl0-l8 acylamidopro-pane (or ethane) dimethyl (or diethyl) betaines.
The sultaines useful in the present invention are those com-pounds having the formula R(R1)2N+R2S03- wherein R is a C6-Clg hydrocarbyl group, preferably a Clo-cl6 alkyl group, more prefer~bly a C12-C13 alkyl group, each Rl is typically Cl-c3 alkyl, pre;eraDly methyl, and R2 is a Cl-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hycr~x~a k~l2ne ~rûup. '~zmples cf suitable sultaines include C12 lS d me-th~la~mrni~-2-hydrovypropyl sulfonate, C12 14 amido propyl am oniû-2-nyarûxypropyl sultaine, C12 14 dihydroxyethylammonio propzne sulfonate, and Cl6-l8 W O 92/06161 2 ~
dimethylammonio hexane sulfonate, with C12 14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
Suitable nonionic detergent surfactants are generally d;sclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1375, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful no~ionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene ox,~c condensates of alkyl phenols. In general, the pol~ethylene oxide concensates are preferred. These compounds include the condensa'-~.
products of alkyl phenols having an a7kyl group containi"g ,-r abou~ ~ to about 12 carbon atoms in either a straignt ch3io cr branched chain configuration with the alkylene oxide. In a pre-ferr~d e~bodiment, the ethylene oxide is present in an amount equ~l 1~ to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all marketed by the Rohm &
Haas Company.
2. The alkyl ethoxylate 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 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of 3~ alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM
24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), ~5 both ~arketed by Union Càrbide Corporation; NeodolTM 45-9 (the cond nsation product of C14-C1s linear alcohol with 9 moles of w o 92/06161 PCT/~S~?1/069Xl ~ a ~ 1 16 -ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of 2~ 12"2 D~id2), ;,co~vl i~
45-7 (the condensation product of Cll-C~ .,?~ L~,~ 7 moles of ethylene oxide), ~leodol~M ~5-~ (th~ o~d2n~~iion ?i~ 3f C14-Cls linear alcohol ~ith ~ ~oles o,~ ?tl~/' ?lî? ~ ilJj~ ?I,~r '~.V
Shell Chemical Company, and ~yro~ tU~ ? ~O~ ?ilSd~:'O.~ ~r~n~c: .Oi' C13~Cls alcohol ~ith 9 ~31'.?~ ?th~ ?~:? C''' ~~
Procter a Gamble Company.
3. Ihe conb~nsation ?ro~u 's ~ ?' n,~
phobic basa for,med by ~h~ o~i~ens propylene 91yCC?l . The hydro?hobis ?or i~ ~ ? ~ n.~
preferably has a molecular :~eig7i 0-l i ;'~m 'iL~ U
and exhibits water insolubilitv. Ihe additi3,, o, ?ol~o~v?.i7~1en~
moieties to tih;is 'nYd'~3?~ ~J~
15 solubility or the mol~cule as 3 ',l~lOle, ~U ~ ;,., oo~_, .,-,~
the product is retained up to the point ~Yher~ the polyoxyethylen~
content is about 50% of the total weight o; ~ne condensaiion prod-uct, 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 PluronicTM surfactants, marketed by BASF.
4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide ~nd ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2O00 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 11,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
5. Alkylpolysaccharides disclosed in U.S. Patent ~,565,647, Llenado, issued January 21, 1986, having a hydrophobic group con-taining from about 6 to about 30 carbon atoms, pr~ferabl~/ F ~ lhoul 10 to about 16 carbon atoms and a pol~sacchar-,d~ ., a pcm/gly-coside, hydrophilic group containir,~ from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 W o 92/06161 PCT/US~1/06981 - 17 ~ 2 ~ ~ ~
to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galac-tosyl moieties can be substituted for the glucosyl moieties.
(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, -to. ,o~itions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., bet.Y~n the one position of the additional saccharide units and .he 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
O~t,onally, and less desirably, there can be a polyalkylene-O oxide ch~in joining the hydrophobic moiety and the polysaccharide "m~.-,,y. T~ prererred alkyleneoxide is ethylene oxide. Typical h~dropnobic groups include al~yl groups, either saturated or unsatu-rate~, ~.a~ched or unbrancned containing From 8 to 18, pre'erably from 10 to 16, carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglu-cosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tr;-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexas lcosides.
The preferred alkylpolyglycosides have the formula R20(Cnl~2nO)t(slYcosyl )x wh~rein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from O to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the g,ucoside (attachment at the l-position). The additional g1ycosyl units can then be attached between their l-position and the w o 92/06161 PCT/US91/06981 2 ~ 9 2 ~ 18 -prec ing glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galac-tosyl moieties can be substituted for the glucosyl moieties.
(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, -to. ,o~itions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., bet.Y~n the one position of the additional saccharide units and .he 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
O~t,onally, and less desirably, there can be a polyalkylene-O oxide ch~in joining the hydrophobic moiety and the polysaccharide "m~.-,,y. T~ prererred alkyleneoxide is ethylene oxide. Typical h~dropnobic groups include al~yl groups, either saturated or unsatu-rate~, ~.a~ched or unbrancned containing From 8 to 18, pre'erably from 10 to 16, carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglu-cosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tr;-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexas lcosides.
The preferred alkylpolyglycosides have the formula R20(Cnl~2nO)t(slYcosyl )x wh~rein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from O to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the g,ucoside (attachment at the l-position). The additional g1ycosyl units can then be attached between their l-position and the w o 92/06161 PCT/US91/06981 2 ~ 9 2 ~ 18 -prec ing glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
6. Fatty acid amide surfactants having the formula:
o S R6 - C - N(R7)2 wherein R6 is an alkyl group containing from 7 to 21, pre-r~rably from 9 to 17 carbon atoms and each R7 is selected frsm t~e ~~eup consisting of hydrogen, Cl-C4 alkyl, C~-C~ hydroxya7'~yi, ~n -(C2H40)XH, where x i5 in the range of from 1 .o 3.
I0 Preferred amides are Cg-C~c ammonia ~mides, mon~e ,~no ~m:
diethanolamides, and isopropanolamides.
~referred suds enhancing agents are C10 13 al',<y7 dim-tl~, 1;.,.
oxides, C10 18 acyl amide alkyl dimethyl amine oxides, betaines, sultaines, condensation products of aliph2tlc ~lc3hsl, mth ~t- ~----oxides, and alkylpolysaccharides, and mixtur~s thereo;.
Liquid Carrier In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions comprise from about 95% to about 35% by weight, preferably from about 90% to about 50% by weight, most preferably from about 85% to about 60% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g, ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred alcohol.
ComPosition DH
- The liquid detergent compositions hereof will preferably be formulated such that during use in a~ueous cleaning operations the wash water will have a pH of between about 6 and about 9, more preferably between about 7 and about 8. Liquid product formulations preferably have a pH in the range of from about 5.0 to about 10.5, more preferably from about 6.0 to about 9.0, most preferably rrom about 6.5 to about 7.5. Techniques for controlling pH at recGm-mended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art.
Thickeninq Aqent The detergent compositions of the present invention may also be in the form of a gel. Such compositions are typically formulated in W O 92/06161 P~r/US91/06981 ~ ~3''~
the same manner as liquid detergent compositions, except they contain an additional thickening agent.
An~ material or materials which can be admixed with the aqueous liquid to provide shear-thinning compositions having sufficient s-n ',e used in the compositions of this invention.
,~ate,ials such as colloidal silica, particulate polymers, such as pOlvs~yr~np and oxidized polystyrene, combinations of cer~ain surfactants, and water-soluble polymers such as polyacrylate are '~noYn a~ , oYidQ ~ield values.
lO~ ?rQ~errPd thic~ening agent useful in tne compositions of the -r~ --~ ;n~ n iS a nigh molecular weight polycarboxylate polymer hlc ~nQ~ 3~ 1g~ moleculan weight" it is meant from about 50~ u~ ~,OvO,~,CO, prer2rably from 2~0ut 750,000 to about 4,000,iO~.
liThQ polycarboxylate polymer may be a carboxyvinyl polymer.
Such compounds are disclosed in U.S. Patent 2,798,053, which is incorporated herein by reference. Methods for making carboxyvinyl polymers are also disclosed in Brown, and are also incorporated herein by ~eference.
20A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0. lZo to about l~/o by weight of the total mono22rs of a polyether of a polyhydric alcohol, wh;ch polyhydric alcohol contains at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule. Other monoolefinic monomeric materials may be present in the monomeric mixture if desired, even in predomi-nant proportion. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more 3~ preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, WO 92/06161 PCl/l~S91/069~1 2 a ~ 20 -it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2~~o to about 2.5'Jo.
Preferred monomeric olefinically unsaturated carboxylic acid, for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolPfinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure R
CH2 = C - COOH
herein R is a substituent selected from ~he group consisting Oir hydrogen and lower alkyl groups; most preferred is acrylic acid.
C~r oxyvinyl pol~mers us2;ul in rormulations or the ?~e ~;~
invention haYe a molecular weight of at least about 750~000. Pr--ferred are highly cross-linked carboxyvinyl polymers having a molecular weight of at least about 1~250~000. Also preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000, which may be less highly cross-linked.
Various carboxyvinyl polymers are commercially available from B. F. Goodrich Company, New York, N.Y., under the trade name Carbopol. Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 750~000; preferred is Carbopol 941 having a molecular weight of about 1,250,000, and more preferred are Carbopols 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respec-tively.
Carbopol 934 is a very slightly cross-linked carboxyvinyl polymer having a molecular weight of about 3,000,000. It has been described as a high molecular weight polyacrylic acid cross-linked with about 1% of polyallyl sucrose having an average of about 5.8 allyl groups for each molecule of sucrose.
Additional polycarboxylate polymers useful in the present invention are Sokolan PHC-25R, a polyacrylic acid available from 3~ BASF Corp., and GantrezR a poly(methyl vinyl ether/maleic acid) interpoiymer available from GAF Corp.
w o 92/06161 PcT/~s91/06s81 - 21 ~ 2 a 61 Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalk~n,l ~ Pther and having a molecular weight of from about 750,000 to lbout 4,000,000.
";~hl~/ profDrrod examples of these polycarboxylate polymer thickenors a-o ~he Carbopol 600 series resins available from B. F.
~oû~ .p~c.~lly pr ferrod ~re Carbopol 616 and 617. It is belieJed ~h t these resins are more highly cross-linked than the 900 seri , ;~ i-, ;nd h~Ya mol?cular ~.~eights bet~een about 1,000,000 and 0 ~,r.GO,:';'n.. !i~-,res ~, ?ol~ca,~xylate polymers as herein described ma~ s~i ln the ~resont in~ention. Particularly preferred is ~ CarooDol ~1O and ol7 seriDs resins.
TaO ~ r~rboxylate polymer thickener is utilized preferably ~ 1 y "o :l.iy -'h,ck~nl"s .~ents. In f~ct, it has been foun~ -;nac i-,' the po7ycarboxylat2 polymers of the present invention are utili~ed ~ith clay in the composition of the present invention, a less desirable product, in terms of phase instability, results.
In other words, the polycarboxylate polymer ;s preferably used instead of clay as a thickening/stabilizing agent in the present compositions.
The polycarboxylate polymer also provides a reduction in what is commonly called "bottle hang-up~. This term refers to the inability to dispense all of the dishwashing detergent product from its container. Without intending to be bound by theory, it is believed that the thickened compositions of the present invention provide this benefit because the force of cohesion of the composi-tion is greater than the force of adhesion to the container wall.
~ith clay thickener systems, which most commercially available products contain, bottle hang-up can be a significant problem under certain conditions.
Without intending to be bound by theory, it is also believed that the long chain molecules of the polycarboxylate polymer thick-ener help suspend solids in the thickened detergent composi-~ ons of the present invention and help keep the matrix expanded. The polymeric material is also les; sensitiYe than clay thickeners to destruction due to repeated shearing, such as occurs when the composition is vigorously mixed.
w o 92/0616] 2 IJ '~ 22 - PCT/~'S91/06981 If the polycarboxylate poly~er is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2~~o to about 2% by weight.
Tine ~nickening agents are used to provide a yield value or from about -a ~ ouc 350 ~nd most preferably from about 75 to a~ut 250.
Y1e,~ n~l~/sis The ~ield value is an indication of the shear stress at ~hich t~.~ J~ ?n9th is exceeded and flow is initiated. It is me~sur-d ilen ;~ 3roGkeielu ~'J~ i,.o '~l /lscom2t2r .~ , a ~ ?'n~l~e 3_ _~-_ '.' i 'l~in9 3 ,iellp~ h Griy2 upward during as,ocia~ed ,~ ~d--ing,. ,,a Sj'5;2m~ iS set to 0.~ rpm and a re2ding is ta~o., .~or ~;~o eomoosition to be testPd after 30 seconds or atter the sysiem is stabl~. The system is stopped and the rpm is reset to 1.0 rpm. A
reading is taken for the same composiLion after 30 seconds or after the system is stable. Stress at zero shear is equal to two times the 0.5 rpm reading minus the reading at 1.0 rpm. The yield value is calculated as the stress at zero shear times 18.8 (conversion factor).
ODtional Com w nents The compositions of the present invention may optionally contain other anionic and nonionic compounds (other than those already disclosed herein).
Other anionic surfactants useful for detersive purposes can also be included in the composition; hereof. Examples of useful anio~ic surfactants include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent Specification No. 1,082,179, Cg-C22 alkylsulfates, Cg- C2 4 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxid~o); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty 2c~l gl~corol sulfates, alkyl phenol ethylene oxide ether c~lfatos, alk~l ~hosphates, isethionates such as the acyl isethion-ates, acyl iaurate~s, fatty acid amides, alkyl succinates and sulfo-succinates, acyl sarcosinates, sulfates of alkylpolysaccharides such WO 92/06161 PCI/US~1/06981 - ~925~1 as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds having already ~e2n described herein), alkyl ether car-bonates, Fatty acids esterified ~ith isethionic acid and neutralized ~ith sodium hydroxide, and -;a~ty acids amides of methyl tauride.
Furtner ~xa~ples ar~ describ~d in ''SUrTaC3 Active Agents and Deter-gent,' i'~oi. . and ~ o~ ar;z~ Pe,r~ ~nd 3erch). A ~/arie~y of such surfactants are also generally disclosed in U.S. Patent 3,329,~,~, ,iaued D~camb~r 30, 9?5 ~o laughlin, et al. at Column 23, 1 no ~ 'hrnu~h Column 29~ line 23 (herein incorporated by r~
~ 3ù~ tQd ~nto th~
de ~ , 5 3 i ~ C ~ d ll ~ j c a ~ be ~'oa u ~, y deSCriDed dS alipha~ic ~eri~;a~ i';QS O; socond~ry or 'ertiary am-ln2s, or ~li??i io ~el i~a~iYPs or o3t~roc~clic secondary and certiary aminos -- Yhich tho aliphatic r~dical can be straight- or branched-chain. One Ot the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one con-tains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, lines 18-35 (herein incorporated by reference) for examples of useful ampholytic surfactants.
Zwitterionic surfactants may also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivativ2s of secondary and tertiary amines, deriva-tives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfoniumcompounds. See U.S. Patent No. 3,329,678 to Laughlin et al., issued December 30, 1975, at column 1g, line 38 through column 22, line 48 (herein incorporated by reference) for examples of useful zwitteri-onic surfactants.
Such ampholytic and zwitterionic surfactants are generally usedin combination with one or more anionic and/or nonionic surfactants.
If included in the compositions of the present invention, these optional additional surfactants are typically present at a concen-tration cf from about 1% to about 10%, preferably from about 2% toabcut 5% by :~eight.
Otner optional ingredients include detergency builders, either of the organic or inorganic type, although such builders in general w o 92/06161 PcT/uss1/0698 ~ 24 -are not preferred for use in the composition of the present inven-tion. Examples of water-soluble inorganic builders which can be used, either alone or in admixture with themselves or with organic al'~alin2 se~u~s-t ant buildor salts, are glycine, alkyl and al~-nyl suc~ln~ ali metal carbonates, phosphates, polyphosphates, and a- ,- c a~m~ s of such salts are sodium tripol~p;,os-phato, sodium carbonate, potassium carbonate, sodium pyrophosphate, ~~~ ? ~~ph3;?h~te, potassium tripolyphosphate, and sodium hexameta3hosphate. r'xamples of organic builder salts which can be iOi'!S-~ ,1 ac",i~-ur~ ~i'h ~ach other, or with the preceding ~~ a ;~ -l'~l n~ er -al's~ aro al~ali metal polycarboxylates, C;ii~ '_' 'U'''~ as iOJ'i;.a~;~ aid pctas,ium citrale, sodium an~ pot~s.iLum ~arir; ~, ~ù~ ,n ~I~d ~a~jiu", ~yi~ d~ c~c~~aac2~a~c~ a~u 1~and DOtaSSi l~m ,'~-(2-hydroxy- ethyl)-ethylene diamine triacetat?s, sodium and potassium nitr,lo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxydi-succinates, and sodium and potassium tartrate mono- and di-succinates, such as those described in U.S. Patent 4,663,071 (Bush 20et al., issued May 5, 1987), the disclosure of which is incorporated herein. Other organic detergency builders, such as water-soluble phosphonates, can be used in the compositions of the present inven-tion. HoweYer, detergency builders in general have limited value when tne compositions of the present invention are in the form of light-duty liquid dishwashing detergent compositions. If included in the compositions of the present invention, these optional buil~ors aro typically present at a concentration of from about 1.0%
to about 10~h, preferably from a~out 2~~/o to about 5% by weight.
Other desi-rable ingredients include diluents, solvents, dyes, perfumes and hydrotropes (preferred). Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, etc. Diluents us~ful n tho ccmpositicns of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 5% by ~eight.
Solvents useful herein include water and lower molecular weight al colhû~ S, rUrh 2S eth~l alcohûl, isopropyl alcohol, etc Solvents useful in the compositions of the present invention are typically w o 92/06161 P~TJ~S~ 69i~1 2~5~ 2 ;j ~1 present at levels of from about 1% to about 60Yo~ preferably from about 5% co about r~o,' by :i21ght.
Hydrotro~es such as odium and potassium toluene sulfonate, sodium and poLassiu~ ~lene sulronat , sodium and potassium cumene sulfonat2, riscdium al,d ripo~assium sulfosuccinate, and related comlpoun~s ; ' . i:iC . ~ ,''i J._7. ''l~ -nL. J~ -;J-~ n2 diSClO.Uf Q C.
which is incorqoratsd 'nerein) can be utilized in the interests of ac,hievil,~, i ci-s,.e~ d~c ;~ t,~ -n~ ~!lscosity. T' has be'2n ~'". d 'h~t 'h? ~ .rot, ~p5~ can ha~/e ~ positi~/e effect on the 0 ~ r ~ .sndinq ~o be s~,.~ ,.. .. , ... ~ . .. ... ......... .... .. ... .
boun~ 5 ~ LI2 in che composiiion~ o,' ~"e p,-,an~ i"v~";1c" ~,e typica.,y ?~osent at 1S~Q~ o~ a~ ' lJ~ to a~out 1~ ?rQ;~raDmJ ~rom aDout 2~~o to abou' ~" by ~eigh'.
Optional ingredients useful when the compos;tions of the present invention aro used in liquid dishwashing detergent applica-tions include drainage promoting ethoxylated nonionic surfactants of the type disclosed in U.S. Patent 4,316,824, issued to Pancheri on February 23, 1982, the disclosure of which is incorporated herein.
While not intending to be bound by theory, it is believed that the claimed compositions of the present invention are beneficial in that they provide unexpected sudsing and cleaning performance and clean dishEs without im?arting a "greasy" feel to the cleaned dish, which is important in consumer markets where the cleanliness of a dish is judged by the lack of such a "greasy" feel. Furthermore, while not intending to be bound by theory, it is believed that further oenefits of the composition of the present invention are ease of rinsing and that they reduce the "slippery" feel associated with typical liquid detergent ~ompositions. The reduced slippery feel is important in consumer markets where such a "slippery" feel is not favor~d and is vie~ed as incomplete rinsing of surfactants from a dish surface.
Additionally, while not ,ntending to be bound by theory, it is 3~ believed that the Ccm?ositions of the present invention offer the benefit of unex~ected unifor,i t~ in sudsing ~erformance across varying temperature and humiait~ conditions, especially at a WO 92/06161 P~/~,iS91/069~1 ~~ ~3 (L3 ~ r ~ 26 -preferred dishwashing temperature in the range of from about 100~F
to about 120~F.
T~ a mathc~ aspoct of this in~/ention, soiled dishes are contact~d ~iLh ~n effective amount, typically from about 0.5 ml. to abou~ l (?Qr ?j dishes being treated), preferably from about 3 ml. ~o ~DOU~ iU ml., O; the composition of the present invention.
Th4 actu a~ ~-~unt ~$ l1,uid detsrg2nt composition used ~ill be based on ~ho v~dgemeni oF user, and ~ill typically depend upon factors ~c;l .a ';-- ~a, ~ .a, rroduc' Formulation of the composition, 1~ lnc,~ a~ o noen-;rl~ion ~T acti~e ingredisnt in ths composit-on, tho -~m o~ ~- ~oi~?d ~ishss to be cleaned, ths degree of soiling on ~ne ~i;n~ ,a ~n~ h~ particular product formulation, in turn. ~ epend upon a number of factors, such as the intended fl~ r-~ r~~4~ c. ) rOr .~5 co~?ositi~n prcduct. T;ia lol~o~iny are axa~,ples of typical methods in which the detergent compositions of the present invention may be used to clean soiled dishes. These examples are for illustrative purposes and are not intended to be limiting.
In a typical U.S. application, from about 3 ml. to about 15 ml., preferably from about 5 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml., of water in a sink havins a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml. The detergent composition has a surfactant mixture concentration of from about 21% to about 44% by weight, preferably from about 2~% to ~bout 40~/O by weight. The water is preferably at a temperature in the range of from about 80~F to about 125~F, more preferably in the range of from about 100~F to about 120~F. The soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being rontacts~ with the dish surface, and is typically contacted with ths dish sur,ac~ for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or WO 92/06161 ~ ,'S91/06981 similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the disn sur;ace.
In a typical Europed,l mar'~-L ppl1cat z , fr~,m about 3 ml. to about 15 ml., preferably from about 3 ml. to aDout 10 ml. of a liqild ~ rger,L comm~s ~ o~ ;c r~?,~in'~ rem about 1,000 ml.
to about 10,000 ml., more t~ r~l7y , rom acc~t ~,l)OO ml. to aooui a,OOO ml., or wa~2f "i a ; ..:~ : .n~ a ~ --t l- -~ ity n the range or from about ~i,OCO m,'. to about ~,390 ml., more typically from ~bout 10,dO~ ml. ~ i-o ~ ,O -". ~~ r 5en~ com.pc~itlon has a aur,~ac~a~ o~ ~' bv ~eiah~ ?re~e,-bl~ ~' '? ~.''~ ' e~ht. The water is preferabl~ ar ~ mper~ .n ? in ~:;le n~no~ ;)r ;nom ~ ûU_ ~0~
to ~o;;t 12~F, ~ ~ o-e'e~h~ ;n thV ~an~e ~f fr~m abollt lOO~F to abûu~ 1 2~'' r . I;12 ~vi~
the detergent composition and ~aa r, i,lere ;h2y are c.ean2d by contacting the soiled surface cr the dish with ~ cloth, sponse, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
In a typical Latin American and Japanese market appl;cation, from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl naving a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 1,000 ml. The detergent composition has a surfactant mixture concentra; on of frûm about 5% to about 40% by - weight, preferably from 3bout 10% to about 30% by weight. The soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or ;i,-milar article. The cloth, sponge, or similar article may be immers-d in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time w o 92/06l6~ PCT/~'S91/06981 ranging from about 1 to about 10 seconds, although the actual time will vary wlti~ each application and user. ~he contacting of the clot~, s~ 3;~ -i,ila~i~ article to the dish surface is preferably accompar,ied ~y a concurrent scru~3bing of the dish surface.
'7l0i~?~ od ~f J~S' '~ill cc~prise immersing the soiled dishes into a l~a,.~r 3a-~n Ynich is at3se,lt any 7iquid dishwashing detergent.
A de~ b ~nL n~ 'i7uid dlshYashing detergent, such as 2 sponne, 1~ p!arad ~iiAecl~iv in'o a separate quantity of undiluted l-lcju . .~ osi iOl ior a ?er;iod of time typically I0 i~ar,s~l~J :~~; -; v~ ; ~a '''i''~l!c . _~C'i-105. ~ne aDsorr3ing device, and c~n~ua~ u~iei~ a li~uid aisf,~ashing composition, is then contao ci , uil; ually ;v ~he ,iin,~3ce o,~ 2ach 3f the soiled dishes to remove ~aid soilina. ~he absorbing device is tyDically contacted ~ C ~ ;m~ r~ ~bout 1 t~
abou~ iO ~G~ ;S~ a~ ;.uugh ~he ~ctual Lime cF application will be dependsnt upon factors such as the degree of soiling of the dish.
The contacting of the absorbing device to the dish surface is preferably accompanied by a concurrent scrubbing.
EXPERIMENTAL
This exemplifies a process for making a N-methyl, 1-deoxyglu-cityl lauramide surfactant for use herein. Although a skilled chemist can vary apparatus configuration, one suitable apparatus for use here1n comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium. The other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution:
a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet. The latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap. A 500 watt heating mantle with a variable transformer temperature controller ("Variac") used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
,I-msthy ! 91 ucamine I195 g ., 1 . O mol 2, Aldrich, M4700-0) and methyl laurate ~rocte, ?~ camDl- cr I270, 220 9 g., 1.0 mole) are p1aced in a flask ~he solid/li~uid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
w o 92/06161 Pcr/us()~/o6~8 - 29 - 2~ r~,J rJ 1 When the melt temperature reaches 145- C, catalyst (anhydrous powdered sodium carbonate, 10.~ 9., 0.1 mole, J. T. ~a~er) is added.
The nitrogen sweep is shut off and thP aspir~tor and nitrogen bleed are adjusted to give 5 inches (~/31 atm.) Hg. vacuum. From this point on, the reaction temperature is held at 1~0 C bv adJusting the Variac and/or by raising or lo~ering ~ne mant7e.
'~ithin 7 minutes, first methannl hllb~l ee ar? .-~9hted 3t ~he meniscus of the reaction mixture. A vigorous reac-~icn soon rollows.
Methanol is distill~d over until l's r~'e ~'U!~'de'. ~',le v-c'i';m i;
adjusted to give about 10 inches '9. ~ ; !
vacuum is incr ased approximatel~ as ;oilo~s (in ilCneS ,tG. a~
minutes): 10 at 3, 20 at 7, 25 at lv. il "lin~s m~ i;; onse; o,-methanol evolution, heating and scirring are discontinued co-incident with some fo~mi,g Th? ?~ o~l~ 7n~
solidifies.
The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
EXAMPLES
~he following examples illustrate the practice of the present invention, but are not intended to be limiting thereof.
EXAMPbE I
The following compositions are ;ormulated on a weight percent basis. These compositions are prepared according to the description set forth below:
A surfactant paste is initially formed by combinins any destred surfactants with water and alcohol. The surfactants contained in this surfactant paste include the polyhydroxy fatty acid amide and suds enhancing agents of the present invention. Ideally the surfactant paste should be pumpable at room or elevated tempera-tures. Separately, in a large mixing vessel having a propeller mixer, three-quarters of the water of the formulated product, one-half of the alcohol of the formulated product, and any required hydrotropes (e.g., xylene, cumene, toluene sulfonates) are combined with mixing to give a clear solution. Any desired optional magne-sium is added next, followed by the surfactant paste, to form a mixture.
w o 92/06161 PCT/US91/06981 ~3~ 30 -If included, the magnesium may be added directly to the mixing vessel as magnesiu.~ chlo-nide. Al ternatiYely~ the magnesium may be added as a m~gn~~ d~ ~~ h~r~~ d~r. This magnesium oxide or hydroxide pcwd?r is -Id~ d to 'he acid form of the surfact-ant salts (?.9' ~ Y~ n? ~nl ,~onat2s, a~ l sulfates, alkyl ethoxylated sulfa~es, me~n~l ?sc~r sui ,'onat~s, ~tC.) in tne surfact-ant past~ dr3Xid~ ?o~der~
a less than stoicliQm~-~r~ -5~ui';'e~ ~mount is added with mixing to ensul cv,~ d~s.c ~r~s m~c~ntaining 0 SUr l-âC~ 'b ? ~ J ~ -3 ~ s~iuticns.
The ~ixt!!r? is ~ ~ci un~i~ 7 ~ ous ~!?~.r solution product is obtaiil2d. ~uu-i iOi1iii i2~ ,.oloi ~"d ~l'r d~s~ d ddltio~al hydrotrooes (added as a solution! ~av then be added to trim the SOl U ~ r ~ , ., ., ., ... _ A ? ~ / h - :J~~
and lOOO c?s, a~ m.~asul 2~ B~ ~ Bnco,~ ld ~isc~..n~r a~ 70~F. The pH of the solution product is then adjusted with either HCl or NaOH
to a level of 7.0 + 0.7 for formulas containing ammonium ions, and 8.5 + 1.5 for formulas which do not contain ammonium ions.
Perfume, dye and other ingredients, e.g., opacifying agents such as Lytron and ethylene glycol distearate, are added as the last step. Lytron can be added directly as a dispersion with mixing.
Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals.
ComPonent A B C D E
C12 14 alkyl N-methyl glucamide 5.0 5.0 10.0 lO.O l5.0 Sodium C11.2 linear alkyl benzene sulfonate 10.0 - - -Ammonium coconut alcohol ethoxylate (1.0 ave.) sulfaie - 2~.0 - - 15.0 Ammonium coconut alcohol sulfate 10.0 5.0 Sodium salt of oo~o-nut acid methyl ester sulfonate - - lS.O
MgCl2 0.5 1.j 0.8 0.6 0.5 WO 92/06161 PCr/1:5~1/069~1 - 31 - ~ 5t3 Sodium C14-l6 alpha olefin sulfonate - - - 20.0 Coconut polyglyco-- side (1.6 ave.
glucose unit per molecule) - 5.0 Dodecyl di~ethyl amine oxide 3.0 3.0 - ~m) ~.b Coconut amidopropyl dimethyl betaine 3.0 - 3.3 Coconut mono-ethanolamide 2.0 Coconut di-ethanolamide Sodium cumene sulfonate 2.0 3.0 3.0 3 0 3.0 Potassium toluene sulfonate - - 2.0 Ethanol 5.0 4.0 - 3.0 4.0 Water ~ misc. --- balance to 100% ---(dye, perfume, etc.) EXAMPLE II
The following compositions are formulated on a weight percent basis. These compositions are prepared in same manner as the compositions of Example I.
ComDonent A B C D
Cl2 14 alkyl N-methyl glucamide 20.0 12.0 4.0 10.0 Sodium C11.2 linear alkyl benzene sulfonate 5.0 Ammonium coconut alcohol ethoxylate (1.0 ave.) sulfate 5.0 - 12.0 Sodium salt of coco-nut acid methyl ester sulfonate - - 15.0 MgCl2 0.7 2.0 1.9 W O 92/06161 PCT/~S~1/06981 ~ 32 -Coconut polyglyco-side (1.6 ave.
glucose unit per molecule) - :~.o 5 o Dodecyl dimethyl amine oxide i.~ - - 3.ù
Coconut amidopropyl dimetnyl be~aine - ~ .û
Hexadecyl dimet~yl betaine ~ - .. ,.~, Coconut di-ethanolamide '.
Sodium cumene sulfonate - - ~. r, Sodium xylen~
sulfonate 3.Q - - 3.0 Potassium toluene sulfonate - 2.0 2.0 Ethanol 3.0 3.0 4.0 5.0 Water & misc. ~ --- balance to 100% ---(dye, perfume, opacifier, etc.) EXAMP~E lIT
The following compositions are formulated on a weight percent 25 basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT A B C D E
Ammonium C1l.2 linear alkyl benzene sulfonate -- 10.0 8.0 13.5 13.5 Cl2 14 fatty acid N-methyl glucamide l6.5 12.5 10.0 12.5 10.0 Ammonium C12 14 alkyl ethoxy (0.8 ave.) sulfate 12.5 11.0 10.0 -- 6.0 Cocoamide propyl betaine 1.5 4.0 3.0 2.0 2.0 Hexadecyl d;methyl beta,ne ~~.0 3.~ 3 0 3.0 2.5 Coconut monoethanolamide ~.~ 3.~ 3.g 2.0 --C12 14 alkyl dimethyl amine oxide -- -- 4.0 2.0 3.0 w o 92/06161 PCT/US91/06981 - 33 - ~ ~ ~ J J ~ I
Sodium cumene sulfonate 1.0 1.0 1.O 1.0 2.0 Ethanol 4 5 5 0 5 0 4 0 4 0 Urea 0 5 0 7 Magnesium hydroxide 1.6 -- --'~ater & Misc. (Perfume, dye, etc.) ----- to lOO~o ~~~~~
EXAMPLE IV
The following detergent compositions are formulated on a~el5h~
percent basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT A B C
Ammonium Cll.2 linear alkyl benzene sulfonate 5.0 -- 10.0 1~.3 --CI2-l4 fatty ~cid N-methyl slucamide 5.0 I5.0 10.0 1'.0 ~.0 Ammonium C12 14 ethoxylated (0.8 ave.) sulfate 5.0 14.0 10.0 -- 12.0 Clo primary alcohol ethoxyl~te (8.0 ave.) 5.0 4.0 -- 4.0 3.0 C12 14 dimethyl betaine -- 2.0 --C12 14 amidopropyl dimethyl betaine 3.0 -- 3.0 -- --Coconut acid monoethanol amide 2.0 2.0 -- -- 2.0 Coconut acid diethanol amide 2.0 -- 2.0 -- 2.0 Coconut dimethyl amine oxide 2.0 2.0 -- 5.0 3.0 Sodium cumene sulfonate 3.0 2.0 2.0 3.0 5.0 Sodium xylene sulfonate 1.0 3.0 3.0 -- --Ethanol 5.0 5.0 3.0 4.0 5.0 Magnesium hydroxide 0.7 0.6 -- -- --Ethy ene glycol distearate -- -- -- 1.O --C16 dimethyl betaine -- -- 3 0 --Urea 2.0 1.5 -- -- --Water ~ misc. (perfume, dye, etc.) -- balance to 100% --w o 92/06161 PCT/~S91/06981 ~ U ~ EXAMPLE V
The following detergent compositions ~ro formu7~tod on ~ ~aight percent basis. These compositions are prepared in the same manner as the compos;tions of Exampl2 I.
COMP~NENT j ~ î, n C14-l6 alpha 012fin sulfonate -- -- 10.' 10.0 C12 14 fatt~ acid ~-me'',~l glucamide î5.0 ~i.O l2.~ 5,0 Ammonium C12 1~ ethox~!la~2à
(0.~ ave.) sulf te C12-14 me~nyi es ;ef sulTonal~ sodium s~ .'J '0.0 5,0 __ C12-14 polyg7ycoside _ jJ ~j Clo primary alcohol ethoxylate ~8.0 ave.) -- -- ~.0 4.0 C12 14 âmi dopropyl dimethyl betaine -- 2 . O - - - -Coconut acid monoethanol amide 3.0 1.0 2.0 --Coconut acid diethanot amide 2.0 1.0 2.0 --Coconut dimethyl amine o%ide 3.0 1.0 3.0 4.0 Sodium cumene sulfonate 2.0 2.0 2.0 2.0 Sodium xylene sulfonate 2.0 2.0 2.0 2.0 Ethanol ~.0 3.0 A . O
Magnesium hydroxide -- -- ,~, ~
Ethylene glycol distearate -- -- ~- 1.0 Water & mfsc. (perfume, dye, etc.) -- balance to 100~h --EXAMPLE VI
The followlng detergent compositions are formulated on a weight percent ~asis. These compositionS arc pr ~pared ln ~he sa",e ,.,ar"ler as the compositions of Example I
COMPONENT A ~ r O
Sodium Cl4 l5 paraffin sulfonate25.0 -- t5 0 Magn~sium C14 i5 paraffin sulfonate -- 26.0 -- --w o 92/06161 pcr/us9l/o69#]
- 35 ~ 3 ~ i Sodium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethoxylated oxide 14.0 -- -- 15.C
Magnesium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethylene oxide ~ -~ 34 0 Sodium coconut glyceryl ether sul~onate 5 0 i~ C12 14 fatty acid N-methyl glucamide 15.0 1~.0 12.0 '~.~
Dimethyldodecylamine oxide ~.0 4.0 4.0 ; .
C12 14 acylamidopropyldimethyl betaine -- 5.0 -- 3.U
Triethanolamine 3.s 3.5 3.5 3 3 Ethanol 5.0 i 0 5 0 3 o Carbopol~ 616 1.5 -- -- --Car.bopol0 617 1.5 2.0 -- --Water & misc. (perfume, dye, etc.) --- balance to 100% ---EXAMPEE VII
The following detergent compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT E E G
Sodium C14 15 paraffin sulfonate 15.0 -- --Magnesium C14 16 paraffin sulfonate --Sodium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethoxylated oxide -- 15.0 10.C
Sodium coconut glyceryl ether sulfonate 5 0 -- --Magnesium coconut glyceryl ether sulfonate 5.0 C12 14 fatty acid N-methyl glucamide 10.0 3.0 10.0 Dimethyldodecylamine oxide 4.0 4.0 2.0 C12 14 acylamidopropyldimethyl betaine -- 5.0 --w o 92/06161 PCT/~S91/069 ~)S~ 36 -Triethanolamine 3.5 3.5 3 5 Ethanol ~.~ 3, Carbopol~ 616 !m~
Carbopol~ 617 -- 2.0 --Water & misc. (perfume, dye, otC.) ~ a'-;l~? ;~ f~
E'A~L,~
An alternate method for ?repa~in~ he ~?'y'~!~~e~y - ~y 'C-.'J
amides used herein is as follo~Ys. ~ re2cvio, ~ ,- e'J.lSi~i,-,j,~ a, 84.879. fatcy acid methyl ester ~source~
ester C~1270), 7~9. ,N-~ec~yl-~-gll~c l n~
Company M4700-0), 1.049. sodiu~ metno~-ine ~ r~ ii ~''.-'~.,1 _?~;~
Company 16,~99-2), and ~8.5ig. .~1e_i7~ CO;iv. ; .__~ ;~ n_i'_.~n vessel comprises a standard reflux se,-uo ~i,tea ~itn a ar~Jina tuce.
condenser and stir ~ar. !~ L~,~ p,~_~,J,~ _ ,.,'"1 _,,~ _"
is combined with methanol '.Yit;l stirring und~; ar~o" ~nd ;; ~
begun with good mixing (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperaiure, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point. The reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 105.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction ma'~es an overall perccntage yield value meaningless. The reaction can be carried out at 80% and 90%
reaction concentrations for periods up to 6 months to yield products with extremely small by-product formation.
The following is not intended to limit the invention herein, but is simply tc further illustrate additional aspects OT the technology which may be considered by the formulator in the manufac-ture of a wide variety of detergent compositions using the polyhy-droxy fatty acid amides.
It will be readily appreci2ted that the poljnydroxy ~alty acidamides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While w o 92/06161 PCT/~S41/069 37 i2~
some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about ll, preferably 10, nor below about 3 for unduly extended periods. Final product pH
(liquids) is typically 7.0-9Ø
During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutrali~--the base catalyst used to form the amide bond. ~hile any acid can be used For this purpose, the detergent formulator will recogni~e that it is a simple and convenient matter to use an acid which 13 provides an anion that is otherwise useful and desirable in ~h5 fi,is'~~ d~tergent composition. For example, citric acid can ~5 ui d ,-~n ?~/~ose; Or n5ULI ali,a'ion and th~ ,esul+ing ci+ra-e i~n (C2. i~'~ ~e allowed to rPmain with a C3. ~0~~ polyhydroxy fat y acib amiae slurry and be pump2d into the later manu.ac u,i,3 î~ stages or the overall detergent-manufacturing process. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
The polyhydroxy fatty acid am;des der;ved from coconut alkyl fatty ac;ds (predominantly Cl2-C1~) are more soluble than their tallow alkyl (predominantly Cl6-C~8) counterparts. Accordingly, the Cl2-C,4 materials are somewhat easier to formulate in liquid compositions, and aré more soluble in cool-water laundering baths.
However, the C16-C18 materials are also qu;te useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C1~-C18 materials may be better detersive surfactants than their Cl2-C1~ counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given 3Q formulation.
It will also be appreciated that the solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation andtor chain branching in the fatty acid moiety.
~hus, materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.
w o 92/06161 PCT/~S91/06g~1 2 ~
Likewise, the solub;lity of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., ~ill o,diharil~
be greater than the solubility of their monos3ceh?.r;~e-~er~ved counterpart materials. This higher solubili~ n ~e o,~
particular assistance when formulating liruid co,.n~-l " on~.
Moreover, the polyhydroxy fa~ty acid a,~i~e; .~ r-."
polyhydroxy group is derived from maltose a~oelr ~ '-nCt,iO~:
especially well as detergents when used in CCI110i~7~'i30 ',~
conventional alkylbenzene sulfona~e ("'AS") ,ui~ ~ - n- ~~
not intending to be limited ~y ~heo,~~
combination of LAS with the polyhydroxy raccv ~ a -~from the higher saccharides such as ma~ os and unexpected lowering Ot interfacial tension in aqueous meciia, thereby enhancing net detorgencv ?er ~rm~nre '~~ n"-~O'~? ?
a polyhydroxy fatty acid ~mide derlved from ~ OJe ~ -'J
hereinafter.) The polyhydroxy fatty acid amides can be manufactur~d nGt only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose" corn syrup, "high maltose" corn syrup, etc. can conveniently and economically be used.
De-lignified, hydrolyzed cellulose pulp can also pro1i~e a raw material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatt~ acid amides derived from the higher saccharides, such as maltose, lactose, etc., are more soluble than their glucose counterparts. Moreover, it appears that the ~,ore soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees. Accordingly, the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more). The resulting mi~ture o,~
polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a oro2~er range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fa~t~
acid amide. Thus, in addition to any economic advantages for usins W 0 92/0~161 ~ ~ ~ 2 ~ ~ ~CT/US9l/06981 sugar mixtures rather than pùre sugar reactants, the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation. In some instances, however, some loss of grease removal per~ormance (dishwashing) may be noted at fatty acid malta-mide ,-~iel, aD~2 ~bout 25% and some loss in sudsing above about 33,5 (said percentages being the percentage of maltamide-derived polyhy-dro~,~ a' L~ acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the IO c~ain l~ngth of the fatty acid moiety. Typically, then, the formu-laLor -, c~-.ny to use such mixtures may find it advantageous to se~-c' ;~3i~Jhydr~y îct~y acid amide mixtures which contain ratios or monos~ccn~ri'es (e.g., ~lucose) to di- and higher saccharides (e.g., maltosej ,rom about ~:l to about 99:1.
The manufacture of preferred, uncyclized polyhydroxy fatty acid amides rrom fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30-C-90'C, preferably about 50-C-80'C. It has now been determined that it may be con-venient for the formulator of, for example, liquid detergents to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation. Like-wise, the formulator of, for example, solid, typically granular, detergent compositions may find it convenient to run the process at 2~ 30-C-90~C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) C12-C1l alcohols, such as those available as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they not contain substantial amounts of unethoxylated alcohol and, most preferably, not contain substantial amounts of mono-ethoxylated alcohol. (~T" designation.) While methods for making polyhydroxy fatty acid amides per se form no part of the invention herein, the formulator can also note other syntheses of polyhydroxy fatty acid amides as described hereinafter.
3~ Typically~ the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty ac;d amides will comprise:
SteD 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the w o 92/06161 PCT/~S'91/06981 ~ ~ t,3 '~ r~
N-alkyl am;ne and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Ste~ 2 - r4ac~ing ~'oe aforesaid polyhydroxy amine ~ith, preferably, a fatt~ ~st~r to form an amide bond. ~hile a variety o-F N-alkyl polyhydrox~ amirie. ~e~~
in Step 2 of the reaction sequence can be pr~pared ~v i~.~~O~;
art-disclosed processes, the ,-ollowing ~rocess is n~ o~
makes use of economical sugar syrup as the raw material. I~ is ~o be understood that, for best r~sults :;hen u.i.,s s c;~
materials, the manufacturer should select syrups t~7' -~re -e~-~
light in color or, preferably, nearly colorless ~"~a ?r~
~reparation of ,'~-Al'~yl ?ol,~,ydi3~j ~";,;
From Plan -~ri~/ed ~ug~r 6~r~l~
I. Adduct ~ormat,on - The ,~ollc~, n5 i; a ~anual d ~'~~Oc _~ , ,.
which about 420 g of about 55% glucoso solution (~orn S'/r!'' _ ,~A~
231 g glucose - about 1.28 moles) having a Gardner Color o6 ~ cc than 1 is reacted with about 119 g OT about 60% aqueous metil~lamin~
(59.5 g of methylamine - 1.92 moles) solution. The methylamine (MMA) solution is purged and shielded with N2 and cooled to about lO-C, or less. The corn syrup is purged and shielded with N2 at a temperature of about 10--20-C. The corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown.
The Gardner Color is measured at the indicated approximate times in minutes.
2~Time in Minutes: L~ 30 60 120 180 240 Reaction TemP. ~C Gardner Color (APProximate~
As can be seen from the above data, the Gardner Color for the adduct is much worse as the temperature is raised aboYe about 30~C
and at aoout ~O-C, the time that the adduct has a Gardner Color below 7 ;s only about 30 minutes. For longer reaction, and/or 3~ holding times, the temperature should be less than about 2~'C. 1he Gardner Color should be less than about 7, and preferably le~s than about 4 for good color glucamine.
w o 92/0~161 Pc~/uss1/06981 - 41 ~ 0 92 ~ ~1 When one uses lower temperatures for forming the adduct, the time to reach substantial equilibrium concentration of the adduct is ahortened by the use of higher ratios of amine to sugar. With the 1.5:1 mole ratio of amine to sugar noted, equilibrium is reached in about tY~ hours at a reaction temperature of about ~O-C. At a 1.2:1 mole r~tio, under the same conditions, the time is at least about thr~e h~urs. ~or good color, the combination of amine:sugar ratio;
reaction temperature; and reaction time is selected to achieve subs~a., ~all~ equilibrium conversion, e.g., more than about 90XO~
io pr~,~a,~ mor~ ~cnan about 95~~O~ eYen more preferably more than about ago~ -s~d unon the sugar, and a color that is less than about 7, prererabiy 12ss ~nan about ~, more preferably less than about 1, for the a~ ct.
~ J 'ha ~b3''!- procass ~t a reaction temperature of less than abou; 'ù'C and corn syrups ~,th different Gardner Colors as indi-cated, the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.
Gardner Color (ADDroximate) Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2 As can be seen from the above, the starting sugar material mustbe very near colorless in order to consistently have adduct that is acceptable. When the sugar has a Gardner Color of about 1, the adduct is sometimes acceptable and sometimes not acceptable. When the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color of the adduct.
II. HYdroqen Reaction - Adduct from the above having a Gardner Color of 1 or less is hydrogenated according to the following procedure.
About 539 9 of adduct in water and about 23.1 g of United Catalyst 649B Ni catalyst are added to a one liter autoclave and purged two times with 200 psig H2 at about 20-C. The H2 pressure is raised to about 1400 psi and tne temperature is raised to about 50'C. The pressure is then raised to about 1600 psig and the temperature is held at about 50-55-C for about three hours. The product is about 95% hydrogenated at this point. The temperature is w o 92/06161 PCT/~'S~1/0698i 2 ~ 3'~r~j 6 ~ - 42 -then raised to about 85-C for about 30 m;nutes and the reaction mixture is decanted and the catalyst is filtered out. The product, after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.
The above procedure is r~peated with about 23.1 g Or Rane~
cat21vst with the following chang3s. The cataly,t is was"2~ ~r--times and the reactor, with the catalyst in the reactor, is purged twice with 200 psig H2 and the reactor is pressurized with H, ~t 1600 psig for two hours, the pressure is released at one hour an~
the '~-actor is r3pressurized to loOO psig. The adduc. is t~5n pumped lnto the re~ctor which is at 200 osig and 20 C. and t~
, a~L ~ ,; y~ 200 y5~,g u2, ~tc., ~s ~hc~J~.
The r2sulting product in each case is sreater th n abcu~ '-~-mc~yl glucamine; ,has 12ss ~han about lO py"l 'li bascd uycn t;, glucamine; and has a solution color of less than about Gardner 2.
The crude N-methyl glucamine is color stable to about l40~C for a short exposure time.
It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about l).
In another reaction, adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N2 at about 10-20-C. About 330 9 of about 70% corn syrup (near water-white) is degassed with N2 at about 50-C and is added slowly to the methylamine solution at a temperature of less than about 20-C. The solution is mixed for abou-: 30 minutes to give about 95~~O
adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20-C. The H2 pressure is raised to about 200 psi and the temperature is raised to about 50-C. The pressure is raised to 250 psi and the temperatu-e is held at about 50-55-C for about three hours. The product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85-C for about 30 minutes and the product, after removal of water and evaporation, is a~out 95% N-methyl glucamine, a white powder.
W O 92tO6161 PCT/~'S91/0698 43 h ~ ~ 2 ~ 6 ~
It is also important to minimize contact between adduct and catalysi when the H2 pressure is less than about IOOO psig to minii"i ',i . on~2nt in the 3lucamine. The nickel content in the N-methyl glucamine in this react;on is about 100 ppm as compared to the l~s. ''~an 10 ?pm in the ~revious reaction The following reactions witn H2 are run for direct comparison o ~ v~ p ~ ~ u, ~ " ~ c ~ 2CO ml autoclave reactor is used following typical procedures simi ~; ;o ~lose ,e~ , O'~~tn ,'bo'/q to make adduct and to run the hyd ~ c'lon at va,iou; ~emperaturqs.
~ f~'~~ "se in m2btng glucamine is prepared by combining abous ;~) 9 of arout j5YO glucose (corn syrup) solution (231 g g~ucose- 1 28 molos~ (the solution is made using 9gDE corn syrup ;rv~ ;-_ svlutio~ ,ia',''.?. 3 col3r las; than Gardner 1) and abou~ 9 o,~ 80~o metnylamine (53.5 9 ~MA; 1.92 moles) (from Air Products).
The reaction procedure is as follows:
1. Add about 119 9 of the 50% methylamine solution to a N2 purged reactor, shield with N2 and cool down to less than about lO-C.
2. Degas and/or purge the 55% corn syrup solution at 10-20-C with N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine solution and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about 1-2 hours.
The adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
The ~lucamine adduct hydrogen reactions are as follows:
1. Add about 134 9 adduct (color less than about 6ardner 1) and about 5.8 9 G49B Ni to a 200 ml autoclave.
2. Purge the reaetion mix with about 200 psi H2 twice at about 20-30-C.
3. Pressure with H2 to about 400 psi and raise the temperature to abGut 50'C.
4 Raise pressure to about 500 psi, react for about 3 hours. Keep temperature at about 50-55'C. ~ake Sample 1.
Raise temperature to about 85'C for about 30 minutes.
w o 92/06161 PCT/~'Sgl/069X
2~ 2 ~ U 1 44 6. Decant and filter out the Ni catalyst. Take Sample 2 Conditions for constant temperature reactions:
1. Add about 134 g adduct and about 5.8 g G49B Ni to a 20~ ml autoclave.
2. Purge ~.~ith about 200 psi H2 twice at low temperature.
3. ~ressure .iith h2 to about 400 psi and raise temperature to about 50~C.
4. ~ ressure to about S00 psi, react for about 3.5 hours.
~ee~ 'em~erature at indicated temperature.
i~ 5. v-os;,' a"d --ilter out the Ni catalyst. Sample 3 is for abou iv-j~'C; ~ample ~ is -ror abou~ 7~~C; and Sample 5 is ,'or a'cout :~ U~ . ~ ~;7~ reaction time ror about 85'C is about 45 minutes.) All runs give similar purity of N-methyl slucamine (abou; 9~O);
the ~rdn~r Colors of the runs are similar right after reaction, but S onlJ~ he t/o-stage he~t treatment gives good color stability; and the 85~C run gives marginal color immediately after reaction.
EXAMPLE IX
- The preparation of the tallow (hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this invention is as follows.
Step 1 - Reactants: Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The react2nts are added to glass liner (250 g maltose, 428 9 2~methylamine solution, 100 9 catalyst s~urry - 50 9 Raney Ni) and placed in 3 L rocking autoclave, which is purged with nitrogen (3X500 psig) and hydrogen (2X500 psig) and rocked under ~2 at room temp2rature over a weekend at temperatures ranging from 28-C to 50-C. The crude reaction mixture is vacuum filtered 2X through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are azetroped off by dissolving the material in methanol and then removins the methanol/~ater on a rotary evaporator. Final drying is done under high vacuum. The crude product is dissolved in refluxing methanol, filtered, cooled to recrystallize, filtered and the filter cake is dried under vacuum at 35'C. This is cut ~1. The filtrate is conc~r,trated until a precipitate begins to form and is stored in a refrigerator overnight The solid is filtered and dried under W O 92~0~161 ~ O ~J 2 a ~,CT/US91/069X1 vacuum. This is cut #2. ~he filtrate is again concentrated to half its volume and a recrystallization is performed. Very little precipitate forms. A small quantity of ethanol is added and the solution is le,~t in the freezer over a weekend. The solid material is filter d ~nd dried under Jacuum. The combined solids comprise ~-m2th\/1 ~îm~ ~;~iee J~;~; is iSed i~ S~e~ 2 ~ he overall synthesis.
SteD 2 - ~eactants~ -,ne~hyl maltamlne (from Step l); hardened tallo~ ~e~hvl esters: soaium metnoxiae (2i~o in methanol); absolute methanol (solvent); mole ratio l:l amine:ester; initial catalyst le~lel 10 ~le ~ ~w~r ~al ~minej, raised to 2~ mole Y; solYent level 50% ~t.~.
In ~ d ba. le~ , a ~ h~ 'allo~.~ mcthyl ester is heated ~ el-~-."~ ?~i~t ':;atQr bat~) and lo~dod into a 250 ml 3-n~c'~ ;~S~ 3'~cm Cla;'; .J-'h ,.,e hanic~l 't~-ri"9. The flas~ is heatea co ca. i~'0 LO ?reve~ h2 es~er ,~ ~; ~olidi;~ing. Separ-ately, 2~.0 9 of ,'I-methyl maltamine is combined with ~5.36 g of methanol, and the rPsulting slurry is added to the tallow ester with good mixing. 1.51 9 of 25% sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an additional 10 mole % of catalyst (to a total of 20 mole %) is added and the reaction is allowed to continue overnight (ca. 68-C) after which time the mixture is clear. The reaction flask is then modi-fied for distillation. The temperature is increased to llO-C.
Distillation at atmospheric pressure is continued for 60 minutes.
2~ High vacuum distillation is then begun and continued for 14 minutes, at which time the product is very thick. The product is allowed to remain in the reaction flask at 110~C (external temperature) for 60 minutes. The product is scraped from the flask and triturated in ethyl ether over a weekend. Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder. Any remaining N-methyl maltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol. A
concentrated sample of the product (20 9 in 100 ml of lOC% methanol) 3~ is loaded onto the silica gel and eluted several times using vacuum and several methanol washes. The collected eluant is evaporated to dryness (rotary evaporator). An~ remainins ;allow ester is removed by trituration in ethyl acetate overnight, followed by filtration.
~ ~ 9 w .~ 46 - PCT/USs1/06981 The filter cake is vacuum dried overnight. The product is the tallowalkyl N-methyl maltamide.
In an altarnate mode, Step 1 of the foregoing reaction sequence can bD conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose. The resultlng oolyhydroxy fatty acid amides and mixtures can be used in any or~ ~he det2rg2ilt compoi1tions ~erein.
In still another mode, Step 2 of the foregoing reaction sequence can oe carried out in 1,2-propylene glycol or NEODOL. At ths d,~ 'ion of the .~ormulator, the prop~lene glycol or NEODOL
need nj ,~ Gied ,m~,," 'he r~action product ?rior to its use to formuiaL~ ce~2rsen-c colnposi-ions. Again, accoroing LO the desirei 'r~ Y' ' .~_n;.~ _3.~, b~le ml2~hGAide catalyst car be neutralized by citric acid to provide sodium ci,rate, which can remain in the - ?olyhydnox~ ttV acid amide.
he -~~rmu'a+or of fabric laundering compositions which can advantageous7y contain soil release agent has a wide variety of known materials to choose from (see, for example, U.S. Patents 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896). Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of C1-C~ alkoxy-terminated polyethoxy units (e.g., CH3[0CH2CH2]160H), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(oxyethylene)oxy units (e.s., polyethylene glycol 1500); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) especially wherein the mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about 0.5:1. Such r,Gnionic soil release agents are of the general formula R10-(CH2CH20)x C ~ CO-CH-CH20 - C ~ CO(CH2CH20)y O O
C ~ C - O (CH2CH20)x-RI
wherein R1 is lower (e.g., C1-C~) alkyl, especially methyl; x and y are e2rh integers from about 6 to about 100; m is an integer of from about 9 75 to aboùt 30; n is an integer from abo~t 0.25 to about 20;
~ o 92/06161 PCT/~'S91/06981 and R2 is a mixture of both H and CH3 ~ pr ~ ~ ~a mole ratio ofoxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substantially free of mor,omer. ol~ he ~.C?0',~ ~e ;hereln ~ is ?r~ylene or higher 21kyl.
Thus, the soil release a5ents of U.S. Patent 4,877,896 can comprise, for e~ample~ the reaction product OT dimethyl terephthalate, ethyl-ene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid, Yhereas ~,ese additional soil release agents can comprise, for evample~ tile reactio1l p~oduct o~~ dimeth~l terephthalate, ethylene ~7'~ O~;t'S'!~ i;O?;l~'.ala~ an~ 3-,odiûsul.oben~oic acid. Such ageni;s ~re or~-fer,ed ~ar use in granular laundry detergents.
,he ,ormula'or ",aj 1;3 ~2t2rmino that it is ~dvant3geous to inciude a non-~erbora-~2 bleac", esp2cialiy in heavy-du~y granuîar laundry detergents. A variet~ of peroxygen bleaches are available, commercially, and can be used herein, but, of these, percarbonate is convenient and economical. Thus, the compositions herein can contain a solid percarbonate bleach, normally in the form of the sodium salt? incorporated at a level of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8%
to 15% by weight of the composition.
Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03. 3H202, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequest~rant such as EDTA, l-hydroxy-ethylidene l,l-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorpo~ated during the manufacturing process. For use herein, the percarbonate can be incorporated into detergent composi-tions without additional protection, but preferred embodiments ofthe invention utilize a stable form of the material (FMC). Although a variety of coatings can be used, the most economical is sodium silicate of SiO2:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution and dried to give a level of from 2%
to 10% (normally from 3% to 5%), of silicate solids by weight of the percarbonate. Magnesium silicate can also be used and a chelant such as one of those mentloned above can also be included in the coating.
Ihe particle size range vf the crys~allln~ p~rcar~on~te i5 frc~
3i3 m1crometers to 450 m~cro~eters with a mean o~ a~proxt~.ately 400 mtcrom~ters. ~hen coatad, the crystala ha~ a slzo 1n the r~n~e from 4G0 to 600 m~cro~e'ers.
~hlle hea~y m~tai; present i,~ '.u~ ~n~r~ uc~ ~o ~anufacture the ~ercarbonate can bP co~trolled by the inclusion ~r sequestrants tn the r~ac'tcr, ~.tV~UrA7 'h~ ~p~rclrbon~t~ still re~utrPs prote~tl~n fr~,n h~,aYy 7,n?tl1s present as lmpurltl2s in other lngredlents o~ tl~,2 ~r~UC~ C ;~.aS ~ n ,'~ nd ~n3t tha .~ta1 1eY~1 of tron, ~opper and mana,inesa 'DnS 1~ e p~cduc~ sh ~ld not excee~
25 ppm and prererabl~ snould :~ i_ii ~,i., ~~ .~'.. i.' ~r~e~ to ~vold an ~naccept~bty advsr~e e~ ct ~ p~ncari~or,~ s~ y.
. 3 EXA~P~ES X A-~
13 Tha follow~ng Exa~ples l~lus~rat~ ,h~ ~s~ ui~ d~t~n~ nt c~mposltlons whtch arP ssp~cially l~Zpt~ r'~ iiS;',n, ',.d ~~.e~
hard sur~ce cl~an~ng operat~ons. in the ~x~pl s ~-2, te~ s~r,~c'-ants co~prtsa various alkyl ethcxy s~lfate s~rr3ct~nta ~n~;;-, ~si~g standard term;nology, ara abbr~Yi~ted to tndlc3te th~1r aver~go tegree of ~thoxylat~on; thus C~2 l3E0~0.8~ sulf~t~ lndlcat~s sulfated ~ix~t Cl~-C~ alc~hol fractlon hav1ng an average degreP of-ethoxylat10n of 0,8. ~hese anion~c ethoxy su~fatcs are prefQrably use~ 1n thelr Na+ or N~+ salt form. ~he C~2 1~ amlne oxide 1s a mixed C~ Ycra~el d~methyl ~lne ox1de. The C~2 ~, AP betalne 2C 1s c~2~l~H2s/~ N~(c~2)~Nl(~H~2c~2~o2H. ~he ~12-~ A~ sutt~lne is C,2/,~H2s/2,CONH~C~2)3N~(CH3)2U~CH~OH)C~2503~. The Cl2.~ DM
beta1ne ~s C~2/~2~/2~N~(cH3)tcH2co~. Th~ ethoxyl~ted non~on;c surf~ctant d~slgnated ~ ~E0(8) refers to ~9-C" a~c~hols ethoxyl-a~et w1th an aYerage of 8 m31es sf ethyl~ne cxide. ~h~ C3+~ and Mg~l catlons ~re convenie~tly 1ntroduced tnt~ the compos~tions as CaCl 2 and ~gCl~. The ~a1~nce ~r the composlt,ons eomprls~ water and cltrate~prspylene glyc~l pr~ssnt ln the gl~c~d~ surfactan~
~1-5X) ~nt 1~3X cumene sulfonate or xylene sul~onata hydrotrop~.
The p~ 1s typ~cally 6.3-7.4 (NH~+ salts) or 7-8.2 ~Na~ s~lts).
Jn~r~d1ent percent (wt~) A ~ C
C~2 ~ H mcthyl gluc~1de 11 8 12.~ 3 C~ E0(0.~) sulf~te ~- 16 lO.C 9 - C,2 s~E~(3) sulfate 11 -- 2.7 14 ~; C~2 l~~0~6.~) sulf~t~ 3 AP beta~nQ ~ 2 --C12 l, AP sulta~ne -- -- . 1.C
C~ m1ne ox1d~ 2.5 -- -- 1.0 ~ 3~ -~j~r1J ~ J~ ~
- ~o -Cl2.l~ D~l betalne -~ 2.0 C~ 1E0(~) 0.5 8 7 -~
Ca~+ -- -- 0.5 I.û
Mgl+ 0.9 0.2; -- --Bal ance aat 6al 23 E XA~Pl E X I
In any of the foregoing examples, the ,atty ac;d Sluc~,ice sur~actant can ~e replaced by an equiY31~nt amount of the mal.a"lde surf~ctant. or mlxtur~s of gl~ica.~1de/maltamide surfar~an~ ~er~e~
1~ from plant sugar sources. In the cornposl~.or.~ the us3 of atri~oia-mldes appears to h~lp cold temperature sta~ ty o, ~"q ;?;SiA~s fo~mulattons. t~loreove~, the usa of sul~obs.a~",e ~3~ 5'1 surfactants pro~/tdes supsrior suds~ng.
EXAI~PLES XI I A-D
Inq~edi ents Percent (wt . ) A ,~ C O
C~2 " alkyl ~tho~w sulfate ~l E0) l~ 9 12 --~12~ alcyl ethoxy sulfate (3 ~0) ~ ~4 -- 11 C~ O al kyl etho~yl tte ~8E0) 7 3 7 20 C~2.l" N-methyl ~luca~1de 8 9 lZ 6 Coconut dl ~thanol ~mite ~ 5 Dimethyl dod~cyl amln~ ox1da -~ 1 2 Cocoamldopropyl hydroxysultatnc -~
- Cocoamidopr~pyl beta1ne 2~ Mg~+ ~~ ~~ I l Ca2+ 0 . 5 Sodtum toluene sulfonate 3 3 3 3 Ethanol 4 ~ ~ 4 Water --- - Balance -- ---3Q As note~ ~bova, for co~posit~ons ~hQrein espec1al1y hish suds1ng is deslrod (e.~., d;shwash1ng3, lt ts pref~rred that no suds SupprQSsing agcnt be usad. Slnc~ C1~, and hlgher, fatty acids can act as suds suppr~sscrs, 1t 1s pr~ferred that dtsh~ash1n~ composi-t1cns contain 1 ess than ~bout 5%, prefar~bly 1 oss than about 2,..
3~ ~ost prafer2bly su~stanttall~ no C~ or kishar fatty acids. Accord-1ngly, the for~ul~tor of htgh sudslng CD~posittons W;ll d~strably aYo1d ~ha introtuctton of suds-suppressing amounts of such fatty ~c1ds into such co~posltions ~tth th~ polyhydrexy fatty ac~d a~ide .
_ . --, ", . ,, ,; ... ..
WO 92/06161 PCr/l,'S91/06981 2 ~ 9 2 ~ ~ ~
and/or will avoid the formation of Cl~ and h;gher fatty acids on storage of the finished compositions. One simple method is to use Cl 2 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can ovecome some of the negative sudsing effects caused by the fatty acids.
The formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10/o and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the bright-ener witn water and the polyhydroxy fatty acid amide, ar,d 'hen tû
add the pre-mix to the final composition.
Polyglutamic acid or polyaspartic acid dispersants can oe usefully employed with zeolite-built detergents.
1~ It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.
o S R6 - C - N(R7)2 wherein R6 is an alkyl group containing from 7 to 21, pre-r~rably from 9 to 17 carbon atoms and each R7 is selected frsm t~e ~~eup consisting of hydrogen, Cl-C4 alkyl, C~-C~ hydroxya7'~yi, ~n -(C2H40)XH, where x i5 in the range of from 1 .o 3.
I0 Preferred amides are Cg-C~c ammonia ~mides, mon~e ,~no ~m:
diethanolamides, and isopropanolamides.
~referred suds enhancing agents are C10 13 al',<y7 dim-tl~, 1;.,.
oxides, C10 18 acyl amide alkyl dimethyl amine oxides, betaines, sultaines, condensation products of aliph2tlc ~lc3hsl, mth ~t- ~----oxides, and alkylpolysaccharides, and mixtur~s thereo;.
Liquid Carrier In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions comprise from about 95% to about 35% by weight, preferably from about 90% to about 50% by weight, most preferably from about 85% to about 60% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g, ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred alcohol.
ComPosition DH
- The liquid detergent compositions hereof will preferably be formulated such that during use in a~ueous cleaning operations the wash water will have a pH of between about 6 and about 9, more preferably between about 7 and about 8. Liquid product formulations preferably have a pH in the range of from about 5.0 to about 10.5, more preferably from about 6.0 to about 9.0, most preferably rrom about 6.5 to about 7.5. Techniques for controlling pH at recGm-mended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art.
Thickeninq Aqent The detergent compositions of the present invention may also be in the form of a gel. Such compositions are typically formulated in W O 92/06161 P~r/US91/06981 ~ ~3''~
the same manner as liquid detergent compositions, except they contain an additional thickening agent.
An~ material or materials which can be admixed with the aqueous liquid to provide shear-thinning compositions having sufficient s-n ',e used in the compositions of this invention.
,~ate,ials such as colloidal silica, particulate polymers, such as pOlvs~yr~np and oxidized polystyrene, combinations of cer~ain surfactants, and water-soluble polymers such as polyacrylate are '~noYn a~ , oYidQ ~ield values.
lO~ ?rQ~errPd thic~ening agent useful in tne compositions of the -r~ --~ ;n~ n iS a nigh molecular weight polycarboxylate polymer hlc ~nQ~ 3~ 1g~ moleculan weight" it is meant from about 50~ u~ ~,OvO,~,CO, prer2rably from 2~0ut 750,000 to about 4,000,iO~.
liThQ polycarboxylate polymer may be a carboxyvinyl polymer.
Such compounds are disclosed in U.S. Patent 2,798,053, which is incorporated herein by reference. Methods for making carboxyvinyl polymers are also disclosed in Brown, and are also incorporated herein by ~eference.
20A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0. lZo to about l~/o by weight of the total mono22rs of a polyether of a polyhydric alcohol, wh;ch polyhydric alcohol contains at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule. Other monoolefinic monomeric materials may be present in the monomeric mixture if desired, even in predomi-nant proportion. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more 3~ preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, WO 92/06161 PCl/l~S91/069~1 2 a ~ 20 -it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2~~o to about 2.5'Jo.
Preferred monomeric olefinically unsaturated carboxylic acid, for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolPfinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure R
CH2 = C - COOH
herein R is a substituent selected from ~he group consisting Oir hydrogen and lower alkyl groups; most preferred is acrylic acid.
C~r oxyvinyl pol~mers us2;ul in rormulations or the ?~e ~;~
invention haYe a molecular weight of at least about 750~000. Pr--ferred are highly cross-linked carboxyvinyl polymers having a molecular weight of at least about 1~250~000. Also preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000, which may be less highly cross-linked.
Various carboxyvinyl polymers are commercially available from B. F. Goodrich Company, New York, N.Y., under the trade name Carbopol. Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 750~000; preferred is Carbopol 941 having a molecular weight of about 1,250,000, and more preferred are Carbopols 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respec-tively.
Carbopol 934 is a very slightly cross-linked carboxyvinyl polymer having a molecular weight of about 3,000,000. It has been described as a high molecular weight polyacrylic acid cross-linked with about 1% of polyallyl sucrose having an average of about 5.8 allyl groups for each molecule of sucrose.
Additional polycarboxylate polymers useful in the present invention are Sokolan PHC-25R, a polyacrylic acid available from 3~ BASF Corp., and GantrezR a poly(methyl vinyl ether/maleic acid) interpoiymer available from GAF Corp.
w o 92/06161 PcT/~s91/06s81 - 21 ~ 2 a 61 Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalk~n,l ~ Pther and having a molecular weight of from about 750,000 to lbout 4,000,000.
";~hl~/ profDrrod examples of these polycarboxylate polymer thickenors a-o ~he Carbopol 600 series resins available from B. F.
~oû~ .p~c.~lly pr ferrod ~re Carbopol 616 and 617. It is belieJed ~h t these resins are more highly cross-linked than the 900 seri , ;~ i-, ;nd h~Ya mol?cular ~.~eights bet~een about 1,000,000 and 0 ~,r.GO,:';'n.. !i~-,res ~, ?ol~ca,~xylate polymers as herein described ma~ s~i ln the ~resont in~ention. Particularly preferred is ~ CarooDol ~1O and ol7 seriDs resins.
TaO ~ r~rboxylate polymer thickener is utilized preferably ~ 1 y "o :l.iy -'h,ck~nl"s .~ents. In f~ct, it has been foun~ -;nac i-,' the po7ycarboxylat2 polymers of the present invention are utili~ed ~ith clay in the composition of the present invention, a less desirable product, in terms of phase instability, results.
In other words, the polycarboxylate polymer ;s preferably used instead of clay as a thickening/stabilizing agent in the present compositions.
The polycarboxylate polymer also provides a reduction in what is commonly called "bottle hang-up~. This term refers to the inability to dispense all of the dishwashing detergent product from its container. Without intending to be bound by theory, it is believed that the thickened compositions of the present invention provide this benefit because the force of cohesion of the composi-tion is greater than the force of adhesion to the container wall.
~ith clay thickener systems, which most commercially available products contain, bottle hang-up can be a significant problem under certain conditions.
Without intending to be bound by theory, it is also believed that the long chain molecules of the polycarboxylate polymer thick-ener help suspend solids in the thickened detergent composi-~ ons of the present invention and help keep the matrix expanded. The polymeric material is also les; sensitiYe than clay thickeners to destruction due to repeated shearing, such as occurs when the composition is vigorously mixed.
w o 92/0616] 2 IJ '~ 22 - PCT/~'S91/06981 If the polycarboxylate poly~er is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2~~o to about 2% by weight.
Tine ~nickening agents are used to provide a yield value or from about -a ~ ouc 350 ~nd most preferably from about 75 to a~ut 250.
Y1e,~ n~l~/sis The ~ield value is an indication of the shear stress at ~hich t~.~ J~ ?n9th is exceeded and flow is initiated. It is me~sur-d ilen ;~ 3roGkeielu ~'J~ i,.o '~l /lscom2t2r .~ , a ~ ?'n~l~e 3_ _~-_ '.' i 'l~in9 3 ,iellp~ h Griy2 upward during as,ocia~ed ,~ ~d--ing,. ,,a Sj'5;2m~ iS set to 0.~ rpm and a re2ding is ta~o., .~or ~;~o eomoosition to be testPd after 30 seconds or atter the sysiem is stabl~. The system is stopped and the rpm is reset to 1.0 rpm. A
reading is taken for the same composiLion after 30 seconds or after the system is stable. Stress at zero shear is equal to two times the 0.5 rpm reading minus the reading at 1.0 rpm. The yield value is calculated as the stress at zero shear times 18.8 (conversion factor).
ODtional Com w nents The compositions of the present invention may optionally contain other anionic and nonionic compounds (other than those already disclosed herein).
Other anionic surfactants useful for detersive purposes can also be included in the composition; hereof. Examples of useful anio~ic surfactants include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent Specification No. 1,082,179, Cg-C22 alkylsulfates, Cg- C2 4 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxid~o); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty 2c~l gl~corol sulfates, alkyl phenol ethylene oxide ether c~lfatos, alk~l ~hosphates, isethionates such as the acyl isethion-ates, acyl iaurate~s, fatty acid amides, alkyl succinates and sulfo-succinates, acyl sarcosinates, sulfates of alkylpolysaccharides such WO 92/06161 PCI/US~1/06981 - ~925~1 as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds having already ~e2n described herein), alkyl ether car-bonates, Fatty acids esterified ~ith isethionic acid and neutralized ~ith sodium hydroxide, and -;a~ty acids amides of methyl tauride.
Furtner ~xa~ples ar~ describ~d in ''SUrTaC3 Active Agents and Deter-gent,' i'~oi. . and ~ o~ ar;z~ Pe,r~ ~nd 3erch). A ~/arie~y of such surfactants are also generally disclosed in U.S. Patent 3,329,~,~, ,iaued D~camb~r 30, 9?5 ~o laughlin, et al. at Column 23, 1 no ~ 'hrnu~h Column 29~ line 23 (herein incorporated by r~
~ 3ù~ tQd ~nto th~
de ~ , 5 3 i ~ C ~ d ll ~ j c a ~ be ~'oa u ~, y deSCriDed dS alipha~ic ~eri~;a~ i';QS O; socond~ry or 'ertiary am-ln2s, or ~li??i io ~el i~a~iYPs or o3t~roc~clic secondary and certiary aminos -- Yhich tho aliphatic r~dical can be straight- or branched-chain. One Ot the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one con-tains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, lines 18-35 (herein incorporated by reference) for examples of useful ampholytic surfactants.
Zwitterionic surfactants may also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivativ2s of secondary and tertiary amines, deriva-tives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfoniumcompounds. See U.S. Patent No. 3,329,678 to Laughlin et al., issued December 30, 1975, at column 1g, line 38 through column 22, line 48 (herein incorporated by reference) for examples of useful zwitteri-onic surfactants.
Such ampholytic and zwitterionic surfactants are generally usedin combination with one or more anionic and/or nonionic surfactants.
If included in the compositions of the present invention, these optional additional surfactants are typically present at a concen-tration cf from about 1% to about 10%, preferably from about 2% toabcut 5% by :~eight.
Otner optional ingredients include detergency builders, either of the organic or inorganic type, although such builders in general w o 92/06161 PcT/uss1/0698 ~ 24 -are not preferred for use in the composition of the present inven-tion. Examples of water-soluble inorganic builders which can be used, either alone or in admixture with themselves or with organic al'~alin2 se~u~s-t ant buildor salts, are glycine, alkyl and al~-nyl suc~ln~ ali metal carbonates, phosphates, polyphosphates, and a- ,- c a~m~ s of such salts are sodium tripol~p;,os-phato, sodium carbonate, potassium carbonate, sodium pyrophosphate, ~~~ ? ~~ph3;?h~te, potassium tripolyphosphate, and sodium hexameta3hosphate. r'xamples of organic builder salts which can be iOi'!S-~ ,1 ac",i~-ur~ ~i'h ~ach other, or with the preceding ~~ a ;~ -l'~l n~ er -al's~ aro al~ali metal polycarboxylates, C;ii~ '_' 'U'''~ as iOJ'i;.a~;~ aid pctas,ium citrale, sodium an~ pot~s.iLum ~arir; ~, ~ù~ ,n ~I~d ~a~jiu", ~yi~ d~ c~c~~aac2~a~c~ a~u 1~and DOtaSSi l~m ,'~-(2-hydroxy- ethyl)-ethylene diamine triacetat?s, sodium and potassium nitr,lo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxydi-succinates, and sodium and potassium tartrate mono- and di-succinates, such as those described in U.S. Patent 4,663,071 (Bush 20et al., issued May 5, 1987), the disclosure of which is incorporated herein. Other organic detergency builders, such as water-soluble phosphonates, can be used in the compositions of the present inven-tion. HoweYer, detergency builders in general have limited value when tne compositions of the present invention are in the form of light-duty liquid dishwashing detergent compositions. If included in the compositions of the present invention, these optional buil~ors aro typically present at a concentration of from about 1.0%
to about 10~h, preferably from a~out 2~~/o to about 5% by weight.
Other desi-rable ingredients include diluents, solvents, dyes, perfumes and hydrotropes (preferred). Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, etc. Diluents us~ful n tho ccmpositicns of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 5% by ~eight.
Solvents useful herein include water and lower molecular weight al colhû~ S, rUrh 2S eth~l alcohûl, isopropyl alcohol, etc Solvents useful in the compositions of the present invention are typically w o 92/06161 P~TJ~S~ 69i~1 2~5~ 2 ;j ~1 present at levels of from about 1% to about 60Yo~ preferably from about 5% co about r~o,' by :i21ght.
Hydrotro~es such as odium and potassium toluene sulfonate, sodium and poLassiu~ ~lene sulronat , sodium and potassium cumene sulfonat2, riscdium al,d ripo~assium sulfosuccinate, and related comlpoun~s ; ' . i:iC . ~ ,''i J._7. ''l~ -nL. J~ -;J-~ n2 diSClO.Uf Q C.
which is incorqoratsd 'nerein) can be utilized in the interests of ac,hievil,~, i ci-s,.e~ d~c ;~ t,~ -n~ ~!lscosity. T' has be'2n ~'". d 'h~t 'h? ~ .rot, ~p5~ can ha~/e ~ positi~/e effect on the 0 ~ r ~ .sndinq ~o be s~,.~ ,.. .. , ... ~ . .. ... ......... .... .. ... .
boun~ 5 ~ LI2 in che composiiion~ o,' ~"e p,-,an~ i"v~";1c" ~,e typica.,y ?~osent at 1S~Q~ o~ a~ ' lJ~ to a~out 1~ ?rQ;~raDmJ ~rom aDout 2~~o to abou' ~" by ~eigh'.
Optional ingredients useful when the compos;tions of the present invention aro used in liquid dishwashing detergent applica-tions include drainage promoting ethoxylated nonionic surfactants of the type disclosed in U.S. Patent 4,316,824, issued to Pancheri on February 23, 1982, the disclosure of which is incorporated herein.
While not intending to be bound by theory, it is believed that the claimed compositions of the present invention are beneficial in that they provide unexpected sudsing and cleaning performance and clean dishEs without im?arting a "greasy" feel to the cleaned dish, which is important in consumer markets where the cleanliness of a dish is judged by the lack of such a "greasy" feel. Furthermore, while not intending to be bound by theory, it is believed that further oenefits of the composition of the present invention are ease of rinsing and that they reduce the "slippery" feel associated with typical liquid detergent ~ompositions. The reduced slippery feel is important in consumer markets where such a "slippery" feel is not favor~d and is vie~ed as incomplete rinsing of surfactants from a dish surface.
Additionally, while not ,ntending to be bound by theory, it is 3~ believed that the Ccm?ositions of the present invention offer the benefit of unex~ected unifor,i t~ in sudsing ~erformance across varying temperature and humiait~ conditions, especially at a WO 92/06161 P~/~,iS91/069~1 ~~ ~3 (L3 ~ r ~ 26 -preferred dishwashing temperature in the range of from about 100~F
to about 120~F.
T~ a mathc~ aspoct of this in~/ention, soiled dishes are contact~d ~iLh ~n effective amount, typically from about 0.5 ml. to abou~ l (?Qr ?j dishes being treated), preferably from about 3 ml. ~o ~DOU~ iU ml., O; the composition of the present invention.
Th4 actu a~ ~-~unt ~$ l1,uid detsrg2nt composition used ~ill be based on ~ho v~dgemeni oF user, and ~ill typically depend upon factors ~c;l .a ';-- ~a, ~ .a, rroduc' Formulation of the composition, 1~ lnc,~ a~ o noen-;rl~ion ~T acti~e ingredisnt in ths composit-on, tho -~m o~ ~- ~oi~?d ~ishss to be cleaned, ths degree of soiling on ~ne ~i;n~ ,a ~n~ h~ particular product formulation, in turn. ~ epend upon a number of factors, such as the intended fl~ r-~ r~~4~ c. ) rOr .~5 co~?ositi~n prcduct. T;ia lol~o~iny are axa~,ples of typical methods in which the detergent compositions of the present invention may be used to clean soiled dishes. These examples are for illustrative purposes and are not intended to be limiting.
In a typical U.S. application, from about 3 ml. to about 15 ml., preferably from about 5 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml., of water in a sink havins a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml. The detergent composition has a surfactant mixture concentration of from about 21% to about 44% by weight, preferably from about 2~% to ~bout 40~/O by weight. The water is preferably at a temperature in the range of from about 80~F to about 125~F, more preferably in the range of from about 100~F to about 120~F. The soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being rontacts~ with the dish surface, and is typically contacted with ths dish sur,ac~ for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or WO 92/06161 ~ ,'S91/06981 similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the disn sur;ace.
In a typical Europed,l mar'~-L ppl1cat z , fr~,m about 3 ml. to about 15 ml., preferably from about 3 ml. to aDout 10 ml. of a liqild ~ rger,L comm~s ~ o~ ;c r~?,~in'~ rem about 1,000 ml.
to about 10,000 ml., more t~ r~l7y , rom acc~t ~,l)OO ml. to aooui a,OOO ml., or wa~2f "i a ; ..:~ : .n~ a ~ --t l- -~ ity n the range or from about ~i,OCO m,'. to about ~,390 ml., more typically from ~bout 10,dO~ ml. ~ i-o ~ ,O -". ~~ r 5en~ com.pc~itlon has a aur,~ac~a~ o~ ~' bv ~eiah~ ?re~e,-bl~ ~' '? ~.''~ ' e~ht. The water is preferabl~ ar ~ mper~ .n ? in ~:;le n~no~ ;)r ;nom ~ ûU_ ~0~
to ~o;;t 12~F, ~ ~ o-e'e~h~ ;n thV ~an~e ~f fr~m abollt lOO~F to abûu~ 1 2~'' r . I;12 ~vi~
the detergent composition and ~aa r, i,lere ;h2y are c.ean2d by contacting the soiled surface cr the dish with ~ cloth, sponse, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
In a typical Latin American and Japanese market appl;cation, from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl naving a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 1,000 ml. The detergent composition has a surfactant mixture concentra; on of frûm about 5% to about 40% by - weight, preferably from 3bout 10% to about 30% by weight. The soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or ;i,-milar article. The cloth, sponge, or similar article may be immers-d in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time w o 92/06l6~ PCT/~'S91/06981 ranging from about 1 to about 10 seconds, although the actual time will vary wlti~ each application and user. ~he contacting of the clot~, s~ 3;~ -i,ila~i~ article to the dish surface is preferably accompar,ied ~y a concurrent scru~3bing of the dish surface.
'7l0i~?~ od ~f J~S' '~ill cc~prise immersing the soiled dishes into a l~a,.~r 3a-~n Ynich is at3se,lt any 7iquid dishwashing detergent.
A de~ b ~nL n~ 'i7uid dlshYashing detergent, such as 2 sponne, 1~ p!arad ~iiAecl~iv in'o a separate quantity of undiluted l-lcju . .~ osi iOl ior a ?er;iod of time typically I0 i~ar,s~l~J :~~; -; v~ ; ~a '''i''~l!c . _~C'i-105. ~ne aDsorr3ing device, and c~n~ua~ u~iei~ a li~uid aisf,~ashing composition, is then contao ci , uil; ually ;v ~he ,iin,~3ce o,~ 2ach 3f the soiled dishes to remove ~aid soilina. ~he absorbing device is tyDically contacted ~ C ~ ;m~ r~ ~bout 1 t~
abou~ iO ~G~ ;S~ a~ ;.uugh ~he ~ctual Lime cF application will be dependsnt upon factors such as the degree of soiling of the dish.
The contacting of the absorbing device to the dish surface is preferably accompanied by a concurrent scrubbing.
EXPERIMENTAL
This exemplifies a process for making a N-methyl, 1-deoxyglu-cityl lauramide surfactant for use herein. Although a skilled chemist can vary apparatus configuration, one suitable apparatus for use here1n comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium. The other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution:
a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet. The latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap. A 500 watt heating mantle with a variable transformer temperature controller ("Variac") used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
,I-msthy ! 91 ucamine I195 g ., 1 . O mol 2, Aldrich, M4700-0) and methyl laurate ~rocte, ?~ camDl- cr I270, 220 9 g., 1.0 mole) are p1aced in a flask ~he solid/li~uid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
w o 92/06161 Pcr/us()~/o6~8 - 29 - 2~ r~,J rJ 1 When the melt temperature reaches 145- C, catalyst (anhydrous powdered sodium carbonate, 10.~ 9., 0.1 mole, J. T. ~a~er) is added.
The nitrogen sweep is shut off and thP aspir~tor and nitrogen bleed are adjusted to give 5 inches (~/31 atm.) Hg. vacuum. From this point on, the reaction temperature is held at 1~0 C bv adJusting the Variac and/or by raising or lo~ering ~ne mant7e.
'~ithin 7 minutes, first methannl hllb~l ee ar? .-~9hted 3t ~he meniscus of the reaction mixture. A vigorous reac-~icn soon rollows.
Methanol is distill~d over until l's r~'e ~'U!~'de'. ~',le v-c'i';m i;
adjusted to give about 10 inches '9. ~ ; !
vacuum is incr ased approximatel~ as ;oilo~s (in ilCneS ,tG. a~
minutes): 10 at 3, 20 at 7, 25 at lv. il "lin~s m~ i;; onse; o,-methanol evolution, heating and scirring are discontinued co-incident with some fo~mi,g Th? ?~ o~l~ 7n~
solidifies.
The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
EXAMPLES
~he following examples illustrate the practice of the present invention, but are not intended to be limiting thereof.
EXAMPbE I
The following compositions are ;ormulated on a weight percent basis. These compositions are prepared according to the description set forth below:
A surfactant paste is initially formed by combinins any destred surfactants with water and alcohol. The surfactants contained in this surfactant paste include the polyhydroxy fatty acid amide and suds enhancing agents of the present invention. Ideally the surfactant paste should be pumpable at room or elevated tempera-tures. Separately, in a large mixing vessel having a propeller mixer, three-quarters of the water of the formulated product, one-half of the alcohol of the formulated product, and any required hydrotropes (e.g., xylene, cumene, toluene sulfonates) are combined with mixing to give a clear solution. Any desired optional magne-sium is added next, followed by the surfactant paste, to form a mixture.
w o 92/06161 PCT/US91/06981 ~3~ 30 -If included, the magnesium may be added directly to the mixing vessel as magnesiu.~ chlo-nide. Al ternatiYely~ the magnesium may be added as a m~gn~~ d~ ~~ h~r~~ d~r. This magnesium oxide or hydroxide pcwd?r is -Id~ d to 'he acid form of the surfact-ant salts (?.9' ~ Y~ n? ~nl ,~onat2s, a~ l sulfates, alkyl ethoxylated sulfa~es, me~n~l ?sc~r sui ,'onat~s, ~tC.) in tne surfact-ant past~ dr3Xid~ ?o~der~
a less than stoicliQm~-~r~ -5~ui';'e~ ~mount is added with mixing to ensul cv,~ d~s.c ~r~s m~c~ntaining 0 SUr l-âC~ 'b ? ~ J ~ -3 ~ s~iuticns.
The ~ixt!!r? is ~ ~ci un~i~ 7 ~ ous ~!?~.r solution product is obtaiil2d. ~uu-i iOi1iii i2~ ,.oloi ~"d ~l'r d~s~ d ddltio~al hydrotrooes (added as a solution! ~av then be added to trim the SOl U ~ r ~ , ., ., ., ... _ A ? ~ / h - :J~~
and lOOO c?s, a~ m.~asul 2~ B~ ~ Bnco,~ ld ~isc~..n~r a~ 70~F. The pH of the solution product is then adjusted with either HCl or NaOH
to a level of 7.0 + 0.7 for formulas containing ammonium ions, and 8.5 + 1.5 for formulas which do not contain ammonium ions.
Perfume, dye and other ingredients, e.g., opacifying agents such as Lytron and ethylene glycol distearate, are added as the last step. Lytron can be added directly as a dispersion with mixing.
Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals.
ComPonent A B C D E
C12 14 alkyl N-methyl glucamide 5.0 5.0 10.0 lO.O l5.0 Sodium C11.2 linear alkyl benzene sulfonate 10.0 - - -Ammonium coconut alcohol ethoxylate (1.0 ave.) sulfaie - 2~.0 - - 15.0 Ammonium coconut alcohol sulfate 10.0 5.0 Sodium salt of oo~o-nut acid methyl ester sulfonate - - lS.O
MgCl2 0.5 1.j 0.8 0.6 0.5 WO 92/06161 PCr/1:5~1/069~1 - 31 - ~ 5t3 Sodium C14-l6 alpha olefin sulfonate - - - 20.0 Coconut polyglyco-- side (1.6 ave.
glucose unit per molecule) - 5.0 Dodecyl di~ethyl amine oxide 3.0 3.0 - ~m) ~.b Coconut amidopropyl dimethyl betaine 3.0 - 3.3 Coconut mono-ethanolamide 2.0 Coconut di-ethanolamide Sodium cumene sulfonate 2.0 3.0 3.0 3 0 3.0 Potassium toluene sulfonate - - 2.0 Ethanol 5.0 4.0 - 3.0 4.0 Water ~ misc. --- balance to 100% ---(dye, perfume, etc.) EXAMPLE II
The following compositions are formulated on a weight percent basis. These compositions are prepared in same manner as the compositions of Example I.
ComDonent A B C D
Cl2 14 alkyl N-methyl glucamide 20.0 12.0 4.0 10.0 Sodium C11.2 linear alkyl benzene sulfonate 5.0 Ammonium coconut alcohol ethoxylate (1.0 ave.) sulfate 5.0 - 12.0 Sodium salt of coco-nut acid methyl ester sulfonate - - 15.0 MgCl2 0.7 2.0 1.9 W O 92/06161 PCT/~S~1/06981 ~ 32 -Coconut polyglyco-side (1.6 ave.
glucose unit per molecule) - :~.o 5 o Dodecyl dimethyl amine oxide i.~ - - 3.ù
Coconut amidopropyl dimetnyl be~aine - ~ .û
Hexadecyl dimet~yl betaine ~ - .. ,.~, Coconut di-ethanolamide '.
Sodium cumene sulfonate - - ~. r, Sodium xylen~
sulfonate 3.Q - - 3.0 Potassium toluene sulfonate - 2.0 2.0 Ethanol 3.0 3.0 4.0 5.0 Water & misc. ~ --- balance to 100% ---(dye, perfume, opacifier, etc.) EXAMP~E lIT
The following compositions are formulated on a weight percent 25 basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT A B C D E
Ammonium C1l.2 linear alkyl benzene sulfonate -- 10.0 8.0 13.5 13.5 Cl2 14 fatty acid N-methyl glucamide l6.5 12.5 10.0 12.5 10.0 Ammonium C12 14 alkyl ethoxy (0.8 ave.) sulfate 12.5 11.0 10.0 -- 6.0 Cocoamide propyl betaine 1.5 4.0 3.0 2.0 2.0 Hexadecyl d;methyl beta,ne ~~.0 3.~ 3 0 3.0 2.5 Coconut monoethanolamide ~.~ 3.~ 3.g 2.0 --C12 14 alkyl dimethyl amine oxide -- -- 4.0 2.0 3.0 w o 92/06161 PCT/US91/06981 - 33 - ~ ~ ~ J J ~ I
Sodium cumene sulfonate 1.0 1.0 1.O 1.0 2.0 Ethanol 4 5 5 0 5 0 4 0 4 0 Urea 0 5 0 7 Magnesium hydroxide 1.6 -- --'~ater & Misc. (Perfume, dye, etc.) ----- to lOO~o ~~~~~
EXAMPLE IV
The following detergent compositions are formulated on a~el5h~
percent basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT A B C
Ammonium Cll.2 linear alkyl benzene sulfonate 5.0 -- 10.0 1~.3 --CI2-l4 fatty ~cid N-methyl slucamide 5.0 I5.0 10.0 1'.0 ~.0 Ammonium C12 14 ethoxylated (0.8 ave.) sulfate 5.0 14.0 10.0 -- 12.0 Clo primary alcohol ethoxyl~te (8.0 ave.) 5.0 4.0 -- 4.0 3.0 C12 14 dimethyl betaine -- 2.0 --C12 14 amidopropyl dimethyl betaine 3.0 -- 3.0 -- --Coconut acid monoethanol amide 2.0 2.0 -- -- 2.0 Coconut acid diethanol amide 2.0 -- 2.0 -- 2.0 Coconut dimethyl amine oxide 2.0 2.0 -- 5.0 3.0 Sodium cumene sulfonate 3.0 2.0 2.0 3.0 5.0 Sodium xylene sulfonate 1.0 3.0 3.0 -- --Ethanol 5.0 5.0 3.0 4.0 5.0 Magnesium hydroxide 0.7 0.6 -- -- --Ethy ene glycol distearate -- -- -- 1.O --C16 dimethyl betaine -- -- 3 0 --Urea 2.0 1.5 -- -- --Water ~ misc. (perfume, dye, etc.) -- balance to 100% --w o 92/06161 PCT/~S91/06981 ~ U ~ EXAMPLE V
The following detergent compositions ~ro formu7~tod on ~ ~aight percent basis. These compositions are prepared in the same manner as the compos;tions of Exampl2 I.
COMP~NENT j ~ î, n C14-l6 alpha 012fin sulfonate -- -- 10.' 10.0 C12 14 fatt~ acid ~-me'',~l glucamide î5.0 ~i.O l2.~ 5,0 Ammonium C12 1~ ethox~!la~2à
(0.~ ave.) sulf te C12-14 me~nyi es ;ef sulTonal~ sodium s~ .'J '0.0 5,0 __ C12-14 polyg7ycoside _ jJ ~j Clo primary alcohol ethoxylate ~8.0 ave.) -- -- ~.0 4.0 C12 14 âmi dopropyl dimethyl betaine -- 2 . O - - - -Coconut acid monoethanol amide 3.0 1.0 2.0 --Coconut acid diethanot amide 2.0 1.0 2.0 --Coconut dimethyl amine o%ide 3.0 1.0 3.0 4.0 Sodium cumene sulfonate 2.0 2.0 2.0 2.0 Sodium xylene sulfonate 2.0 2.0 2.0 2.0 Ethanol ~.0 3.0 A . O
Magnesium hydroxide -- -- ,~, ~
Ethylene glycol distearate -- -- ~- 1.0 Water & mfsc. (perfume, dye, etc.) -- balance to 100~h --EXAMPLE VI
The followlng detergent compositions are formulated on a weight percent ~asis. These compositionS arc pr ~pared ln ~he sa",e ,.,ar"ler as the compositions of Example I
COMPONENT A ~ r O
Sodium Cl4 l5 paraffin sulfonate25.0 -- t5 0 Magn~sium C14 i5 paraffin sulfonate -- 26.0 -- --w o 92/06161 pcr/us9l/o69#]
- 35 ~ 3 ~ i Sodium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethoxylated oxide 14.0 -- -- 15.C
Magnesium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethylene oxide ~ -~ 34 0 Sodium coconut glyceryl ether sul~onate 5 0 i~ C12 14 fatty acid N-methyl glucamide 15.0 1~.0 12.0 '~.~
Dimethyldodecylamine oxide ~.0 4.0 4.0 ; .
C12 14 acylamidopropyldimethyl betaine -- 5.0 -- 3.U
Triethanolamine 3.s 3.5 3.5 3 3 Ethanol 5.0 i 0 5 0 3 o Carbopol~ 616 1.5 -- -- --Car.bopol0 617 1.5 2.0 -- --Water & misc. (perfume, dye, etc.) --- balance to 100% ---EXAMPEE VII
The following detergent compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I.
COMPONENT E E G
Sodium C14 15 paraffin sulfonate 15.0 -- --Magnesium C14 16 paraffin sulfonate --Sodium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethoxylated oxide -- 15.0 10.C
Sodium coconut glyceryl ether sulfonate 5 0 -- --Magnesium coconut glyceryl ether sulfonate 5.0 C12 14 fatty acid N-methyl glucamide 10.0 3.0 10.0 Dimethyldodecylamine oxide 4.0 4.0 2.0 C12 14 acylamidopropyldimethyl betaine -- 5.0 --w o 92/06161 PCT/~S91/069 ~)S~ 36 -Triethanolamine 3.5 3.5 3 5 Ethanol ~.~ 3, Carbopol~ 616 !m~
Carbopol~ 617 -- 2.0 --Water & misc. (perfume, dye, otC.) ~ a'-;l~? ;~ f~
E'A~L,~
An alternate method for ?repa~in~ he ~?'y'~!~~e~y - ~y 'C-.'J
amides used herein is as follo~Ys. ~ re2cvio, ~ ,- e'J.lSi~i,-,j,~ a, 84.879. fatcy acid methyl ester ~source~
ester C~1270), 7~9. ,N-~ec~yl-~-gll~c l n~
Company M4700-0), 1.049. sodiu~ metno~-ine ~ r~ ii ~''.-'~.,1 _?~;~
Company 16,~99-2), and ~8.5ig. .~1e_i7~ CO;iv. ; .__~ ;~ n_i'_.~n vessel comprises a standard reflux se,-uo ~i,tea ~itn a ar~Jina tuce.
condenser and stir ~ar. !~ L~,~ p,~_~,J,~ _ ,.,'"1 _,,~ _"
is combined with methanol '.Yit;l stirring und~; ar~o" ~nd ;; ~
begun with good mixing (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperaiure, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point. The reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 105.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction ma'~es an overall perccntage yield value meaningless. The reaction can be carried out at 80% and 90%
reaction concentrations for periods up to 6 months to yield products with extremely small by-product formation.
The following is not intended to limit the invention herein, but is simply tc further illustrate additional aspects OT the technology which may be considered by the formulator in the manufac-ture of a wide variety of detergent compositions using the polyhy-droxy fatty acid amides.
It will be readily appreci2ted that the poljnydroxy ~alty acidamides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While w o 92/06161 PCT/~S41/069 37 i2~
some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about ll, preferably 10, nor below about 3 for unduly extended periods. Final product pH
(liquids) is typically 7.0-9Ø
During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutrali~--the base catalyst used to form the amide bond. ~hile any acid can be used For this purpose, the detergent formulator will recogni~e that it is a simple and convenient matter to use an acid which 13 provides an anion that is otherwise useful and desirable in ~h5 fi,is'~~ d~tergent composition. For example, citric acid can ~5 ui d ,-~n ?~/~ose; Or n5ULI ali,a'ion and th~ ,esul+ing ci+ra-e i~n (C2. i~'~ ~e allowed to rPmain with a C3. ~0~~ polyhydroxy fat y acib amiae slurry and be pump2d into the later manu.ac u,i,3 î~ stages or the overall detergent-manufacturing process. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
The polyhydroxy fatty acid am;des der;ved from coconut alkyl fatty ac;ds (predominantly Cl2-C1~) are more soluble than their tallow alkyl (predominantly Cl6-C~8) counterparts. Accordingly, the Cl2-C,4 materials are somewhat easier to formulate in liquid compositions, and aré more soluble in cool-water laundering baths.
However, the C16-C18 materials are also qu;te useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C1~-C18 materials may be better detersive surfactants than their Cl2-C1~ counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given 3Q formulation.
It will also be appreciated that the solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation andtor chain branching in the fatty acid moiety.
~hus, materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.
w o 92/06161 PCT/~S91/06g~1 2 ~
Likewise, the solub;lity of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., ~ill o,diharil~
be greater than the solubility of their monos3ceh?.r;~e-~er~ved counterpart materials. This higher solubili~ n ~e o,~
particular assistance when formulating liruid co,.n~-l " on~.
Moreover, the polyhydroxy fa~ty acid a,~i~e; .~ r-."
polyhydroxy group is derived from maltose a~oelr ~ '-nCt,iO~:
especially well as detergents when used in CCI110i~7~'i30 ',~
conventional alkylbenzene sulfona~e ("'AS") ,ui~ ~ - n- ~~
not intending to be limited ~y ~heo,~~
combination of LAS with the polyhydroxy raccv ~ a -~from the higher saccharides such as ma~ os and unexpected lowering Ot interfacial tension in aqueous meciia, thereby enhancing net detorgencv ?er ~rm~nre '~~ n"-~O'~? ?
a polyhydroxy fatty acid ~mide derlved from ~ OJe ~ -'J
hereinafter.) The polyhydroxy fatty acid amides can be manufactur~d nGt only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose" corn syrup, "high maltose" corn syrup, etc. can conveniently and economically be used.
De-lignified, hydrolyzed cellulose pulp can also pro1i~e a raw material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatt~ acid amides derived from the higher saccharides, such as maltose, lactose, etc., are more soluble than their glucose counterparts. Moreover, it appears that the ~,ore soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees. Accordingly, the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more). The resulting mi~ture o,~
polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a oro2~er range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fa~t~
acid amide. Thus, in addition to any economic advantages for usins W 0 92/0~161 ~ ~ ~ 2 ~ ~ ~CT/US9l/06981 sugar mixtures rather than pùre sugar reactants, the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation. In some instances, however, some loss of grease removal per~ormance (dishwashing) may be noted at fatty acid malta-mide ,-~iel, aD~2 ~bout 25% and some loss in sudsing above about 33,5 (said percentages being the percentage of maltamide-derived polyhy-dro~,~ a' L~ acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the IO c~ain l~ngth of the fatty acid moiety. Typically, then, the formu-laLor -, c~-.ny to use such mixtures may find it advantageous to se~-c' ;~3i~Jhydr~y îct~y acid amide mixtures which contain ratios or monos~ccn~ri'es (e.g., ~lucose) to di- and higher saccharides (e.g., maltosej ,rom about ~:l to about 99:1.
The manufacture of preferred, uncyclized polyhydroxy fatty acid amides rrom fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30-C-90'C, preferably about 50-C-80'C. It has now been determined that it may be con-venient for the formulator of, for example, liquid detergents to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation. Like-wise, the formulator of, for example, solid, typically granular, detergent compositions may find it convenient to run the process at 2~ 30-C-90~C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) C12-C1l alcohols, such as those available as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they not contain substantial amounts of unethoxylated alcohol and, most preferably, not contain substantial amounts of mono-ethoxylated alcohol. (~T" designation.) While methods for making polyhydroxy fatty acid amides per se form no part of the invention herein, the formulator can also note other syntheses of polyhydroxy fatty acid amides as described hereinafter.
3~ Typically~ the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty ac;d amides will comprise:
SteD 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the w o 92/06161 PCT/~S'91/06981 ~ ~ t,3 '~ r~
N-alkyl am;ne and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Ste~ 2 - r4ac~ing ~'oe aforesaid polyhydroxy amine ~ith, preferably, a fatt~ ~st~r to form an amide bond. ~hile a variety o-F N-alkyl polyhydrox~ amirie. ~e~~
in Step 2 of the reaction sequence can be pr~pared ~v i~.~~O~;
art-disclosed processes, the ,-ollowing ~rocess is n~ o~
makes use of economical sugar syrup as the raw material. I~ is ~o be understood that, for best r~sults :;hen u.i.,s s c;~
materials, the manufacturer should select syrups t~7' -~re -e~-~
light in color or, preferably, nearly colorless ~"~a ?r~
~reparation of ,'~-Al'~yl ?ol,~,ydi3~j ~";,;
From Plan -~ri~/ed ~ug~r 6~r~l~
I. Adduct ~ormat,on - The ,~ollc~, n5 i; a ~anual d ~'~~Oc _~ , ,.
which about 420 g of about 55% glucoso solution (~orn S'/r!'' _ ,~A~
231 g glucose - about 1.28 moles) having a Gardner Color o6 ~ cc than 1 is reacted with about 119 g OT about 60% aqueous metil~lamin~
(59.5 g of methylamine - 1.92 moles) solution. The methylamine (MMA) solution is purged and shielded with N2 and cooled to about lO-C, or less. The corn syrup is purged and shielded with N2 at a temperature of about 10--20-C. The corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown.
The Gardner Color is measured at the indicated approximate times in minutes.
2~Time in Minutes: L~ 30 60 120 180 240 Reaction TemP. ~C Gardner Color (APProximate~
As can be seen from the above data, the Gardner Color for the adduct is much worse as the temperature is raised aboYe about 30~C
and at aoout ~O-C, the time that the adduct has a Gardner Color below 7 ;s only about 30 minutes. For longer reaction, and/or 3~ holding times, the temperature should be less than about 2~'C. 1he Gardner Color should be less than about 7, and preferably le~s than about 4 for good color glucamine.
w o 92/0~161 Pc~/uss1/06981 - 41 ~ 0 92 ~ ~1 When one uses lower temperatures for forming the adduct, the time to reach substantial equilibrium concentration of the adduct is ahortened by the use of higher ratios of amine to sugar. With the 1.5:1 mole ratio of amine to sugar noted, equilibrium is reached in about tY~ hours at a reaction temperature of about ~O-C. At a 1.2:1 mole r~tio, under the same conditions, the time is at least about thr~e h~urs. ~or good color, the combination of amine:sugar ratio;
reaction temperature; and reaction time is selected to achieve subs~a., ~all~ equilibrium conversion, e.g., more than about 90XO~
io pr~,~a,~ mor~ ~cnan about 95~~O~ eYen more preferably more than about ago~ -s~d unon the sugar, and a color that is less than about 7, prererabiy 12ss ~nan about ~, more preferably less than about 1, for the a~ ct.
~ J 'ha ~b3''!- procass ~t a reaction temperature of less than abou; 'ù'C and corn syrups ~,th different Gardner Colors as indi-cated, the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.
Gardner Color (ADDroximate) Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2 As can be seen from the above, the starting sugar material mustbe very near colorless in order to consistently have adduct that is acceptable. When the sugar has a Gardner Color of about 1, the adduct is sometimes acceptable and sometimes not acceptable. When the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color of the adduct.
II. HYdroqen Reaction - Adduct from the above having a Gardner Color of 1 or less is hydrogenated according to the following procedure.
About 539 9 of adduct in water and about 23.1 g of United Catalyst 649B Ni catalyst are added to a one liter autoclave and purged two times with 200 psig H2 at about 20-C. The H2 pressure is raised to about 1400 psi and tne temperature is raised to about 50'C. The pressure is then raised to about 1600 psig and the temperature is held at about 50-55-C for about three hours. The product is about 95% hydrogenated at this point. The temperature is w o 92/06161 PCT/~'S~1/0698i 2 ~ 3'~r~j 6 ~ - 42 -then raised to about 85-C for about 30 m;nutes and the reaction mixture is decanted and the catalyst is filtered out. The product, after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.
The above procedure is r~peated with about 23.1 g Or Rane~
cat21vst with the following chang3s. The cataly,t is was"2~ ~r--times and the reactor, with the catalyst in the reactor, is purged twice with 200 psig H2 and the reactor is pressurized with H, ~t 1600 psig for two hours, the pressure is released at one hour an~
the '~-actor is r3pressurized to loOO psig. The adduc. is t~5n pumped lnto the re~ctor which is at 200 osig and 20 C. and t~
, a~L ~ ,; y~ 200 y5~,g u2, ~tc., ~s ~hc~J~.
The r2sulting product in each case is sreater th n abcu~ '-~-mc~yl glucamine; ,has 12ss ~han about lO py"l 'li bascd uycn t;, glucamine; and has a solution color of less than about Gardner 2.
The crude N-methyl glucamine is color stable to about l40~C for a short exposure time.
It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about l).
In another reaction, adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N2 at about 10-20-C. About 330 9 of about 70% corn syrup (near water-white) is degassed with N2 at about 50-C and is added slowly to the methylamine solution at a temperature of less than about 20-C. The solution is mixed for abou-: 30 minutes to give about 95~~O
adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20-C. The H2 pressure is raised to about 200 psi and the temperature is raised to about 50-C. The pressure is raised to 250 psi and the temperatu-e is held at about 50-55-C for about three hours. The product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85-C for about 30 minutes and the product, after removal of water and evaporation, is a~out 95% N-methyl glucamine, a white powder.
W O 92tO6161 PCT/~'S91/0698 43 h ~ ~ 2 ~ 6 ~
It is also important to minimize contact between adduct and catalysi when the H2 pressure is less than about IOOO psig to minii"i ',i . on~2nt in the 3lucamine. The nickel content in the N-methyl glucamine in this react;on is about 100 ppm as compared to the l~s. ''~an 10 ?pm in the ~revious reaction The following reactions witn H2 are run for direct comparison o ~ v~ p ~ ~ u, ~ " ~ c ~ 2CO ml autoclave reactor is used following typical procedures simi ~; ;o ~lose ,e~ , O'~~tn ,'bo'/q to make adduct and to run the hyd ~ c'lon at va,iou; ~emperaturqs.
~ f~'~~ "se in m2btng glucamine is prepared by combining abous ;~) 9 of arout j5YO glucose (corn syrup) solution (231 g g~ucose- 1 28 molos~ (the solution is made using 9gDE corn syrup ;rv~ ;-_ svlutio~ ,ia',''.?. 3 col3r las; than Gardner 1) and abou~ 9 o,~ 80~o metnylamine (53.5 9 ~MA; 1.92 moles) (from Air Products).
The reaction procedure is as follows:
1. Add about 119 9 of the 50% methylamine solution to a N2 purged reactor, shield with N2 and cool down to less than about lO-C.
2. Degas and/or purge the 55% corn syrup solution at 10-20-C with N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine solution and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about 1-2 hours.
The adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
The ~lucamine adduct hydrogen reactions are as follows:
1. Add about 134 9 adduct (color less than about 6ardner 1) and about 5.8 9 G49B Ni to a 200 ml autoclave.
2. Purge the reaetion mix with about 200 psi H2 twice at about 20-30-C.
3. Pressure with H2 to about 400 psi and raise the temperature to abGut 50'C.
4 Raise pressure to about 500 psi, react for about 3 hours. Keep temperature at about 50-55'C. ~ake Sample 1.
Raise temperature to about 85'C for about 30 minutes.
w o 92/06161 PCT/~'Sgl/069X
2~ 2 ~ U 1 44 6. Decant and filter out the Ni catalyst. Take Sample 2 Conditions for constant temperature reactions:
1. Add about 134 g adduct and about 5.8 g G49B Ni to a 20~ ml autoclave.
2. Purge ~.~ith about 200 psi H2 twice at low temperature.
3. ~ressure .iith h2 to about 400 psi and raise temperature to about 50~C.
4. ~ ressure to about S00 psi, react for about 3.5 hours.
~ee~ 'em~erature at indicated temperature.
i~ 5. v-os;,' a"d --ilter out the Ni catalyst. Sample 3 is for abou iv-j~'C; ~ample ~ is -ror abou~ 7~~C; and Sample 5 is ,'or a'cout :~ U~ . ~ ~;7~ reaction time ror about 85'C is about 45 minutes.) All runs give similar purity of N-methyl slucamine (abou; 9~O);
the ~rdn~r Colors of the runs are similar right after reaction, but S onlJ~ he t/o-stage he~t treatment gives good color stability; and the 85~C run gives marginal color immediately after reaction.
EXAMPLE IX
- The preparation of the tallow (hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this invention is as follows.
Step 1 - Reactants: Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The react2nts are added to glass liner (250 g maltose, 428 9 2~methylamine solution, 100 9 catalyst s~urry - 50 9 Raney Ni) and placed in 3 L rocking autoclave, which is purged with nitrogen (3X500 psig) and hydrogen (2X500 psig) and rocked under ~2 at room temp2rature over a weekend at temperatures ranging from 28-C to 50-C. The crude reaction mixture is vacuum filtered 2X through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are azetroped off by dissolving the material in methanol and then removins the methanol/~ater on a rotary evaporator. Final drying is done under high vacuum. The crude product is dissolved in refluxing methanol, filtered, cooled to recrystallize, filtered and the filter cake is dried under vacuum at 35'C. This is cut ~1. The filtrate is conc~r,trated until a precipitate begins to form and is stored in a refrigerator overnight The solid is filtered and dried under W O 92~0~161 ~ O ~J 2 a ~,CT/US91/069X1 vacuum. This is cut #2. ~he filtrate is again concentrated to half its volume and a recrystallization is performed. Very little precipitate forms. A small quantity of ethanol is added and the solution is le,~t in the freezer over a weekend. The solid material is filter d ~nd dried under Jacuum. The combined solids comprise ~-m2th\/1 ~îm~ ~;~iee J~;~; is iSed i~ S~e~ 2 ~ he overall synthesis.
SteD 2 - ~eactants~ -,ne~hyl maltamlne (from Step l); hardened tallo~ ~e~hvl esters: soaium metnoxiae (2i~o in methanol); absolute methanol (solvent); mole ratio l:l amine:ester; initial catalyst le~lel 10 ~le ~ ~w~r ~al ~minej, raised to 2~ mole Y; solYent level 50% ~t.~.
In ~ d ba. le~ , a ~ h~ 'allo~.~ mcthyl ester is heated ~ el-~-."~ ?~i~t ':;atQr bat~) and lo~dod into a 250 ml 3-n~c'~ ;~S~ 3'~cm Cla;'; .J-'h ,.,e hanic~l 't~-ri"9. The flas~ is heatea co ca. i~'0 LO ?reve~ h2 es~er ,~ ~; ~olidi;~ing. Separ-ately, 2~.0 9 of ,'I-methyl maltamine is combined with ~5.36 g of methanol, and the rPsulting slurry is added to the tallow ester with good mixing. 1.51 9 of 25% sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an additional 10 mole % of catalyst (to a total of 20 mole %) is added and the reaction is allowed to continue overnight (ca. 68-C) after which time the mixture is clear. The reaction flask is then modi-fied for distillation. The temperature is increased to llO-C.
Distillation at atmospheric pressure is continued for 60 minutes.
2~ High vacuum distillation is then begun and continued for 14 minutes, at which time the product is very thick. The product is allowed to remain in the reaction flask at 110~C (external temperature) for 60 minutes. The product is scraped from the flask and triturated in ethyl ether over a weekend. Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder. Any remaining N-methyl maltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol. A
concentrated sample of the product (20 9 in 100 ml of lOC% methanol) 3~ is loaded onto the silica gel and eluted several times using vacuum and several methanol washes. The collected eluant is evaporated to dryness (rotary evaporator). An~ remainins ;allow ester is removed by trituration in ethyl acetate overnight, followed by filtration.
~ ~ 9 w .~ 46 - PCT/USs1/06981 The filter cake is vacuum dried overnight. The product is the tallowalkyl N-methyl maltamide.
In an altarnate mode, Step 1 of the foregoing reaction sequence can bD conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose. The resultlng oolyhydroxy fatty acid amides and mixtures can be used in any or~ ~he det2rg2ilt compoi1tions ~erein.
In still another mode, Step 2 of the foregoing reaction sequence can oe carried out in 1,2-propylene glycol or NEODOL. At ths d,~ 'ion of the .~ormulator, the prop~lene glycol or NEODOL
need nj ,~ Gied ,m~,," 'he r~action product ?rior to its use to formuiaL~ ce~2rsen-c colnposi-ions. Again, accoroing LO the desirei 'r~ Y' ' .~_n;.~ _3.~, b~le ml2~hGAide catalyst car be neutralized by citric acid to provide sodium ci,rate, which can remain in the - ?olyhydnox~ ttV acid amide.
he -~~rmu'a+or of fabric laundering compositions which can advantageous7y contain soil release agent has a wide variety of known materials to choose from (see, for example, U.S. Patents 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896). Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of C1-C~ alkoxy-terminated polyethoxy units (e.g., CH3[0CH2CH2]160H), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(oxyethylene)oxy units (e.s., polyethylene glycol 1500); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) especially wherein the mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about 0.5:1. Such r,Gnionic soil release agents are of the general formula R10-(CH2CH20)x C ~ CO-CH-CH20 - C ~ CO(CH2CH20)y O O
C ~ C - O (CH2CH20)x-RI
wherein R1 is lower (e.g., C1-C~) alkyl, especially methyl; x and y are e2rh integers from about 6 to about 100; m is an integer of from about 9 75 to aboùt 30; n is an integer from abo~t 0.25 to about 20;
~ o 92/06161 PCT/~'S91/06981 and R2 is a mixture of both H and CH3 ~ pr ~ ~ ~a mole ratio ofoxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substantially free of mor,omer. ol~ he ~.C?0',~ ~e ;hereln ~ is ?r~ylene or higher 21kyl.
Thus, the soil release a5ents of U.S. Patent 4,877,896 can comprise, for e~ample~ the reaction product OT dimethyl terephthalate, ethyl-ene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid, Yhereas ~,ese additional soil release agents can comprise, for evample~ tile reactio1l p~oduct o~~ dimeth~l terephthalate, ethylene ~7'~ O~;t'S'!~ i;O?;l~'.ala~ an~ 3-,odiûsul.oben~oic acid. Such ageni;s ~re or~-fer,ed ~ar use in granular laundry detergents.
,he ,ormula'or ",aj 1;3 ~2t2rmino that it is ~dvant3geous to inciude a non-~erbora-~2 bleac", esp2cialiy in heavy-du~y granuîar laundry detergents. A variet~ of peroxygen bleaches are available, commercially, and can be used herein, but, of these, percarbonate is convenient and economical. Thus, the compositions herein can contain a solid percarbonate bleach, normally in the form of the sodium salt? incorporated at a level of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8%
to 15% by weight of the composition.
Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03. 3H202, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequest~rant such as EDTA, l-hydroxy-ethylidene l,l-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorpo~ated during the manufacturing process. For use herein, the percarbonate can be incorporated into detergent composi-tions without additional protection, but preferred embodiments ofthe invention utilize a stable form of the material (FMC). Although a variety of coatings can be used, the most economical is sodium silicate of SiO2:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution and dried to give a level of from 2%
to 10% (normally from 3% to 5%), of silicate solids by weight of the percarbonate. Magnesium silicate can also be used and a chelant such as one of those mentloned above can also be included in the coating.
Ihe particle size range vf the crys~allln~ p~rcar~on~te i5 frc~
3i3 m1crometers to 450 m~cro~eters with a mean o~ a~proxt~.ately 400 mtcrom~ters. ~hen coatad, the crystala ha~ a slzo 1n the r~n~e from 4G0 to 600 m~cro~e'ers.
~hlle hea~y m~tai; present i,~ '.u~ ~n~r~ uc~ ~o ~anufacture the ~ercarbonate can bP co~trolled by the inclusion ~r sequestrants tn the r~ac'tcr, ~.tV~UrA7 'h~ ~p~rclrbon~t~ still re~utrPs prote~tl~n fr~,n h~,aYy 7,n?tl1s present as lmpurltl2s in other lngredlents o~ tl~,2 ~r~UC~ C ;~.aS ~ n ,'~ nd ~n3t tha .~ta1 1eY~1 of tron, ~opper and mana,inesa 'DnS 1~ e p~cduc~ sh ~ld not excee~
25 ppm and prererabl~ snould :~ i_ii ~,i., ~~ .~'.. i.' ~r~e~ to ~vold an ~naccept~bty advsr~e e~ ct ~ p~ncari~or,~ s~ y.
. 3 EXA~P~ES X A-~
13 Tha follow~ng Exa~ples l~lus~rat~ ,h~ ~s~ ui~ d~t~n~ nt c~mposltlons whtch arP ssp~cially l~Zpt~ r'~ iiS;',n, ',.d ~~.e~
hard sur~ce cl~an~ng operat~ons. in the ~x~pl s ~-2, te~ s~r,~c'-ants co~prtsa various alkyl ethcxy s~lfate s~rr3ct~nta ~n~;;-, ~si~g standard term;nology, ara abbr~Yi~ted to tndlc3te th~1r aver~go tegree of ~thoxylat~on; thus C~2 l3E0~0.8~ sulf~t~ lndlcat~s sulfated ~ix~t Cl~-C~ alc~hol fractlon hav1ng an average degreP of-ethoxylat10n of 0,8. ~hese anion~c ethoxy su~fatcs are prefQrably use~ 1n thelr Na+ or N~+ salt form. ~he C~2 1~ amlne oxide 1s a mixed C~ Ycra~el d~methyl ~lne ox1de. The C~2 ~, AP betalne 2C 1s c~2~l~H2s/~ N~(c~2)~Nl(~H~2c~2~o2H. ~he ~12-~ A~ sutt~lne is C,2/,~H2s/2,CONH~C~2)3N~(CH3)2U~CH~OH)C~2503~. The Cl2.~ DM
beta1ne ~s C~2/~2~/2~N~(cH3)tcH2co~. Th~ ethoxyl~ted non~on;c surf~ctant d~slgnated ~ ~E0(8) refers to ~9-C" a~c~hols ethoxyl-a~et w1th an aYerage of 8 m31es sf ethyl~ne cxide. ~h~ C3+~ and Mg~l catlons ~re convenie~tly 1ntroduced tnt~ the compos~tions as CaCl 2 and ~gCl~. The ~a1~nce ~r the composlt,ons eomprls~ water and cltrate~prspylene glyc~l pr~ssnt ln the gl~c~d~ surfactan~
~1-5X) ~nt 1~3X cumene sulfonate or xylene sul~onata hydrotrop~.
The p~ 1s typ~cally 6.3-7.4 (NH~+ salts) or 7-8.2 ~Na~ s~lts).
Jn~r~d1ent percent (wt~) A ~ C
C~2 ~ H mcthyl gluc~1de 11 8 12.~ 3 C~ E0(0.~) sulf~te ~- 16 lO.C 9 - C,2 s~E~(3) sulfate 11 -- 2.7 14 ~; C~2 l~~0~6.~) sulf~t~ 3 AP beta~nQ ~ 2 --C12 l, AP sulta~ne -- -- . 1.C
C~ m1ne ox1d~ 2.5 -- -- 1.0 ~ 3~ -~j~r1J ~ J~ ~
- ~o -Cl2.l~ D~l betalne -~ 2.0 C~ 1E0(~) 0.5 8 7 -~
Ca~+ -- -- 0.5 I.û
Mgl+ 0.9 0.2; -- --Bal ance aat 6al 23 E XA~Pl E X I
In any of the foregoing examples, the ,atty ac;d Sluc~,ice sur~actant can ~e replaced by an equiY31~nt amount of the mal.a"lde surf~ctant. or mlxtur~s of gl~ica.~1de/maltamide surfar~an~ ~er~e~
1~ from plant sugar sources. In the cornposl~.or.~ the us3 of atri~oia-mldes appears to h~lp cold temperature sta~ ty o, ~"q ;?;SiA~s fo~mulattons. t~loreove~, the usa of sul~obs.a~",e ~3~ 5'1 surfactants pro~/tdes supsrior suds~ng.
EXAI~PLES XI I A-D
Inq~edi ents Percent (wt . ) A ,~ C O
C~2 " alkyl ~tho~w sulfate ~l E0) l~ 9 12 --~12~ alcyl ethoxy sulfate (3 ~0) ~ ~4 -- 11 C~ O al kyl etho~yl tte ~8E0) 7 3 7 20 C~2.l" N-methyl ~luca~1de 8 9 lZ 6 Coconut dl ~thanol ~mite ~ 5 Dimethyl dod~cyl amln~ ox1da -~ 1 2 Cocoamldopropyl hydroxysultatnc -~
- Cocoamidopr~pyl beta1ne 2~ Mg~+ ~~ ~~ I l Ca2+ 0 . 5 Sodtum toluene sulfonate 3 3 3 3 Ethanol 4 ~ ~ 4 Water --- - Balance -- ---3Q As note~ ~bova, for co~posit~ons ~hQrein espec1al1y hish suds1ng is deslrod (e.~., d;shwash1ng3, lt ts pref~rred that no suds SupprQSsing agcnt be usad. Slnc~ C1~, and hlgher, fatty acids can act as suds suppr~sscrs, 1t 1s pr~ferred that dtsh~ash1n~ composi-t1cns contain 1 ess than ~bout 5%, prefar~bly 1 oss than about 2,..
3~ ~ost prafer2bly su~stanttall~ no C~ or kishar fatty acids. Accord-1ngly, the for~ul~tor of htgh sudslng CD~posittons W;ll d~strably aYo1d ~ha introtuctton of suds-suppressing amounts of such fatty ~c1ds into such co~posltions ~tth th~ polyhydrexy fatty ac~d a~ide .
_ . --, ", . ,, ,; ... ..
WO 92/06161 PCr/l,'S91/06981 2 ~ 9 2 ~ ~ ~
and/or will avoid the formation of Cl~ and h;gher fatty acids on storage of the finished compositions. One simple method is to use Cl 2 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can ovecome some of the negative sudsing effects caused by the fatty acids.
The formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10/o and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the bright-ener witn water and the polyhydroxy fatty acid amide, ar,d 'hen tû
add the pre-mix to the final composition.
Polyglutamic acid or polyaspartic acid dispersants can oe usefully employed with zeolite-built detergents.
1~ It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.
Claims (16)
1. A detergent composition having enhanced sudsing, characterized in that it comprises from 5% to 65% by weight of a surfactant mixture comprising:
(a) from 5% to 95% by weight of one or more anionic sulfate or sulfonate surfactants; and (b) from 5% to 95% by weight of one or more polyhydroxy fatty acid amides having the formula wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydroxycarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (c) from 1% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, alkylpolysaccharides, and fatty acid amides;
and mixtures thereof.
(a) from 5% to 95% by weight of one or more anionic sulfate or sulfonate surfactants; and (b) from 5% to 95% by weight of one or more polyhydroxy fatty acid amides having the formula wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydroxycarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (c) from 1% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, alkylpolysaccharides, and fatty acid amides;
and mixtures thereof.
2. A composition according to Claim 1 wherein the detergent composition is in the form of a liquid and comprises from 10% to 50% by weight of the surfactant mixture and from 90% to 50% by weight of a liquid carrier, said carrier preferably being water or a mixture of water and a C1-C4 alcohol.
3. A composition according to Claim 1 wherein, with respect to said polyhydroxy fatty acid amide, Z is derived from maltose.
4. A composition according to Claim 1 wherein, with respect to said polyhydroxy fatty acid amide, Z is derived from a mixture of monosaccharides, disaccharides and, optionally, higher sacchariaes, said mixture comprising at least 1% of at least one disaccharide.
5. A composition according to Claim 2 wherein the surfactant mixture comprises from 20% to 80% by weight of the anionic sulfate or sulfonate component, from 20% to 80% by weight of the polyhydroxy fatty acid amide component, and from 2% to 20% by weight of the suds enhancing agent.
6. A composition according to Claim 1 wherein the detergent contains one or more additional anionic or nonionic surfactants.
7. A composition according to Claim 6 wherein the suds enhancing agent is selected from a C10C18 alkyl dimethyl amine oxide, a C10-C18 acyl amide alkyl dimethyl amine oxide, a betaine, a sultaine, the condensation product of an aliphatic alcohol with ethylene oxide, an alkylpolysaccharide, and mixtures thereof.
8. A composition according to Claim 7 wherein the polyhydroxy fatty acid amide is of the formula wherein R2 is a straight-chain C11-C17 alkyl or alkenyl group and Z is derived from glucose, maltose or mixtures thereof.
9. A composition according to Claim 1 which is substantially free of suds-suppressing amounts of C14 and higher fatty acids.
A method for cleaning soiled dishes characterized in that said dishes are contacted with water containing an effective amount of a detergent composition comprising from 5% to 65% by weight of a surfactant mixture comprising:
(a) from 5% to 95% by weight of one or more anionic sulfate or sulfonate surfactants; and (b) from 5% to 95% by weight of one or more polyhydroxy fatty acid amides having the formula wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydroxycarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, preferably C11-C17 N-methyl glucamide, C11-C17 N-methyl maltamide, or mixtures of said glucamide and maltamide, or an alkoxylated derivative thereof; and (c) from 1% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, alkylpolysaccharides, and fatty acid amides; and mixtures thereof.
(a) from 5% to 95% by weight of one or more anionic sulfate or sulfonate surfactants; and (b) from 5% to 95% by weight of one or more polyhydroxy fatty acid amides having the formula wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-C31 hydroxycarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, preferably C11-C17 N-methyl glucamide, C11-C17 N-methyl maltamide, or mixtures of said glucamide and maltamide, or an alkoxylated derivative thereof; and (c) from 1% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides;
betaines; sultaines; and nonionic compounds selected from polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols, the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, alkylpolysaccharides, and fatty acid amides; and mixtures thereof.
11. A method according to Claim 10 wherein said Z moiety in said polyhydroxy fatty acid amide is derived from mixed monosaccharides, disaccharides and polysaccharides available from plant sources.
12. A method according to Claim 10 wherein said R2 moiety in said polyhydroxy fatty acid amide is C15-C17 alkyl, alkenyl, or mixtures thereof.
13. A method according to Claim 10 wherein the water additionally contains one or more additional sulfate or sulfonated detersive surfactants.
14. A method according to Claim 10 wherein the composition is substantially free of suds-suppressing amounts of C14 and higher fatty acids.
15. The composition of Claim 4 wherein, with respect to said polyhydroxy fatty acid amide, Z is derived from a mixture of monosaccharides, disaccharides, and optionally, higher saccharides said mixture comprising at least 1%
maltose.
maltose.
16. The composition according to Claim 2 wherein said carrier is water or a mixture of water and a C1-C4 alcohol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59061690A | 1990-09-28 | 1990-09-28 | |
| US590,616 | 1990-09-28 | ||
| US75589391A | 1991-09-06 | 1991-09-06 | |
| US755,893 | 1991-09-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2092561A1 CA2092561A1 (en) | 1992-03-29 |
| CA2092561C true CA2092561C (en) | 1998-01-20 |
Family
ID=27080892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2092561 Expired - Fee Related CA2092561C (en) | 1990-09-28 | 1991-09-25 | Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and a critically selected suds enhancing agent |
Country Status (10)
| Country | Link |
|---|---|
| KR (1) | KR100225999B1 (en) |
| CN (1) | CN1030929C (en) |
| CA (1) | CA2092561C (en) |
| EG (1) | EG19863A (en) |
| IE (1) | IE64994B1 (en) |
| MA (1) | MA22306A1 (en) |
| PL (1) | PL170492B1 (en) |
| PT (1) | PT99100B (en) |
| RU (1) | RU2108372C1 (en) |
| SK (1) | SK24893A3 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100768069B1 (en) | 2005-12-26 | 2007-10-18 | 그린스웰 주식회사 | Oil emulsifier for emulsifying natural product and the method of production thereof |
| US20100080767A1 (en) * | 2006-11-13 | 2010-04-01 | Croda Uniqema, Inc. | Compounds |
| EP3107986A1 (en) * | 2014-02-20 | 2016-12-28 | Henkel AG & Co. KGaA | Washing or cleaning composition having improved foaming characteristics with a high level of soiling |
| EP3680314B1 (en) | 2017-09-06 | 2023-10-25 | Kao Corporation | Treatment method for textile product |
| CN107997974A (en) * | 2017-12-04 | 2018-05-08 | 广州天赐高新材料股份有限公司 | Contain a kind of detergent composition of polyol |
| RU2727285C1 (en) * | 2019-11-15 | 2020-07-21 | Лаврик Елена Валерьевна | Method for cleaning combustion chamber of internal combustion engine |
| CN116096703A (en) * | 2020-08-28 | 2023-05-09 | 联合利华知识产权控股有限公司 | Surfactant and detergent composition |
-
1991
- 1991-09-25 PL PL91298527A patent/PL170492B1/en unknown
- 1991-09-25 KR KR1019930700968A patent/KR100225999B1/en not_active IP Right Cessation
- 1991-09-25 RU RU93004988A patent/RU2108372C1/en active
- 1991-09-25 SK SK24893A patent/SK24893A3/en unknown
- 1991-09-25 CA CA 2092561 patent/CA2092561C/en not_active Expired - Fee Related
- 1991-09-27 CN CN 91108488 patent/CN1030929C/en not_active Expired - Fee Related
- 1991-09-27 IE IE341991A patent/IE64994B1/en not_active IP Right Cessation
- 1991-09-27 MA MA22589A patent/MA22306A1/en unknown
- 1991-09-27 PT PT9910091A patent/PT99100B/en not_active IP Right Cessation
- 1991-10-05 EG EG60591A patent/EG19863A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030929C (en) | 1996-02-07 |
| MA22306A1 (en) | 1992-04-01 |
| PT99100B (en) | 1999-02-26 |
| CA2092561A1 (en) | 1992-03-29 |
| RU2108372C1 (en) | 1998-04-10 |
| IE913419A1 (en) | 1992-04-08 |
| KR100225999B1 (en) | 1999-10-15 |
| PT99100A (en) | 1992-08-31 |
| CN1061240A (en) | 1992-05-20 |
| PL170492B1 (en) | 1996-12-31 |
| EG19863A (en) | 1999-06-30 |
| SK24893A3 (en) | 1993-07-07 |
| IE64994B1 (en) | 1995-09-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |