CA1190450A - Foaming surfactant compositions - Google Patents
Foaming surfactant compositionsInfo
- Publication number
- CA1190450A CA1190450A CA000407166A CA407166A CA1190450A CA 1190450 A CA1190450 A CA 1190450A CA 000407166 A CA000407166 A CA 000407166A CA 407166 A CA407166 A CA 407166A CA 1190450 A CA1190450 A CA 1190450A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- carbon atoms
- group
- mixtures
- sulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Detergent Compositions (AREA)
Abstract
FOAMING SURFACTANT COMPOSITIONS
Abstract of the Disclosures An agglomerated light-duty detergent granule composition containing an alkylpolysaccharide surfactant, an alkylbenzene sulfonate cosurfactant, an alkylpolyethoxylate sulfate cosurfactant and a water soluble inorganic salt.
Abstract of the Disclosures An agglomerated light-duty detergent granule composition containing an alkylpolysaccharide surfactant, an alkylbenzene sulfonate cosurfactant, an alkylpolyethoxylate sulfate cosurfactant and a water soluble inorganic salt.
Description
~o~s~
FOAMING SURFA(::TANT COMPOSITIONS
TechnicaL Field This invention relates to sur~actant combinations which provide controllable aqueous foams. ,Such compositions can be used in any situation where foams are desirable, includ-ing the laundry, personal cleaning products, dishwashing, fire fightingt oil well drilling, ore beneficiation, solu-tion mining, washing hair, preparation of foamed solid structures, etc.
Description of the Prior Art Alkylpolyglycosides which are surfactants have been disclosed in U~S. Patents 3,598,86S; 3,721,633; ancl 3~772/269O These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent composi~ions containing these surfactants.
U.S. Patent 3,219,656 discloses alkylmonoglucosides and suggests their utility as foam stabilizers for other surfactants~ Various polyglycoside surfactant structures and processes for making them are disclosed in U,S.
Patents 2,974,134; 3,640,998; 3,839,318: 3,314,936;
3,34~,558; 4,011,389; 4,2~3,129.
~11 percentages, parts and ratios used herein are by weight unless otherwise specified.
Summary of the Invention This invention relates to the discovery of certain combinations of surfactants which provide urlusual foams.
Specifically this invention relates to foam~ng compositions comprising (1) an alkylpolysaccharide surfactant having the formula RO(RlO)tZx wherein Z is a moiety derived from a reducing saccharide containing from 5 to 6 carbon atoms, preferably a glucose, galactose, glucosyll or galactosyl residue or mixtures thereof; R is a hydrophobic group selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl phenyl or hydroxy ~2;,' ' "' !
~`
all<yl groups or mixtures thereof in which said all<yl~
yroups contain from about ~ to abou-t 20 carbon atoms preferably from about 10 to aboLIt 16 carbon atoms, most preferably from about 12 to about 14 carbon ` ator7s; F~ contains from 2 to ~I carbon atoms, preferably ethylene, propylene ancl/or glyceryl, t is from 0 to about 30, preferably 0 to about 10, most preferably 0;
wl-erein x is a number from about 1 5 to to about 10, preferably 1 5 to 4, most preferably 1 6 to 2 7; and
FOAMING SURFA(::TANT COMPOSITIONS
TechnicaL Field This invention relates to sur~actant combinations which provide controllable aqueous foams. ,Such compositions can be used in any situation where foams are desirable, includ-ing the laundry, personal cleaning products, dishwashing, fire fightingt oil well drilling, ore beneficiation, solu-tion mining, washing hair, preparation of foamed solid structures, etc.
Description of the Prior Art Alkylpolyglycosides which are surfactants have been disclosed in U~S. Patents 3,598,86S; 3,721,633; ancl 3~772/269O These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent composi~ions containing these surfactants.
U.S. Patent 3,219,656 discloses alkylmonoglucosides and suggests their utility as foam stabilizers for other surfactants~ Various polyglycoside surfactant structures and processes for making them are disclosed in U,S.
Patents 2,974,134; 3,640,998; 3,839,318: 3,314,936;
3,34~,558; 4,011,389; 4,2~3,129.
~11 percentages, parts and ratios used herein are by weight unless otherwise specified.
Summary of the Invention This invention relates to the discovery of certain combinations of surfactants which provide urlusual foams.
Specifically this invention relates to foam~ng compositions comprising (1) an alkylpolysaccharide surfactant having the formula RO(RlO)tZx wherein Z is a moiety derived from a reducing saccharide containing from 5 to 6 carbon atoms, preferably a glucose, galactose, glucosyll or galactosyl residue or mixtures thereof; R is a hydrophobic group selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl phenyl or hydroxy ~2;,' ' "' !
~`
all<yl groups or mixtures thereof in which said all<yl~
yroups contain from about ~ to abou-t 20 carbon atoms preferably from about 10 to aboLIt 16 carbon atoms, most preferably from about 12 to about 14 carbon ` ator7s; F~ contains from 2 to ~I carbon atoms, preferably ethylene, propylene ancl/or glyceryl, t is from 0 to about 30, preferably 0 to about 10, most preferably 0;
wl-erein x is a number from about 1 5 to to about 10, preferably 1 5 to 4, most preferably 1 6 to 2 7; and
(2) an anionic cosurfactant which is a sulFate, sulfonate andlor carboxylate or mixtures thereof neutralized with one or more cationic moieties (M) to complete the formula, preferably the anionic cosurfactant has the forrnula R (5O3)y(COO)zl~Jlq;
wherein R is an alkyl, allcylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl, or mixtures -thereof, said alkyl groups containing from about 6 to about 30 carbon atoms, preferably about 10 to about 18 carbon atoms; y is a number from 0 to about Ll, z is a number from 0 to about 4, y + z is at least I, ancl ~1 is a ca tionic moiety with q bein~ selected to complete the formula, wherein the ratio of (2, to (I) is from about l lO to about 25 I0 1 (i e, 0.1 to 10.0) ~xcept that when the cosurfactant is an all~ylbenzene sulfonate, the ratio of (2) to (I) is at least about 1 2 (i.e, at least about 0 5) and when y is 0 and z is one, the ratio of (2) to (I) is at least about 1 2 (i e, at least about 0 5), and when the anionic cosurfactant does not contain sulfonate or carboxylate ~3roup x must be from I 5 to 3 and the all<ylpoh~saccharide surfactant must have a free fatty alcohol content of less than about 2% by wei~ht 5~
It llas surprisingly been found that the cosur-factants inter-~act with the alkylpolysaccharide surfactant of this inven-tion to provide a relatively stable foam which is readily rinsecl.
The invention also relates to the process of producing foams utili7illg aqueous solutions containing from about 0.019~ to about 95~ of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpolysaccharide Surfactant The all<ylpolysaccharides are those having a hydrophobic group IO containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and a polysaccharide hydrophilic group containing from about 1 . 5 to about 10, preferably from 1 . 5 to 4, most preferably from 1.6 to 2.7 saccharide units (e.g., gaiacto-IS side, glucoside, ~ructoside, glucosyl, fructosyl and/or galactosyl units). Mixtures of saccharide moie-ties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkylpolysaccharide surfac-tant.
For a particular allcylpolysaccharide molecule x can only assume a~ integral values. In any physical sample of alkylpolysaccharide surfactants -there will in general be molecules haviny dif-Ferent x values. The physical sample can be characteri~ed by the average value of x and this average value can assume non-integral values.
In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or ~-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or ~alactoside). However, attachment through the 1-position, i.e., glucosides, galactosides, fructosides, etc., is preferred. In the ~o preferred product the additional saccharide units are predomin-ately attached to the previous saccharide unit's 2-position.
Attachment through the 3~ -, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic rnoiety ( R) and the polysaccharide-chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups inclucie allcyl groups, either,~
saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 16 carbon atoms. Preferably, the all<yl cJroup is a straiqht chain 5 ~ saturated allcyl ~roup. The alkyl group can contain up to 3 hydroxy groups ancl/or the polyaikoxide chain can contain up -to about 30, preferably less than 10, most preferably 0, allcoxide moieties .
Suitable all<yl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexa~lu-cosides, galactosicies, lactosides, fructosides, fructosyls, !ac-tosyls, glucosyls and/or galactosyls and mixtures thereof.
The alkylrnonosaccharides are relatively less soluble in water than the higher aikylpolysaccharides. When used in aclmixture with alkylpolysaccharides, the all<ylmonosaccharides are solubilized to some exten-t. The use of alkylmonosaccharides in admixture with alkylpolysaccharides is a preferrecl mocie of carrying out the inven-tion. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaylucosides ancl tallo~,v alkyl -tetra-, penta-, and hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides havin~ the formula R O(Cn~l2nO)t(z2)x wherein Z is derived from glucose, R is a hydrophobic group 2~ selected from the group consisting of alkyl, alkylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures thereof in which said aikyl ~r oups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from 1 . 5 to about 8, preferably frorn 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2O~i) can be reacted with glucose, in tile presence of an acid catalyst to form the desired ylucoside. Alternativeh/ the alkylpolyglucosicies can be prepared by a two step procedure in which a short chain alcohol (C1 6) is ~5 reacted with ~lucose or a poly~lucoside (x=2 to 4) to yield a s~
short chain allcyl ylucoside ~x=1 to l~) which can in turn b~
reacted with a longer chain alcohol (R O~l) to displace the short chain alcohol and obtain the desired alkylpolyglucosicle. If this two step procedure is ~Ised, the short chain alkyl~lucoside con-r tent of the final alkylpolyglucoside material should be less than 50~, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkylpolyglucoside.
The al~ount of unreacted alcohol (the fr~e fatty alcohol conten~) in the desired alkylpolysaccharide surfactant is pre-l(; ferably less than about 2~6, more preferably less than about 0.5 by weight of ~he total of the alkyl polysaccharide plus unreac-ted alcohol. The amount of alkylmonosaccharide is about 20~ to about 709~, preferably 30% to 60~6, most preferably 309s -to 50% by weight of the total of the alkylpolysaccharide. For some uses it is l i desirable to have the alkylmonosaccharide content less than about 10%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preEerred glucose and g~lactose derived surfactants and the less preEerred ~C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosides because the stero chemistry of the saccharide moiet.y is changed during the preparation reaction.
THE ANIONIC COSURFACTANTS
Anionic cosurfactants can be selected from the group consisting of sulfates, sulfonates/ carboxylates and mixtures thereof. The cosurfactants are neutralized with a cationic moiety or moieties selected Erom the group consis-ting oE
alkali metal, eOg. sodium or potassium, a~kaline earth metal, e.g. calcium or magnesium, ammonium, substituted ammonium, including mono~, di-, or tri~, ethanolamrnonium cations.
Mixutres oE cations can be desirable. The anionic cosurEactants useful in the present inven-tion all have
wherein R is an alkyl, allcylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl, or mixtures -thereof, said alkyl groups containing from about 6 to about 30 carbon atoms, preferably about 10 to about 18 carbon atoms; y is a number from 0 to about Ll, z is a number from 0 to about 4, y + z is at least I, ancl ~1 is a ca tionic moiety with q bein~ selected to complete the formula, wherein the ratio of (2, to (I) is from about l lO to about 25 I0 1 (i e, 0.1 to 10.0) ~xcept that when the cosurfactant is an all~ylbenzene sulfonate, the ratio of (2) to (I) is at least about 1 2 (i.e, at least about 0 5) and when y is 0 and z is one, the ratio of (2) to (I) is at least about 1 2 (i e, at least about 0 5), and when the anionic cosurfactant does not contain sulfonate or carboxylate ~3roup x must be from I 5 to 3 and the all<ylpoh~saccharide surfactant must have a free fatty alcohol content of less than about 2% by wei~ht 5~
It llas surprisingly been found that the cosur-factants inter-~act with the alkylpolysaccharide surfactant of this inven-tion to provide a relatively stable foam which is readily rinsecl.
The invention also relates to the process of producing foams utili7illg aqueous solutions containing from about 0.019~ to about 95~ of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpolysaccharide Surfactant The all<ylpolysaccharides are those having a hydrophobic group IO containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and a polysaccharide hydrophilic group containing from about 1 . 5 to about 10, preferably from 1 . 5 to 4, most preferably from 1.6 to 2.7 saccharide units (e.g., gaiacto-IS side, glucoside, ~ructoside, glucosyl, fructosyl and/or galactosyl units). Mixtures of saccharide moie-ties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkylpolysaccharide surfac-tant.
For a particular allcylpolysaccharide molecule x can only assume a~ integral values. In any physical sample of alkylpolysaccharide surfactants -there will in general be molecules haviny dif-Ferent x values. The physical sample can be characteri~ed by the average value of x and this average value can assume non-integral values.
In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or ~-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or ~alactoside). However, attachment through the 1-position, i.e., glucosides, galactosides, fructosides, etc., is preferred. In the ~o preferred product the additional saccharide units are predomin-ately attached to the previous saccharide unit's 2-position.
Attachment through the 3~ -, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic rnoiety ( R) and the polysaccharide-chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups inclucie allcyl groups, either,~
saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 16 carbon atoms. Preferably, the all<yl cJroup is a straiqht chain 5 ~ saturated allcyl ~roup. The alkyl group can contain up to 3 hydroxy groups ancl/or the polyaikoxide chain can contain up -to about 30, preferably less than 10, most preferably 0, allcoxide moieties .
Suitable all<yl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexa~lu-cosides, galactosicies, lactosides, fructosides, fructosyls, !ac-tosyls, glucosyls and/or galactosyls and mixtures thereof.
The alkylrnonosaccharides are relatively less soluble in water than the higher aikylpolysaccharides. When used in aclmixture with alkylpolysaccharides, the all<ylmonosaccharides are solubilized to some exten-t. The use of alkylmonosaccharides in admixture with alkylpolysaccharides is a preferrecl mocie of carrying out the inven-tion. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaylucosides ancl tallo~,v alkyl -tetra-, penta-, and hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides havin~ the formula R O(Cn~l2nO)t(z2)x wherein Z is derived from glucose, R is a hydrophobic group 2~ selected from the group consisting of alkyl, alkylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures thereof in which said aikyl ~r oups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from 1 . 5 to about 8, preferably frorn 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2O~i) can be reacted with glucose, in tile presence of an acid catalyst to form the desired ylucoside. Alternativeh/ the alkylpolyglucosicies can be prepared by a two step procedure in which a short chain alcohol (C1 6) is ~5 reacted with ~lucose or a poly~lucoside (x=2 to 4) to yield a s~
short chain allcyl ylucoside ~x=1 to l~) which can in turn b~
reacted with a longer chain alcohol (R O~l) to displace the short chain alcohol and obtain the desired alkylpolyglucosicle. If this two step procedure is ~Ised, the short chain alkyl~lucoside con-r tent of the final alkylpolyglucoside material should be less than 50~, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkylpolyglucoside.
The al~ount of unreacted alcohol (the fr~e fatty alcohol conten~) in the desired alkylpolysaccharide surfactant is pre-l(; ferably less than about 2~6, more preferably less than about 0.5 by weight of ~he total of the alkyl polysaccharide plus unreac-ted alcohol. The amount of alkylmonosaccharide is about 20~ to about 709~, preferably 30% to 60~6, most preferably 309s -to 50% by weight of the total of the alkylpolysaccharide. For some uses it is l i desirable to have the alkylmonosaccharide content less than about 10%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preEerred glucose and g~lactose derived surfactants and the less preEerred ~C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosides because the stero chemistry of the saccharide moiet.y is changed during the preparation reaction.
THE ANIONIC COSURFACTANTS
Anionic cosurfactants can be selected from the group consisting of sulfates, sulfonates/ carboxylates and mixtures thereof. The cosurfactants are neutralized with a cationic moiety or moieties selected Erom the group consis-ting oE
alkali metal, eOg. sodium or potassium, a~kaline earth metal, e.g. calcium or magnesium, ammonium, substituted ammonium, including mono~, di-, or tri~, ethanolamrnonium cations.
Mixutres oE cations can be desirable. The anionic cosurEactants useful in the present inven-tion all have
3~ detergent properties and are all wa-ter soluble or dispersible in water.
- 5a -Alkylbenzene Sulfonates One of the preferred cosurfactants for use in this invention is an alkylbenzene sulfonate. The alkyl group can be either saturated or unsa-turated, branched or straight chain and is optionally substituted with a hydroxy group. Middle phenyl positions are generally preferred for volume of foaming in light soil conditions.
However in heavier soil conditions, phenyl attachment at the 1- or 2 position is preferred.
` The preferred alkylt>enzene sulfollates contain a straight alkyl chain containing from about 9 to about 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, and the cation is sodiur~, potassium, ammonium, mono~, di-, or triethanolammon-ium, calcium or magnesium and mi,ctures thereof. Ma~nesium is the preferred cationic moiety. These same cations are preferred for other anionic surfactants and ingredients. The maynesium alkyl-benzene sulfonates ~,vhere the phenyl group is attached near the middle of the alkyl chain are surprisingly better than the ones with the phenyl near the end of the chain when the polysaccharide chain averages ~reater than about 3 saccharide units. Suitable alkylbenzene sulfonates include C~ll alkylbenzene sul fonates ~vith low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the foaming compositions of -the inven~!on since the foams producecl 2() therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These corrlpositions are particularly desirable for industrial and commercial processes as discussecl llereinafter. The volume of foam produced using the alicylbenzene sulfonate cosurfactant is lar~er than for any other 2 ~ cosurfactant.
Soap -Other preferred cosurfactants for use in this invention are carbo~ylates, e.g. fatty acid soaps and sir,lilar surfactants. The soaps can be saturated or unsaturated and can contain various '~ substituents such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straignt chain saturated or unsaturatecJ hydrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon ator.1s, preferably from about 10 to about 13 carbon atoms.
3 . Tbe use of carboxylate cosurfactants is especially valuable since the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety (M) ~or carboxylate cosurfactants is selected from the group consisting of alkali metal, for example, sodium or potassium, alkaline earth metal, for example, calcium or magnesium, ammonium, or substituted ammonium, including mono , di-, or triethanolammonium cations. Mixtures of cations can be desirable~
In addition to the preferred alkylbenzene sulfonate and soap cosurfactants many other surfactants which contain sulfonate or carboxylate groups can be used in the foaming compositions of the invention. Generally the use of these latter cosurfactants produces less foam volume than does the u5e of the preferred cosurfactants. However, the alkylpolysaccharide surfactant stabilizes the foams which are produced and allows the foams to be rinsed more quickly.
One group of cosurfactants that are of interest because of their superior detergency are the zwitterionic deter-gents which contain both a cationic group, either ammonium, phosphonium, sulfonium or mixtures thereof and a sulfonate or carboxylate group. Preferably there are at least about four atoms separating the cationic and anionic groups.
Suitable zwitterionic surfactants are disclosed in U.S.
Patents 4,159,277, 3,928,251; 3,925,262; 3,929,678;
3,227,749; 3,539,521; 3,383,321; 3~390/094; and 3,239,560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfac~ants are the ampho~erio detergents which have the same general structure as the zwitterionic surfactants but with an amine group instead of the quaternary ammonium group.
Yet other cosurfactants are the alkyl (paraffin or olefin) sul~onates, pre~erably with a more central hydro-philic group, containing from about 6 to about 30 carbon atoms. Compositions containing these cosur~actants pro-duce the least volume of foam, if that is desired. The hydrophobic group can contain up to about 10 hydroxy groups and/or e-ther linkages. Examples includè~
C1l1 15 paraffin sulfonates and Clll 16 olefin sulfonates.
Still another cosurfactant is a soap structure containin~3 up to about 10 ~ther linka~es in the chain and from about I to about
- 5a -Alkylbenzene Sulfonates One of the preferred cosurfactants for use in this invention is an alkylbenzene sulfonate. The alkyl group can be either saturated or unsa-turated, branched or straight chain and is optionally substituted with a hydroxy group. Middle phenyl positions are generally preferred for volume of foaming in light soil conditions.
However in heavier soil conditions, phenyl attachment at the 1- or 2 position is preferred.
` The preferred alkylt>enzene sulfollates contain a straight alkyl chain containing from about 9 to about 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, and the cation is sodiur~, potassium, ammonium, mono~, di-, or triethanolammon-ium, calcium or magnesium and mi,ctures thereof. Ma~nesium is the preferred cationic moiety. These same cations are preferred for other anionic surfactants and ingredients. The maynesium alkyl-benzene sulfonates ~,vhere the phenyl group is attached near the middle of the alkyl chain are surprisingly better than the ones with the phenyl near the end of the chain when the polysaccharide chain averages ~reater than about 3 saccharide units. Suitable alkylbenzene sulfonates include C~ll alkylbenzene sul fonates ~vith low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the foaming compositions of -the inven~!on since the foams producecl 2() therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These corrlpositions are particularly desirable for industrial and commercial processes as discussecl llereinafter. The volume of foam produced using the alicylbenzene sulfonate cosurfactant is lar~er than for any other 2 ~ cosurfactant.
Soap -Other preferred cosurfactants for use in this invention are carbo~ylates, e.g. fatty acid soaps and sir,lilar surfactants. The soaps can be saturated or unsaturated and can contain various '~ substituents such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straignt chain saturated or unsaturatecJ hydrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon ator.1s, preferably from about 10 to about 13 carbon atoms.
3 . Tbe use of carboxylate cosurfactants is especially valuable since the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety (M) ~or carboxylate cosurfactants is selected from the group consisting of alkali metal, for example, sodium or potassium, alkaline earth metal, for example, calcium or magnesium, ammonium, or substituted ammonium, including mono , di-, or triethanolammonium cations. Mixtures of cations can be desirable~
In addition to the preferred alkylbenzene sulfonate and soap cosurfactants many other surfactants which contain sulfonate or carboxylate groups can be used in the foaming compositions of the invention. Generally the use of these latter cosurfactants produces less foam volume than does the u5e of the preferred cosurfactants. However, the alkylpolysaccharide surfactant stabilizes the foams which are produced and allows the foams to be rinsed more quickly.
One group of cosurfactants that are of interest because of their superior detergency are the zwitterionic deter-gents which contain both a cationic group, either ammonium, phosphonium, sulfonium or mixtures thereof and a sulfonate or carboxylate group. Preferably there are at least about four atoms separating the cationic and anionic groups.
Suitable zwitterionic surfactants are disclosed in U.S.
Patents 4,159,277, 3,928,251; 3,925,262; 3,929,678;
3,227,749; 3,539,521; 3,383,321; 3~390/094; and 3,239,560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfac~ants are the ampho~erio detergents which have the same general structure as the zwitterionic surfactants but with an amine group instead of the quaternary ammonium group.
Yet other cosurfactants are the alkyl (paraffin or olefin) sul~onates, pre~erably with a more central hydro-philic group, containing from about 6 to about 30 carbon atoms. Compositions containing these cosur~actants pro-duce the least volume of foam, if that is desired. The hydrophobic group can contain up to about 10 hydroxy groups and/or e-ther linkages. Examples includè~
C1l1 15 paraffin sulfonates and Clll 16 olefin sulfonates.
Still another cosurfactant is a soap structure containin~3 up to about 10 ~ther linka~es in the chain and from about I to about
4 carbon atoms between ether linka~es wi-th from about 6 to about 30 carbon atoms in a terminal portion containing no ether link-ages .
The preFerred alkylpolyglucosides that contain an average of from 1.5 to 4 glucoside units, preferably from 1.6 to 2.7 10 glucoside units; less than about 50% short chain alkylpolyglu-cosides less than about 10%, preferably less than about 2%, most preferably less than about 0.5% unreacted fatty alcohol, increase the sudsing ability of conventional sulfate deter~ent cosurfact-ants, especially alkyl sulfate and alkyl polye-ther sulfate cosur-15 factants having the formula:
3 R O(cnH2nO)t 53 M
wherein R is an alkyl or hydroxyalkyl group containing from about 8 to about 18 carbon atoms, n is 2 or 3, t can vary from 0 to about 30, and M is a cationic moiety as defined above, the 20 cosurfactant being water soluble or dispersible.
A preferred foaming composition of the inven-tion herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(R1O)t(Z)X whe~ein Z is a moiety derived from a reducing saccharide containing from S to 6 carbon atoms ancl wherein R is a hydrophobic group selected from t~e group consis-ting of alkyl, alkylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 1~ carbon atoms; K1 contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from about 1.5 to about 10, preferably 1.5 to 4, most pre-f~rably 1.6 to 2.7; ancl (2) a mixture of cosurfactants neutralized with one or more cationic moielies consisting essentially of:
(a) frorn about 1~ to about 95% preferably about 10% to
The preFerred alkylpolyglucosides that contain an average of from 1.5 to 4 glucoside units, preferably from 1.6 to 2.7 10 glucoside units; less than about 50% short chain alkylpolyglu-cosides less than about 10%, preferably less than about 2%, most preferably less than about 0.5% unreacted fatty alcohol, increase the sudsing ability of conventional sulfate deter~ent cosurfact-ants, especially alkyl sulfate and alkyl polye-ther sulfate cosur-15 factants having the formula:
3 R O(cnH2nO)t 53 M
wherein R is an alkyl or hydroxyalkyl group containing from about 8 to about 18 carbon atoms, n is 2 or 3, t can vary from 0 to about 30, and M is a cationic moiety as defined above, the 20 cosurfactant being water soluble or dispersible.
A preferred foaming composition of the inven-tion herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(R1O)t(Z)X whe~ein Z is a moiety derived from a reducing saccharide containing from S to 6 carbon atoms ancl wherein R is a hydrophobic group selected from t~e group consis-ting of alkyl, alkylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 1~ carbon atoms; K1 contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from about 1.5 to about 10, preferably 1.5 to 4, most pre-f~rably 1.6 to 2.7; ancl (2) a mixture of cosurfactants neutralized with one or more cationic moielies consisting essentially of:
(a) frorn about 1~ to about 95% preferably about 10% to
5~
about 50% of a water soluble alkylbenzene sulfonate~
cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 596 to about 999~, preferably 50-90~ of a cosurfactant selected from the group consisting of an allcyl glyceryl ether sulfonate in which the alkyl group contains from about ~3 to about 18 carbon atoms, an alpha-oleFin sul-fonate in which the olefin group contains from about 10 to about 18 carbon atoms, an alkyl polyethoxylate carboxylate in which the alkyl group contains from about 10 to about 18 carbon atoms, and the polyethoxylate chain contains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
Such compositions have improved suds mileage as compared to compositions containing only -the alkyl benzene sulfonate cosur-factant and the alkylpolysaccharide surfactan-t.
Another preferred embodimen-t of a foaming composition of -the invention herein comprises 20 ( 1 ) an alkylpolysaccharide sur-factant havin~ the forrnula RO(R1O)t(Z3X wherein Z is a moie-ty derived from a reducing saccharide containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from abou t 1 . 5 to about 10;
30 (2) an anionic cosurfactant selected from the group con-sisting of sulfates, sul~onates, carboxylates and mix-tures thereof neutrali~ed with one or more cationic moieties M -to comple~e the formula, the ratio oF (2) to ( 1 ) beir7g from about 1 :10 to about 10 :1; and s~
(3) from about 2% -to about 10% of an auxiliary foam booster"
selected from the group consisting oF:
~a) amides having the formula R7-C-N- ( RS ) 2 wherein R7 is an alkyl ~roup containin~3 from about ~ to about 1~ carbon atoms, preferably about 12 to about 14 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1 3 alkyl, C1 3 alkanol, and (C2H4O-~1_4H groups and mixtures thereof;
(b) amine oxides having -the formula:
R4~oR )bN(R )2 wherein R ~ is an alkyl group containin~ from abou-t to about 1~ carbon atoms, preferably from 12 to 14 carbon atoms, each R5 con-tains two or three carbon atoms, b is from 0 to about 30, each R is the same or different and is selected from the group consisting of C1_3 al~yl, C1_3 -(C2H40)1_6H groups and mixtures thereof; and (c) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mileage.
Preferred anionic cosurfactants are alkylbenzene sulfonate, alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sul-fates and paraffin sulfonates and mixtures thereof. The cationic moieties are selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, 30 triethanolammonium, calcium, magnesium and mixtures thereof.
Preferred compositions of this embodiment of the invention cornprise from 1~ to abou-t 95%, preferably 5P~ to about 50% of an -alkylpolysaccharicie surfactant in which the alkyl group contains from 12 to 14 carbon atoms, x is from 1 . 5 to 4, more preferably 35 1.6 to 2.7; from 1O to about 95~O, preferably from about 10% to about 50% of an anionic cosurfac-tant neutralized with one or more~
cationic moieties and which is a mixture of ~1) from 16 to about 95~, preferably from about 5% to about 50~6 of an alkyl benzene sulfonate in which the allcyl group contains from about 8 to about 13 carbon atoms or an alpha-olefin sulfonate in which the olefin group contains from about 10 to about 18 carbon a~oms, or mixtures thereof; and (2) frorr 1% to about 95%, preferably from about 5% to about 50% of an alkyl polyethoxylate sulfate in which the alkyl group contains from about 8 to about 18 carbon atoms, preferably from 12 to 1 L~ carbon atoms and from about one to about six ethoxylate moieties and wherein from about 1% -to about 100%, preferably from about 10% to about 80% of the cationic rnoieties are magnesium: and wherein the auxiliary foam booster is an amide.
Another pre-ferred foaming composition of the invention herein is an ayglomerated light duty detergen-t granule composi-tion cornprising ( 1 ) from about 56 to about 60%, preferably from 1 OP6 to about 20-6 of an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x wherein Z is a moiety derived from a reducing saccharide moiety containing from 5 to 6 car;bon atoms and wherein R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl or hydroxyalkyl grups or mixtures thereof in which said alkyl groups contain from about ~3 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms; R
contains from 2 to about 4 carbon atoms; -t is from 0 to about 30; and x is a number frorn about 1.5 to about 10, preferably 1.5 to 4, most preferably 1 6 to 2.7;
(2) frorn about 5% to abou~ 60P6 of an alkyl ben~ene sul-fonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, said alkyl ~ 12 ~
benzene sulfonate neutralized with one or more cationic moieties (M) to balance the formula;
(3) from about 5~ to about ~0%, preferably from about 10% to about 20% of an alkylpolyethoxylate sulfate cosurfactant in which the alkyl group contains from about 10 to about 16 carbon atoms and in which there are from 1 to about 6 ethoxylate groups, said alkylpolyethoxylate sulfate neu~ra-lized with one or more catlonic moieties M to complete the formula.
(4) from about 5% to about 80% of a water soluble inorganic salt selected from the group consisting of sodi~l and potassium sulfates, chlorides, carbonates, phosphates; and mixtures thereof.
The Processes Mixtures of alkylbenzene sulfonate and/or the soap cosurfactant and the alkylpolysaccharide surfactant can be used at levels of from about 0.01% to about 95%, in ratios of cosurfactant to alkylpolysaccharide of from about 10:1 to about 1:10, in water with agitation to provide foamsO
These foams are relatively stable and, iE not disturbed, can exist for several days~ Furthermore, the foam has structural integrity and do~s not spread out. The foams prepared using mixtures of alkylbenzene sulfonate and ~he alkylpolysaccharide are unique in that they do not have a "slippery" feel. All of the foams rinse ~u.ickly~
The unusual properties of the foams of this invention make them valuable for use not only in soap bars, bubble baths, shaving creams, laundry, dishwashing, and washing hair, where a good volume of stable suds and quick rins-ability are desirable, but also in a large number of fields unrelated to detergency.
The compositions and processes of this invention are particularly valuable for use in the "foam" or "mist" well drilling processes in which the foam is used to carry water and/or soil particles to the surface of the bore hole. A
description of such a drilling method can be found in U.S.
, ~,,,;~
Patents 3,303,896; 3,111,178; 3,130,798; and 3,215,200. In such a process, the surfactants are present at a level of from about 0.01% to about 5~, preferably from about 0.01~
to about 2~, most preferably from about 0.05% to about 0.5%.
The preferred cosurfactant is an alkylbenzene sulfonate.
The compositions and processes of this invention are also of considerable value in fire fighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting o~f the oxygen supply. This includes fire fighting and foaming runways for crash~landings as disclosed in U.SO Patents 2,514,310; 3,186,943; 3,422,011;
3,457,172; 3,479,285; and 3,541,010. Concentrations of from about 0.1% to about 5~ are use~ul.
The compositions and processes of this invention are also especially valuable in the field oE preparing gypsum board, plastic, and resin foams. The foams of this invention pro-vide a stable rela~ively thick structure permitting solid-ification of the resins, plastics, cellulosic particles, etc., into stable oam structures having light densities, thick cell walls and good structural lntegrity. Examples of forming processes which utilize foaming agents are described in U.S. Patents 3,669 J 898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concen~rate the mineral valuesr e.g., in the Eoam (beneficiation), can be carried out advantageously using the compositions and processes of this invention. Such processes are described in U.5. Patents 4,147~644; 4,139,482; 4,139,481; 4,138,350;
4,090,972 and 3,640,862.
A special advantage of the compositions and processes of this invention involves makin~ use of their exceptional stablility to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preferred cosurfactant and the foam can be applied ~o the foliage etc., of the plan~s. Such a process is disclosed in U.S. Patent 3,669 t 898.
: i -The range of utilities which are possible with the composi-tions and processes of this invention include all of the above and many more.
Typical compositions for use as light duty liquid detergent 5 ~ compositions in washing dishes comprise from about 5% to about 50%, preferably -from about 10~ to about l~0~ of the mixture of surfactants disclosed hereinbefore. From about 1% to about 50% of a solvent selected from the group consisting of Cl 3 alkanols, C~ 3 alkanolamines, C2 4 polyols, mixtures thereof, and the balallce water. It is a special advanta~3e of the compositions of this invention that they can be made in concentrated form ~up to about 50~ by wt. of the mixture of surfactants) Yvith only very Iow levels of organic solvents and without the addi-tion of expen-sive hydrotropic materials. Additional suds boosters or builders such as trialkyl amine oxides and fatty acid amides can also be used in amounts up to about 20~6. Fatty alcohols should not be used .
Shampoo compositions comprise from about 1% to about 95%, preferably from about 5% to about 20% of the mixture of surfac-tan ts mentioned hereinbefore, from about 1~ to abou t 5~ of an alkanol amide, from about 0 . 5% to about 3~ of a polymeric thick-ener, and the balance water. I t is a special advantage of the shampoos that they rinse quickly and readily.
Additional Ingredien-ts The compositions and processes of this invention can utili~e other compatible ingredients, including other surfactants, in addition to the mixture of surfactants herein disclosed . I n de tergent compositions -the compositions can contain any of the well known ingredients including minor amounts of other surfactants, c3etergency builders, soil suspending agents, brighteners, abras-ives, dyes, fabric conditioning agents, hair conditioning agen-ts, hydro-tropes, solvents, fillers, clays, perfumes, etc. Suil:able ingredients are disclosed in U.S. ~atents 4,166,039--~Vise;
4,157,978-'Llenaclo; 4,056,481--Tate; 4,049,586--Collier;
~L9~
4,035,257--Cherney; 4,019,~98--Benson et al; 4,000,080--Bartolotta et al; and 3,983,078--Collins. The shampoo compositions oE this invention can contain any of the additional ingredients known to the art to be suitable for use in shampoos. Listings of suitable additional ingred-ients, including low levels of other surfactants can be found in U.S~ Patents 4,089,945; 3,987,161; and 3,962,418.
Of special interest are ingredients which modify the feel of aqueous solutions containing the foaming compositions of this invention. ~or example, raising the pH to above about 8.5 by alkaline materials or incorporating the ter~iary alco-hols of the Jones et al, Canadian Patent 1,160,131 issued January 10~ 1984 Such ingredients are desirable for some consumers since the solutions do not have the normal "soapy"
feel associated with surfactant solutions.
The following nonlimiting examples illustrate the foaming compositions of the present invention.
Relative Volume of Suds Comparison and Consumer Preferance A B C
Generic ~remium Product Commercial Commercial of the Product Product Invention U.S. Crystal U.S.
Whi~ ~Palmoliv ~
FORMULA Weight %Weight ~Weight %
Sodi~n Cll 8 alkyl benzene sulfonate 10.5 13.0 18.0 C12_13 alkylpoly-~lucoside~ 3(>2%
free fatty alcohol) - - 12.0 Sodium 14-15 Y
polyethoxylate3 sul fate5.5 12.0 Balance of forrnula inc. water 84.0 70,0 70.0 SUDSI NG
Rela-tive Volume of Suds(m!) 110 125 220 0.2% solutions CONSUMER TEST
Overall preference, % 10 18 23 Favorable sudsing 10 comments, % 711 85 90 Favorable rinsing comments, ~ 3 6 10 The foaming composition of the invention is superior to a 15 representative generic product and at least equivalent to a representative premium commercial product and is preferred by consumers for rinsing reasons. The test involved 50 consumers washing soiled dishes in the test solutions. The consumers wore rubber gloves during -the test. The differences are significant at 20 the 95% confidence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test prccedure:
100 ml of the test solution at 115F is placed in a 500 ml 25 graduated cyliner: the solution is agitated by repea-ted inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds hei~ht is measured directly on the cylinder scale making allowance for the height o-f liquid remaining in the cylinder. The test solution is 30 made by adding the test product to water having a hardn~ss oF 7 gr. per U.S. gallon (Ca/l~/lg = 3/1) .
EXAMPLE l l -~
LAS Suds Boosting lVt, % of: A B C D E F G
_ 5Sodium C11 8 all~yl-benzene sulfonate 0 20 40 50 60 80 100 C12-l 5 alkYlPoly2-3 ylucoside 100 80 60 50 40 20 0 Relative Volume of suds ~ml) 140 220 280 300 310300 240 The suds (foam) were genera-ted as clescribed in Ex. I using 300 ppm of the surfactant mixtures in ci-ty water (~9 grains per gallon). The results clearly show the sudsing syner~ism For lS ratios greater than about 1 :2, i.e. for -the foaming composition of the invention herein.
EXAMPLE l l l Soap Sucls Boosting ~Vt. ~ of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 Cl 2-l 5 al kYIPI`/2-3 glucoside l O0 80 60 40 20 0 Relative Volurne of suds (ml.) ~ 160 270 280 300 310260 The suds were genera~ed as in Ex. I using 50û ppm. of the surfactant mixtures. This clata clearly indicates the sudsing synergism for the foaming composition of the invention herein, s~
EXAMPLE I V
FoamincJ wi-th Soap Effect of ~lardness on Relative Volume of Suds grains harclness 0 2 ~I 6 Sodium oleate 225 lO O O
Sodium oleate plus Cl 2-15 all<ylpoly2_3 glucoside (3:2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
EXAMPLE V
Allcyl Polyglucosidy (Cl2 15 alkYIPIY 2 3 g Suds E3Oosting for the Following Representative CosurFactants (3:2 ratio; 500 ppm) % increase in Foaming Sodium C11 8 all<ylbenzene sulfonate 100-150 Socliurn oleate 50-75 2 0 3-lN -coconuta I kyl-N,N-di methy I ] -2-hydroxy-1-sulfonate 40-60 Soclium C1L~ 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 10-30 Sodium coconut aiky! polyethoxylate3 sulfate 0-20 The above data clearly dernonstrate the criticality of utilizing a carboxylate or sulfonate anionic detergent cosurfactant for sudsing synergism with the alkyl polyglucoside surfactant.
EXAMPLE Vl Glucoside Chain Length Criticality 40:60 wt. ratio of C12_15 alkyl polyglucoside to sodium C12 alkylbenzene sulfonate (500 ppm. concentration) where the gluco~
sicle portion is:
S~
_ 19 _ Relative Vol-ime of Suds (ml) Monoglucoside 180 Diglucoside 240 S Pentaglucoside 260 Decag lucoside 170 Sodium C11 8 alkylbenzene sulfonate alone 160 10 "Diglucoside" etc. indicates the average glucoside chain length in the sample is two, etc. As can be seen from the above, significant synergism is obtained only with 1.5 or more glucoside units and preferably less than abou-t 10, more preFer-ably less than about 8 glucoside units.
EXAMPLE Vl l Alkylbenzene sulfonates (LAS) Homologs/phenyl-position (3:2 ratio; 500 ppm) Relative Volume of Suds ( ml ) 20 Ex . I l 's alkylpoly~lucoside plus:
Sodium C11 LAS, high 2-phenyl210 Sodium C11 LA5, low 2-phenyl 250 Sodium C12 LAS, high 2-phenyl225 Sodium C12 LAS, iow 2-phenyl 225 25 Sodium C14 LAS, high 2-phenyl210 Sodium C1LI LAS, low 2-phenyl215 As can be seen from the above, in ~3eneral C11, low 2-phenyl LAS is preferred for sudsing.
~9~5~
EXAMPLE Vl l l ;
Suds Boosting of Alkyl Poiyglucosides and Effect of Soil Relative Volume of Suds (ml) ~lithou t 5Oil Witl~ Soil 0.5% 1.0 0.2% aqueous solution of a detergent composition lO formulated with:
15% sodium C11 8 allcyl-benzene su I fonate 11.8 L ) 120 50 25 9~ C11.8 LAS %
Ex. I l 's alkyl poly~lucoside 310 130 70 30% C11.8 LAS 190 140 100 20~ C11 8 LAS -~ 12%
Ex. I's all<ylpolyglucoside 380 170 100 *
Test method of Ex. I modified by adding to the test solu-tion the indicated amount of soil. % is w-t. % of test solution.
The soil is a 44~/56% by weicJht mixture of Fluffo~) and PRE~) both of which products are available in the United States from The Procter ~ Camble Company.
As can be seen from the above, the benefit for the invention is even more remarkable when soil is present.
EXAMPLE I X
Relative Volume of Suds (ml) No Soil 1% Soil Present Ceneric commercial product (Crystal ~Yhite~)** 110 30 Premiurn commerical product B
(Palrnolive Liquic)~) 120 100 f'rcmilJM commercial product C
3L~g~;34~
12~ C11 8 LAS/8~ Ex. Il's -~
alkyl poly~lucoside 180 120 18% C11 8 LAS/12% Ex. Il's allcyl polyglucoside 240 150 5~ 24% C11 g LAS/16% Ex. Il's alkyl polyglucoside 300 180 Soil is added as described in Ex. Vl 1.
Crystal V~hite(~3 is available from Colgate-Palmolive Co.
Palmolive Liquid~3 is available from Colgate-Palmolive Co.
10 Joy~ is available from The Procter Gamble Company.
Suds ~enerated as in Ex. I usin~3 a test solution containing 0.2% by wt. of the indicated commercial product or 0.2% of a product formulated with the surractant mixtures shown.
15 As can be seen, the simple mixtures of surfactants represen-tative of this invention can be formulated to be superior, or at least equal, to even the best light-duty dishwashing liquids.
EXAMPLE X
Wt. ~ of: A B C D E F
20 C1 1 8 LAS (Sodium) 20 40 6080 100 Sucrose monolaurate 100 80 60 4020 0 Relative Volume of suds [ml.) 30 100 150 190210220 300 ppm of surfactant mixture used in test solution of Ex. I.
The above demonstrates that structures which are sirnilar to the alkyl polyglucosides do not provide the benefi~s of this in-vention .
EXAl\iIPLE Xl Shampoo Cocamido propyl betaine (30% aqueous solution) 50.00%
Ex. I's alkyl polyglucoside 5-00~
Polyethylene ~Iycol clistearate 1 . 00%
35 Preservative ~ 03%
Distille~ water q.s. 100.00%
S~
EXAMPLE Xl l Shampoo Alpha-olefin sulfonate (40% aqueous solu-tion) 30.00%
Ex. I's alkyl polyglucoside 3.00%
Hydroxyethyl cellulose 0.80%
Perfume ' 1 . 00%
Preservative 0.04~
~istilled water q.s. 100.00%
EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. % of: P~ B C D E F
Mixture of sodium C14_15 15 paraffin sul-fonate 0 20 40 60 80 100 C12-15 G4_5 100 80 60 40 20 0 Relative Vol. of Suds (ml) 185 250 275 275 235 210 Test Conditions:
Total concentration o-F 300 ppm; water having 8 grains of 20 mixed hardness.
C12 15G4_5 is a notation for an alkyl polysaccharide surfactant in ~/hich there are 4-5 glucoside uni-ts and in which the alkyl group has 12-15 carbons.
EXAMPLE XIV
Sodium vs. I~lagnes~um Alkylbenzene Sulfonate Relative Volume of Suds (ml.) Without Soil ~Vith Soil 0.6% 1.0%
0.2% aqueous solution of a 30 detergent compos;tion with:
15Q~ Ex. Il's alkyl poly-glucoside; 22% C11 ~
alkylbenzene sulfonate with the benzene group attached primarily to the center ~;~
of the alkyl chain, sodium neutralized 450 150 75 15~ Ex. Il's alkyl polyglucoside;
22~ C~ 8 alkylbenzene sulfonate with the ben~ene group attached primarily to the center of the alkyl chain, magnesium neutralized 450 200 110 10 Premium product ~Joy(~)) 350 120 75 *
Soil added to the test solution as in Ex. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially alkylpolygluco-sides have an HLB of from about 6 to about 27 and a critical **
micelie concentration ~CMC) of less than about 1000ppm, prefer-ably less than about 50Q. Short chain alkylpolysaccharides in which ti1e alkyl group contains less than about 8 carbon atoms have unacceptably high CMC's and those alkylpolysaccharides haviny more than about 4 saccharide units have unaccep-tably high 20 HLB's as is shown in the following table in which the alkyl group and the glucoside chain length were varied.
X of GL~ G1 G2 G3 GL~ G5 Glucosides X of 25Carbons ` ~--C4 HLE 5.1 12.4 17.9 23.3 28.834.2 C6 HLB 4.2 11.4 17.0 22.4 27.833.2 C8 HLB 3.2 10.5 16.0 21.4 26.932.3 30CI~IC ~7000 C10 HLB 2.2 9.6 15.0 20.4 26.031.4 CMC ~700 2000E
C12 ~ILB 1.3 8.6 lL~.1 19.5 25.030.'~
CMC ~6 . 0 ~70 ~200 225E ~250 -- 2~ -C~ lLB 0.4 7.6 13.2 18.6 24.0 29.4 ChlC ~6 ~20 25-60E
C16HLB 0.0 6.7 12.2 17.6 23.1 28.5 CMC ~0.3 ~0.6 ~4 5~ C HLi3 0 0 5.8 11.2 16.6 22.2 27,6 CMC
E=Estimated HLB determined according -to Davies: Proc. ~ International Congress, SurFace Activity 1,426, But-terwor-ths, London, 1957.
10 pprn As can be seen above, (1) longer pure glucoside chain lengths raise the HLi, and lower the molecule's surface activity (high CMC) and ~2) the shorter alkyl chain lengths have extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A i3 C
Magnesium linear Cl 1 2 alkylbenzene sulfonate 22.4 22.4 22,4 20 C12 13 all<ylpolyyluco-side (Gl 7~ (<2g6 free fatty alcohol) 14.9 14.9 14.9 Cg_l l alkoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkyldihydrOXY !-ethyl amine oxide - - 4 Ethanol 5 5 5 ~`~ater balance balance balance Formulas A, B and C were compared by generating suds with a constant source of agitation under standard conditions (1 gal. water, 115F. (46.1C) 7 gr. hardness in a 3 gal. dishpan using a standardized mixture of fat plus prol:ein, carb~)hydrate and edible acid). Dinner plates are washed with 4 rnl. of soil on 35 each plate and the suds height is measured after each five plates.
5~
30 plates in t~tal are washed and the integral of the suds height talcen over the nurnber of plates washed is reported as the SDW
grade ~SD~Y = Suds During Washing).
A B C
SDW g rade 2I~ 28 . ~ 28 . 4 This shows -that the addition of a small amo~lnt of -these amine oxides dramatically increases the amount of dishes that can be washed. Similar results are obtained when a fa-tty acid amide, e.g., a coconut -Fatty acid amide, diethanol amide, and/or isopro-panol amide is substituted, at least in part for the specific amine oxides .
EXAMPLE XVI I
105 grams of sodium dodecylbenzene sulfonate are mixed with 350 grams of anhydrous sodium sulfate. After the mixture is ground into a fine powder, 70 g of C12_13 alkylpolyglucosicle (G2 2) (<2~6 free fatty alcohol) are then mixed in. The mixture is transferred into a fluid bed dryer operated at room temperature (e.g., Aeromatic Inc., IModel STREA-1 ), then 100 grams of a 50%
solution of said allcylpolyglucosicle is sprayed onto the powder.
20 7.5 milliliters of a 1% polar blue solution are sprayed onto the powder and a small portion of perfume is then added. The resulting granule is dried in a vacuum oven a-t 30 in. of Hg vacuum at 50"C for ten hours to remove excess waterO
In a similar manner 60 grams of a 50% solution of said alkyi-25 polyglucoside is sprayed ont~ 100 gram of Berkite and 50 grams of sodium dodecylbenzene sul-fonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1 1 2 linear alkyl benzene sulfonate was admixed 30 with C12 alkylpolyglucoside G3 5 in a ratio of about ~:1. The mixture was used a-t a level of 400 ppm in ci ty water. The initial suds volume was more than 300 ml., but after the addition of about 1.25 grams of a standard grease soil per 200 ml. of wash solution, the suds had disappeared. Substitution of a sodium 35 C12 16 alkyl glyceryl ether sulfonate for 25g~ and 40% of the mixture extended tlle point at which there was no suds to 1.5 and~
1.75 grams of soil per 200 ml. of wash solution respectively.
Similar results are obtained when a sodium, potassium, ammonium, or monoetllanolammonium C1 2-1 6 alkylpolyethoxy3 acetate, or C1LI_16 olefin sulfonate or mixtures thereof is substitutecl for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides having 0 . 3% ancl 1% free fatty alcohol respectively .
~,Vt. %
Ammonium C1 1 2 linear alkyl benzene sulfonate 17 . 5 Magnesium Cl 1 2 linear alkyl benzene sulfonate 6 . 4 15 Ammonium C12 13 alkyl poly-ethoxy I ate ( 0 . 8 ) su I fate 6 . 1 C12 13 alkYIPIY~IUCside G1.7 Minors and water balance The SDW values for the low and high alcohol samples were 20 12.9 and 12.2 respecively with an LSDo 05 at 0.6. See Ex. XVI
for test method.
EXAMPLE XX
The following formulas were prepared:
% by weight ` f-A B C D
_ Ammonium/magnesium C11 2 linear alkyl benzene sulfonate 24. 221 . 8 Ammonium/magnesium C12-15 30 olefin sulfonate - - 12 . 8 10 . 6 Ammonium/magnesiUm C12_13 alkyl sulfonate - - 19 . 2 15 ~ 9 Ammonium C1 2-13 alkyl polyethoxylate ~0.8) 35 sulfate 6 . 55 . 8 ~9C~ 450 C12 fatty acid diethanol- ,~
amide - 3.8 - 5.5 C12_l 3 al~;ylpolyglucoside Gl 7 ~free fatty 5~ alcohol <O.S~) 5.34.8 4 3.3 ~llinors and water balance A B C D
The SD~ I ndex 79 89 97 107 The SD~V index is the SDW grade for each product as a l O percentage of the SDW value of a standard commercial product.
The following are examples of particularly preferred compo-sitions . The broad and preferred ranges of ing redients which can be used are given in the second and third columns, respec-tively, in each example.
EXAMPLE XX I
% by Weight Ammonium C11 L~ alkyl benzene sulfonate 17.5 10-3512-25 Magnesium C11 4 alkyl benzene sulfonate 6.4 0-11 3-9 Ammonium C12 13 alkyl poly-ethoxylate (0.8) sul fates 6.1 2-11 3-9 C12-13 alkyl polyglucoside (1.7) derived from glucose ( <0.5% free fatty alcohol ) ~.0 2-11 2-7 Ethanol 3.7 0-10 0-5 Ammonium xylene sulfonate 3.0 0-10 0-5 H2O ~ minor components, e.g., perfume Balance EXAMPLE XX I i ~ by l,Yeight Ammoniurn C1 2 13 alkyl suifate 15.7 7-23 10-20 Sociiurn C14 16 olefin sulfonate 10.4 4-19 6-13 ~c~
-- 2~3 --MgC12 6H2 5. 6 0-11 2-10 Coconut monoethanol amide 5 . 5 2-8 3-7 C12_13 alkyl polyglycoside (1.7) derived from glucose 5 ` ( ~0 . 5% free fatty alcohol ) 5 . 9 2~12 3-9 Ethanol 4. 0 0-l O 0-l O
~12O and rninor components, e.g., perfume Baiance The allcyl groups in the surfactants of Examples XXI and 10 XXII can vary from about 10 to about 16 carbon atoms and the cations can be ammcnium, sodium, potassium, monoethanolammonium, diethanolammonium, triethanolammonium, magnesium, or preferably, mixtures therof. ~ny of the preferred alkyl polyglycosides can be used and other known amine oxide and amide suds boosters 15 disclosed herein can be used.
~Vhen a 2:1 mixture of an ammonium C11 2 alkylbenzene C12-13 a~l<YIPOIy~l~lcoside ~2-4) (>2~6 f f alcohol) are tested under the conditions of Example l l the ini-tial 20 suds volur,~e is good, but -the SDW grade is not as good as some premium commercial products. Substi-tution of between 25~6 and 50% of the mixture with a sodium C12-16 alkyl glyceryl eth sulfonate, or sodiurn C14 16 olefin sulfonate, or sodium C12 13 alkyl polyethoxylate(3) acetate increases the SD~,V grade without ~5 lo~,vering the initial sudsing excessively.
I'nown analytical techniques can be used to determine the structures of the alkylpolysaccharide surfactants herein; for example, to determine the glycosidîc chain length, the amount of butyl glucoside, the free fatty alcohol con-tent, and the level of 30 unreacted polysaccharide. More specifically, gas or liquid chromatography can be used to determine the unreacted alcohol content and the unreacted polysaccharide content respectively.
Proton nmr can be used to determine the average glycosidic chain length. The point of attachment of the hydrophilic portion of the 35 molecule to t~le hydrophobic portion of the molecule can be determined by 3C nmr.
5~
The aikylpolysaccharide surfactants are complex mixtures`
Their components vary dependin~ upon the nature of the startiny materials and the reaction by which they are prepared. Analyti-c21 standards which are useful in calibrating instruments for 5 ~ analyzin~ the components. of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behring Co. L aJolla, California. These standards include those for octyl~lucoside (Calbiocherm ~494559), decylglucoside [Calbiochem ~252715), dodecylmaltoside (Calbiochem #32~13555).
The HLBs of alkylpolysaccharide surfactants useful in the foaming compositions of this invention have the values given in EXAMPLE XV; the CMCs will approximate those values given in the same example. Alkylpolysaccharide surfactants having the structures specified in the claims and characterized by one or 15 more of the standard analytical techniques will give the resul-ts indicated in the examples.
, . . .
about 50% of a water soluble alkylbenzene sulfonate~
cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 596 to about 999~, preferably 50-90~ of a cosurfactant selected from the group consisting of an allcyl glyceryl ether sulfonate in which the alkyl group contains from about ~3 to about 18 carbon atoms, an alpha-oleFin sul-fonate in which the olefin group contains from about 10 to about 18 carbon atoms, an alkyl polyethoxylate carboxylate in which the alkyl group contains from about 10 to about 18 carbon atoms, and the polyethoxylate chain contains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
Such compositions have improved suds mileage as compared to compositions containing only -the alkyl benzene sulfonate cosur-factant and the alkylpolysaccharide surfactan-t.
Another preferred embodimen-t of a foaming composition of -the invention herein comprises 20 ( 1 ) an alkylpolysaccharide sur-factant havin~ the forrnula RO(R1O)t(Z3X wherein Z is a moie-ty derived from a reducing saccharide containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from abou t 1 . 5 to about 10;
30 (2) an anionic cosurfactant selected from the group con-sisting of sulfates, sul~onates, carboxylates and mix-tures thereof neutrali~ed with one or more cationic moieties M -to comple~e the formula, the ratio oF (2) to ( 1 ) beir7g from about 1 :10 to about 10 :1; and s~
(3) from about 2% -to about 10% of an auxiliary foam booster"
selected from the group consisting oF:
~a) amides having the formula R7-C-N- ( RS ) 2 wherein R7 is an alkyl ~roup containin~3 from about ~ to about 1~ carbon atoms, preferably about 12 to about 14 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1 3 alkyl, C1 3 alkanol, and (C2H4O-~1_4H groups and mixtures thereof;
(b) amine oxides having -the formula:
R4~oR )bN(R )2 wherein R ~ is an alkyl group containin~ from abou-t to about 1~ carbon atoms, preferably from 12 to 14 carbon atoms, each R5 con-tains two or three carbon atoms, b is from 0 to about 30, each R is the same or different and is selected from the group consisting of C1_3 al~yl, C1_3 -(C2H40)1_6H groups and mixtures thereof; and (c) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mileage.
Preferred anionic cosurfactants are alkylbenzene sulfonate, alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sul-fates and paraffin sulfonates and mixtures thereof. The cationic moieties are selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, 30 triethanolammonium, calcium, magnesium and mixtures thereof.
Preferred compositions of this embodiment of the invention cornprise from 1~ to abou-t 95%, preferably 5P~ to about 50% of an -alkylpolysaccharicie surfactant in which the alkyl group contains from 12 to 14 carbon atoms, x is from 1 . 5 to 4, more preferably 35 1.6 to 2.7; from 1O to about 95~O, preferably from about 10% to about 50% of an anionic cosurfac-tant neutralized with one or more~
cationic moieties and which is a mixture of ~1) from 16 to about 95~, preferably from about 5% to about 50~6 of an alkyl benzene sulfonate in which the allcyl group contains from about 8 to about 13 carbon atoms or an alpha-olefin sulfonate in which the olefin group contains from about 10 to about 18 carbon a~oms, or mixtures thereof; and (2) frorr 1% to about 95%, preferably from about 5% to about 50% of an alkyl polyethoxylate sulfate in which the alkyl group contains from about 8 to about 18 carbon atoms, preferably from 12 to 1 L~ carbon atoms and from about one to about six ethoxylate moieties and wherein from about 1% -to about 100%, preferably from about 10% to about 80% of the cationic rnoieties are magnesium: and wherein the auxiliary foam booster is an amide.
Another pre-ferred foaming composition of the invention herein is an ayglomerated light duty detergen-t granule composi-tion cornprising ( 1 ) from about 56 to about 60%, preferably from 1 OP6 to about 20-6 of an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x wherein Z is a moiety derived from a reducing saccharide moiety containing from 5 to 6 car;bon atoms and wherein R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl or hydroxyalkyl grups or mixtures thereof in which said alkyl groups contain from about ~3 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms; R
contains from 2 to about 4 carbon atoms; -t is from 0 to about 30; and x is a number frorn about 1.5 to about 10, preferably 1.5 to 4, most preferably 1 6 to 2.7;
(2) frorn about 5% to abou~ 60P6 of an alkyl ben~ene sul-fonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, said alkyl ~ 12 ~
benzene sulfonate neutralized with one or more cationic moieties (M) to balance the formula;
(3) from about 5~ to about ~0%, preferably from about 10% to about 20% of an alkylpolyethoxylate sulfate cosurfactant in which the alkyl group contains from about 10 to about 16 carbon atoms and in which there are from 1 to about 6 ethoxylate groups, said alkylpolyethoxylate sulfate neu~ra-lized with one or more catlonic moieties M to complete the formula.
(4) from about 5% to about 80% of a water soluble inorganic salt selected from the group consisting of sodi~l and potassium sulfates, chlorides, carbonates, phosphates; and mixtures thereof.
The Processes Mixtures of alkylbenzene sulfonate and/or the soap cosurfactant and the alkylpolysaccharide surfactant can be used at levels of from about 0.01% to about 95%, in ratios of cosurfactant to alkylpolysaccharide of from about 10:1 to about 1:10, in water with agitation to provide foamsO
These foams are relatively stable and, iE not disturbed, can exist for several days~ Furthermore, the foam has structural integrity and do~s not spread out. The foams prepared using mixtures of alkylbenzene sulfonate and ~he alkylpolysaccharide are unique in that they do not have a "slippery" feel. All of the foams rinse ~u.ickly~
The unusual properties of the foams of this invention make them valuable for use not only in soap bars, bubble baths, shaving creams, laundry, dishwashing, and washing hair, where a good volume of stable suds and quick rins-ability are desirable, but also in a large number of fields unrelated to detergency.
The compositions and processes of this invention are particularly valuable for use in the "foam" or "mist" well drilling processes in which the foam is used to carry water and/or soil particles to the surface of the bore hole. A
description of such a drilling method can be found in U.S.
, ~,,,;~
Patents 3,303,896; 3,111,178; 3,130,798; and 3,215,200. In such a process, the surfactants are present at a level of from about 0.01% to about 5~, preferably from about 0.01~
to about 2~, most preferably from about 0.05% to about 0.5%.
The preferred cosurfactant is an alkylbenzene sulfonate.
The compositions and processes of this invention are also of considerable value in fire fighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting o~f the oxygen supply. This includes fire fighting and foaming runways for crash~landings as disclosed in U.SO Patents 2,514,310; 3,186,943; 3,422,011;
3,457,172; 3,479,285; and 3,541,010. Concentrations of from about 0.1% to about 5~ are use~ul.
The compositions and processes of this invention are also especially valuable in the field oE preparing gypsum board, plastic, and resin foams. The foams of this invention pro-vide a stable rela~ively thick structure permitting solid-ification of the resins, plastics, cellulosic particles, etc., into stable oam structures having light densities, thick cell walls and good structural lntegrity. Examples of forming processes which utilize foaming agents are described in U.S. Patents 3,669 J 898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concen~rate the mineral valuesr e.g., in the Eoam (beneficiation), can be carried out advantageously using the compositions and processes of this invention. Such processes are described in U.5. Patents 4,147~644; 4,139,482; 4,139,481; 4,138,350;
4,090,972 and 3,640,862.
A special advantage of the compositions and processes of this invention involves makin~ use of their exceptional stablility to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preferred cosurfactant and the foam can be applied ~o the foliage etc., of the plan~s. Such a process is disclosed in U.S. Patent 3,669 t 898.
: i -The range of utilities which are possible with the composi-tions and processes of this invention include all of the above and many more.
Typical compositions for use as light duty liquid detergent 5 ~ compositions in washing dishes comprise from about 5% to about 50%, preferably -from about 10~ to about l~0~ of the mixture of surfactants disclosed hereinbefore. From about 1% to about 50% of a solvent selected from the group consisting of Cl 3 alkanols, C~ 3 alkanolamines, C2 4 polyols, mixtures thereof, and the balallce water. It is a special advanta~3e of the compositions of this invention that they can be made in concentrated form ~up to about 50~ by wt. of the mixture of surfactants) Yvith only very Iow levels of organic solvents and without the addi-tion of expen-sive hydrotropic materials. Additional suds boosters or builders such as trialkyl amine oxides and fatty acid amides can also be used in amounts up to about 20~6. Fatty alcohols should not be used .
Shampoo compositions comprise from about 1% to about 95%, preferably from about 5% to about 20% of the mixture of surfac-tan ts mentioned hereinbefore, from about 1~ to abou t 5~ of an alkanol amide, from about 0 . 5% to about 3~ of a polymeric thick-ener, and the balance water. I t is a special advantage of the shampoos that they rinse quickly and readily.
Additional Ingredien-ts The compositions and processes of this invention can utili~e other compatible ingredients, including other surfactants, in addition to the mixture of surfactants herein disclosed . I n de tergent compositions -the compositions can contain any of the well known ingredients including minor amounts of other surfactants, c3etergency builders, soil suspending agents, brighteners, abras-ives, dyes, fabric conditioning agents, hair conditioning agen-ts, hydro-tropes, solvents, fillers, clays, perfumes, etc. Suil:able ingredients are disclosed in U.S. ~atents 4,166,039--~Vise;
4,157,978-'Llenaclo; 4,056,481--Tate; 4,049,586--Collier;
~L9~
4,035,257--Cherney; 4,019,~98--Benson et al; 4,000,080--Bartolotta et al; and 3,983,078--Collins. The shampoo compositions oE this invention can contain any of the additional ingredients known to the art to be suitable for use in shampoos. Listings of suitable additional ingred-ients, including low levels of other surfactants can be found in U.S~ Patents 4,089,945; 3,987,161; and 3,962,418.
Of special interest are ingredients which modify the feel of aqueous solutions containing the foaming compositions of this invention. ~or example, raising the pH to above about 8.5 by alkaline materials or incorporating the ter~iary alco-hols of the Jones et al, Canadian Patent 1,160,131 issued January 10~ 1984 Such ingredients are desirable for some consumers since the solutions do not have the normal "soapy"
feel associated with surfactant solutions.
The following nonlimiting examples illustrate the foaming compositions of the present invention.
Relative Volume of Suds Comparison and Consumer Preferance A B C
Generic ~remium Product Commercial Commercial of the Product Product Invention U.S. Crystal U.S.
Whi~ ~Palmoliv ~
FORMULA Weight %Weight ~Weight %
Sodi~n Cll 8 alkyl benzene sulfonate 10.5 13.0 18.0 C12_13 alkylpoly-~lucoside~ 3(>2%
free fatty alcohol) - - 12.0 Sodium 14-15 Y
polyethoxylate3 sul fate5.5 12.0 Balance of forrnula inc. water 84.0 70,0 70.0 SUDSI NG
Rela-tive Volume of Suds(m!) 110 125 220 0.2% solutions CONSUMER TEST
Overall preference, % 10 18 23 Favorable sudsing 10 comments, % 711 85 90 Favorable rinsing comments, ~ 3 6 10 The foaming composition of the invention is superior to a 15 representative generic product and at least equivalent to a representative premium commercial product and is preferred by consumers for rinsing reasons. The test involved 50 consumers washing soiled dishes in the test solutions. The consumers wore rubber gloves during -the test. The differences are significant at 20 the 95% confidence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test prccedure:
100 ml of the test solution at 115F is placed in a 500 ml 25 graduated cyliner: the solution is agitated by repea-ted inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds hei~ht is measured directly on the cylinder scale making allowance for the height o-f liquid remaining in the cylinder. The test solution is 30 made by adding the test product to water having a hardn~ss oF 7 gr. per U.S. gallon (Ca/l~/lg = 3/1) .
EXAMPLE l l -~
LAS Suds Boosting lVt, % of: A B C D E F G
_ 5Sodium C11 8 all~yl-benzene sulfonate 0 20 40 50 60 80 100 C12-l 5 alkYlPoly2-3 ylucoside 100 80 60 50 40 20 0 Relative Volume of suds ~ml) 140 220 280 300 310300 240 The suds (foam) were genera-ted as clescribed in Ex. I using 300 ppm of the surfactant mixtures in ci-ty water (~9 grains per gallon). The results clearly show the sudsing syner~ism For lS ratios greater than about 1 :2, i.e. for -the foaming composition of the invention herein.
EXAMPLE l l l Soap Sucls Boosting ~Vt. ~ of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 Cl 2-l 5 al kYIPI`/2-3 glucoside l O0 80 60 40 20 0 Relative Volurne of suds (ml.) ~ 160 270 280 300 310260 The suds were genera~ed as in Ex. I using 50û ppm. of the surfactant mixtures. This clata clearly indicates the sudsing synergism for the foaming composition of the invention herein, s~
EXAMPLE I V
FoamincJ wi-th Soap Effect of ~lardness on Relative Volume of Suds grains harclness 0 2 ~I 6 Sodium oleate 225 lO O O
Sodium oleate plus Cl 2-15 all<ylpoly2_3 glucoside (3:2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
EXAMPLE V
Allcyl Polyglucosidy (Cl2 15 alkYIPIY 2 3 g Suds E3Oosting for the Following Representative CosurFactants (3:2 ratio; 500 ppm) % increase in Foaming Sodium C11 8 all<ylbenzene sulfonate 100-150 Socliurn oleate 50-75 2 0 3-lN -coconuta I kyl-N,N-di methy I ] -2-hydroxy-1-sulfonate 40-60 Soclium C1L~ 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 10-30 Sodium coconut aiky! polyethoxylate3 sulfate 0-20 The above data clearly dernonstrate the criticality of utilizing a carboxylate or sulfonate anionic detergent cosurfactant for sudsing synergism with the alkyl polyglucoside surfactant.
EXAMPLE Vl Glucoside Chain Length Criticality 40:60 wt. ratio of C12_15 alkyl polyglucoside to sodium C12 alkylbenzene sulfonate (500 ppm. concentration) where the gluco~
sicle portion is:
S~
_ 19 _ Relative Vol-ime of Suds (ml) Monoglucoside 180 Diglucoside 240 S Pentaglucoside 260 Decag lucoside 170 Sodium C11 8 alkylbenzene sulfonate alone 160 10 "Diglucoside" etc. indicates the average glucoside chain length in the sample is two, etc. As can be seen from the above, significant synergism is obtained only with 1.5 or more glucoside units and preferably less than abou-t 10, more preFer-ably less than about 8 glucoside units.
EXAMPLE Vl l Alkylbenzene sulfonates (LAS) Homologs/phenyl-position (3:2 ratio; 500 ppm) Relative Volume of Suds ( ml ) 20 Ex . I l 's alkylpoly~lucoside plus:
Sodium C11 LAS, high 2-phenyl210 Sodium C11 LA5, low 2-phenyl 250 Sodium C12 LAS, high 2-phenyl225 Sodium C12 LAS, iow 2-phenyl 225 25 Sodium C14 LAS, high 2-phenyl210 Sodium C1LI LAS, low 2-phenyl215 As can be seen from the above, in ~3eneral C11, low 2-phenyl LAS is preferred for sudsing.
~9~5~
EXAMPLE Vl l l ;
Suds Boosting of Alkyl Poiyglucosides and Effect of Soil Relative Volume of Suds (ml) ~lithou t 5Oil Witl~ Soil 0.5% 1.0 0.2% aqueous solution of a detergent composition lO formulated with:
15% sodium C11 8 allcyl-benzene su I fonate 11.8 L ) 120 50 25 9~ C11.8 LAS %
Ex. I l 's alkyl poly~lucoside 310 130 70 30% C11.8 LAS 190 140 100 20~ C11 8 LAS -~ 12%
Ex. I's all<ylpolyglucoside 380 170 100 *
Test method of Ex. I modified by adding to the test solu-tion the indicated amount of soil. % is w-t. % of test solution.
The soil is a 44~/56% by weicJht mixture of Fluffo~) and PRE~) both of which products are available in the United States from The Procter ~ Camble Company.
As can be seen from the above, the benefit for the invention is even more remarkable when soil is present.
EXAMPLE I X
Relative Volume of Suds (ml) No Soil 1% Soil Present Ceneric commercial product (Crystal ~Yhite~)** 110 30 Premiurn commerical product B
(Palrnolive Liquic)~) 120 100 f'rcmilJM commercial product C
3L~g~;34~
12~ C11 8 LAS/8~ Ex. Il's -~
alkyl poly~lucoside 180 120 18% C11 8 LAS/12% Ex. Il's allcyl polyglucoside 240 150 5~ 24% C11 g LAS/16% Ex. Il's alkyl polyglucoside 300 180 Soil is added as described in Ex. Vl 1.
Crystal V~hite(~3 is available from Colgate-Palmolive Co.
Palmolive Liquid~3 is available from Colgate-Palmolive Co.
10 Joy~ is available from The Procter Gamble Company.
Suds ~enerated as in Ex. I usin~3 a test solution containing 0.2% by wt. of the indicated commercial product or 0.2% of a product formulated with the surractant mixtures shown.
15 As can be seen, the simple mixtures of surfactants represen-tative of this invention can be formulated to be superior, or at least equal, to even the best light-duty dishwashing liquids.
EXAMPLE X
Wt. ~ of: A B C D E F
20 C1 1 8 LAS (Sodium) 20 40 6080 100 Sucrose monolaurate 100 80 60 4020 0 Relative Volume of suds [ml.) 30 100 150 190210220 300 ppm of surfactant mixture used in test solution of Ex. I.
The above demonstrates that structures which are sirnilar to the alkyl polyglucosides do not provide the benefi~s of this in-vention .
EXAl\iIPLE Xl Shampoo Cocamido propyl betaine (30% aqueous solution) 50.00%
Ex. I's alkyl polyglucoside 5-00~
Polyethylene ~Iycol clistearate 1 . 00%
35 Preservative ~ 03%
Distille~ water q.s. 100.00%
S~
EXAMPLE Xl l Shampoo Alpha-olefin sulfonate (40% aqueous solu-tion) 30.00%
Ex. I's alkyl polyglucoside 3.00%
Hydroxyethyl cellulose 0.80%
Perfume ' 1 . 00%
Preservative 0.04~
~istilled water q.s. 100.00%
EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. % of: P~ B C D E F
Mixture of sodium C14_15 15 paraffin sul-fonate 0 20 40 60 80 100 C12-15 G4_5 100 80 60 40 20 0 Relative Vol. of Suds (ml) 185 250 275 275 235 210 Test Conditions:
Total concentration o-F 300 ppm; water having 8 grains of 20 mixed hardness.
C12 15G4_5 is a notation for an alkyl polysaccharide surfactant in ~/hich there are 4-5 glucoside uni-ts and in which the alkyl group has 12-15 carbons.
EXAMPLE XIV
Sodium vs. I~lagnes~um Alkylbenzene Sulfonate Relative Volume of Suds (ml.) Without Soil ~Vith Soil 0.6% 1.0%
0.2% aqueous solution of a 30 detergent compos;tion with:
15Q~ Ex. Il's alkyl poly-glucoside; 22% C11 ~
alkylbenzene sulfonate with the benzene group attached primarily to the center ~;~
of the alkyl chain, sodium neutralized 450 150 75 15~ Ex. Il's alkyl polyglucoside;
22~ C~ 8 alkylbenzene sulfonate with the ben~ene group attached primarily to the center of the alkyl chain, magnesium neutralized 450 200 110 10 Premium product ~Joy(~)) 350 120 75 *
Soil added to the test solution as in Ex. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially alkylpolygluco-sides have an HLB of from about 6 to about 27 and a critical **
micelie concentration ~CMC) of less than about 1000ppm, prefer-ably less than about 50Q. Short chain alkylpolysaccharides in which ti1e alkyl group contains less than about 8 carbon atoms have unacceptably high CMC's and those alkylpolysaccharides haviny more than about 4 saccharide units have unaccep-tably high 20 HLB's as is shown in the following table in which the alkyl group and the glucoside chain length were varied.
X of GL~ G1 G2 G3 GL~ G5 Glucosides X of 25Carbons ` ~--C4 HLE 5.1 12.4 17.9 23.3 28.834.2 C6 HLB 4.2 11.4 17.0 22.4 27.833.2 C8 HLB 3.2 10.5 16.0 21.4 26.932.3 30CI~IC ~7000 C10 HLB 2.2 9.6 15.0 20.4 26.031.4 CMC ~700 2000E
C12 ~ILB 1.3 8.6 lL~.1 19.5 25.030.'~
CMC ~6 . 0 ~70 ~200 225E ~250 -- 2~ -C~ lLB 0.4 7.6 13.2 18.6 24.0 29.4 ChlC ~6 ~20 25-60E
C16HLB 0.0 6.7 12.2 17.6 23.1 28.5 CMC ~0.3 ~0.6 ~4 5~ C HLi3 0 0 5.8 11.2 16.6 22.2 27,6 CMC
E=Estimated HLB determined according -to Davies: Proc. ~ International Congress, SurFace Activity 1,426, But-terwor-ths, London, 1957.
10 pprn As can be seen above, (1) longer pure glucoside chain lengths raise the HLi, and lower the molecule's surface activity (high CMC) and ~2) the shorter alkyl chain lengths have extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A i3 C
Magnesium linear Cl 1 2 alkylbenzene sulfonate 22.4 22.4 22,4 20 C12 13 all<ylpolyyluco-side (Gl 7~ (<2g6 free fatty alcohol) 14.9 14.9 14.9 Cg_l l alkoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkyldihydrOXY !-ethyl amine oxide - - 4 Ethanol 5 5 5 ~`~ater balance balance balance Formulas A, B and C were compared by generating suds with a constant source of agitation under standard conditions (1 gal. water, 115F. (46.1C) 7 gr. hardness in a 3 gal. dishpan using a standardized mixture of fat plus prol:ein, carb~)hydrate and edible acid). Dinner plates are washed with 4 rnl. of soil on 35 each plate and the suds height is measured after each five plates.
5~
30 plates in t~tal are washed and the integral of the suds height talcen over the nurnber of plates washed is reported as the SDW
grade ~SD~Y = Suds During Washing).
A B C
SDW g rade 2I~ 28 . ~ 28 . 4 This shows -that the addition of a small amo~lnt of -these amine oxides dramatically increases the amount of dishes that can be washed. Similar results are obtained when a fa-tty acid amide, e.g., a coconut -Fatty acid amide, diethanol amide, and/or isopro-panol amide is substituted, at least in part for the specific amine oxides .
EXAMPLE XVI I
105 grams of sodium dodecylbenzene sulfonate are mixed with 350 grams of anhydrous sodium sulfate. After the mixture is ground into a fine powder, 70 g of C12_13 alkylpolyglucosicle (G2 2) (<2~6 free fatty alcohol) are then mixed in. The mixture is transferred into a fluid bed dryer operated at room temperature (e.g., Aeromatic Inc., IModel STREA-1 ), then 100 grams of a 50%
solution of said allcylpolyglucosicle is sprayed onto the powder.
20 7.5 milliliters of a 1% polar blue solution are sprayed onto the powder and a small portion of perfume is then added. The resulting granule is dried in a vacuum oven a-t 30 in. of Hg vacuum at 50"C for ten hours to remove excess waterO
In a similar manner 60 grams of a 50% solution of said alkyi-25 polyglucoside is sprayed ont~ 100 gram of Berkite and 50 grams of sodium dodecylbenzene sul-fonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1 1 2 linear alkyl benzene sulfonate was admixed 30 with C12 alkylpolyglucoside G3 5 in a ratio of about ~:1. The mixture was used a-t a level of 400 ppm in ci ty water. The initial suds volume was more than 300 ml., but after the addition of about 1.25 grams of a standard grease soil per 200 ml. of wash solution, the suds had disappeared. Substitution of a sodium 35 C12 16 alkyl glyceryl ether sulfonate for 25g~ and 40% of the mixture extended tlle point at which there was no suds to 1.5 and~
1.75 grams of soil per 200 ml. of wash solution respectively.
Similar results are obtained when a sodium, potassium, ammonium, or monoetllanolammonium C1 2-1 6 alkylpolyethoxy3 acetate, or C1LI_16 olefin sulfonate or mixtures thereof is substitutecl for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides having 0 . 3% ancl 1% free fatty alcohol respectively .
~,Vt. %
Ammonium C1 1 2 linear alkyl benzene sulfonate 17 . 5 Magnesium Cl 1 2 linear alkyl benzene sulfonate 6 . 4 15 Ammonium C12 13 alkyl poly-ethoxy I ate ( 0 . 8 ) su I fate 6 . 1 C12 13 alkYIPIY~IUCside G1.7 Minors and water balance The SDW values for the low and high alcohol samples were 20 12.9 and 12.2 respecively with an LSDo 05 at 0.6. See Ex. XVI
for test method.
EXAMPLE XX
The following formulas were prepared:
% by weight ` f-A B C D
_ Ammonium/magnesium C11 2 linear alkyl benzene sulfonate 24. 221 . 8 Ammonium/magnesium C12-15 30 olefin sulfonate - - 12 . 8 10 . 6 Ammonium/magnesiUm C12_13 alkyl sulfonate - - 19 . 2 15 ~ 9 Ammonium C1 2-13 alkyl polyethoxylate ~0.8) 35 sulfate 6 . 55 . 8 ~9C~ 450 C12 fatty acid diethanol- ,~
amide - 3.8 - 5.5 C12_l 3 al~;ylpolyglucoside Gl 7 ~free fatty 5~ alcohol <O.S~) 5.34.8 4 3.3 ~llinors and water balance A B C D
The SD~ I ndex 79 89 97 107 The SD~V index is the SDW grade for each product as a l O percentage of the SDW value of a standard commercial product.
The following are examples of particularly preferred compo-sitions . The broad and preferred ranges of ing redients which can be used are given in the second and third columns, respec-tively, in each example.
EXAMPLE XX I
% by Weight Ammonium C11 L~ alkyl benzene sulfonate 17.5 10-3512-25 Magnesium C11 4 alkyl benzene sulfonate 6.4 0-11 3-9 Ammonium C12 13 alkyl poly-ethoxylate (0.8) sul fates 6.1 2-11 3-9 C12-13 alkyl polyglucoside (1.7) derived from glucose ( <0.5% free fatty alcohol ) ~.0 2-11 2-7 Ethanol 3.7 0-10 0-5 Ammonium xylene sulfonate 3.0 0-10 0-5 H2O ~ minor components, e.g., perfume Balance EXAMPLE XX I i ~ by l,Yeight Ammoniurn C1 2 13 alkyl suifate 15.7 7-23 10-20 Sociiurn C14 16 olefin sulfonate 10.4 4-19 6-13 ~c~
-- 2~3 --MgC12 6H2 5. 6 0-11 2-10 Coconut monoethanol amide 5 . 5 2-8 3-7 C12_13 alkyl polyglycoside (1.7) derived from glucose 5 ` ( ~0 . 5% free fatty alcohol ) 5 . 9 2~12 3-9 Ethanol 4. 0 0-l O 0-l O
~12O and rninor components, e.g., perfume Baiance The allcyl groups in the surfactants of Examples XXI and 10 XXII can vary from about 10 to about 16 carbon atoms and the cations can be ammcnium, sodium, potassium, monoethanolammonium, diethanolammonium, triethanolammonium, magnesium, or preferably, mixtures therof. ~ny of the preferred alkyl polyglycosides can be used and other known amine oxide and amide suds boosters 15 disclosed herein can be used.
~Vhen a 2:1 mixture of an ammonium C11 2 alkylbenzene C12-13 a~l<YIPOIy~l~lcoside ~2-4) (>2~6 f f alcohol) are tested under the conditions of Example l l the ini-tial 20 suds volur,~e is good, but -the SDW grade is not as good as some premium commercial products. Substi-tution of between 25~6 and 50% of the mixture with a sodium C12-16 alkyl glyceryl eth sulfonate, or sodiurn C14 16 olefin sulfonate, or sodium C12 13 alkyl polyethoxylate(3) acetate increases the SD~,V grade without ~5 lo~,vering the initial sudsing excessively.
I'nown analytical techniques can be used to determine the structures of the alkylpolysaccharide surfactants herein; for example, to determine the glycosidîc chain length, the amount of butyl glucoside, the free fatty alcohol con-tent, and the level of 30 unreacted polysaccharide. More specifically, gas or liquid chromatography can be used to determine the unreacted alcohol content and the unreacted polysaccharide content respectively.
Proton nmr can be used to determine the average glycosidic chain length. The point of attachment of the hydrophilic portion of the 35 molecule to t~le hydrophobic portion of the molecule can be determined by 3C nmr.
5~
The aikylpolysaccharide surfactants are complex mixtures`
Their components vary dependin~ upon the nature of the startiny materials and the reaction by which they are prepared. Analyti-c21 standards which are useful in calibrating instruments for 5 ~ analyzin~ the components. of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behring Co. L aJolla, California. These standards include those for octyl~lucoside (Calbiocherm ~494559), decylglucoside [Calbiochem ~252715), dodecylmaltoside (Calbiochem #32~13555).
The HLBs of alkylpolysaccharide surfactants useful in the foaming compositions of this invention have the values given in EXAMPLE XV; the CMCs will approximate those values given in the same example. Alkylpolysaccharide surfactants having the structures specified in the claims and characterized by one or 15 more of the standard analytical techniques will give the resul-ts indicated in the examples.
, . . .
Claims (5)
1. An agglomerated light-duty detergent granule composition comprising (1) from about 5% to about 60% of an alkylpolysaccharide surfactant having the formula RO(RlO)t(Z)x where Z
is a moiety derived from a reducing saccharide con-taining from 5 to 6 carbon atoms and wherein R is an alkyl, alkylphenyl, hydroxy alkylphenyl or hydroxy-alkyl hydrophobic group or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R1 contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from about 1.5 to about 10;
(2) from about 5% to about 60% of an alkyl benzene sulfonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, said alkyl benzene sulfonate neutralized with one or more cationic moieties;
(3) from about 5% to about 60% of an alkylpolyethoxy-late sulfate cosurfactant in which the alkyl group contains from about 10 to about 16 carbon atoms and there are from about 1 to about 6 ethoxylate groups, said alkylpolyethoxylate sulfates neutralized with one or more cationic moieties; and (4) from about 5% to about 80% water soluble inorganic salt selected from the group consisting of sodium and potassium sulfates, chlorides, carbonates, phosphates, and mixtures thereof.
is a moiety derived from a reducing saccharide con-taining from 5 to 6 carbon atoms and wherein R is an alkyl, alkylphenyl, hydroxy alkylphenyl or hydroxy-alkyl hydrophobic group or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R1 contains from 2 to about 4 carbon atoms; t is from 0 to about 30; and x is a number from about 1.5 to about 10;
(2) from about 5% to about 60% of an alkyl benzene sulfonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, said alkyl benzene sulfonate neutralized with one or more cationic moieties;
(3) from about 5% to about 60% of an alkylpolyethoxy-late sulfate cosurfactant in which the alkyl group contains from about 10 to about 16 carbon atoms and there are from about 1 to about 6 ethoxylate groups, said alkylpolyethoxylate sulfates neutralized with one or more cationic moieties; and (4) from about 5% to about 80% water soluble inorganic salt selected from the group consisting of sodium and potassium sulfates, chlorides, carbonates, phosphates, and mixtures thereof.
2. The composition of Claim 1 wherein the cationic moieties for the cosurfactants (2) and (3) are selected from the group consisting of sodium, potassium, ammonium, monoethanol-ammonium, diethanolammonium, triethanolammonium, magnesium and mixtures theeof.
3. The composition of Claim 2 wherein the phenyl portion of the alkylbenzene sulfonate is attached near the middle of the alkyl chain and the cationic moiety is magnesium.
4. A composition according to Claims 1-3 wherein x is a number of from 1. 5 to 4.
5. The composition of Claims 1-3 wherein x is a number from 1.6 to 2.7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37169682A | 1982-04-26 | 1982-04-26 | |
| US271,696 | 1982-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1190450A true CA1190450A (en) | 1985-07-16 |
Family
ID=23465041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407166A Expired CA1190450A (en) | 1982-04-26 | 1982-07-13 | Foaming surfactant compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58187500A (en) |
| CA (1) | CA1190450A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2657495B2 (en) * | 1987-09-09 | 1997-09-24 | 株式会社資生堂 | Detergent composition |
| JP2824192B2 (en) * | 1993-05-31 | 1998-11-11 | 花王株式会社 | Detergent composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3170915A (en) * | 1960-04-11 | 1965-02-23 | Monsanto Co | Sucrose ethers |
| US3219656A (en) * | 1963-08-12 | 1965-11-23 | Rohm & Haas | Alkylpolyalkoxyalkyl glucosides and process of preparation therefor |
-
1982
- 1982-07-13 JP JP12197782A patent/JPS58187500A/en active Granted
- 1982-07-13 CA CA000407166A patent/CA1190450A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPH037719B2 (en) | 1991-02-04 |
| JPS58187500A (en) | 1983-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1180973A (en) | Foaming surfactant compositions | |
| US4536318A (en) | Foaming surfactant compositions | |
| US4663069A (en) | Light-duty liquid detergent and shampoo compositions | |
| US4565647A (en) | Foaming surfactant compositions | |
| US4599188A (en) | Foaming surfactant compositions | |
| US4536317A (en) | Foaming surfactant compositions | |
| EP0070077B1 (en) | Light-duty detergent granule composition | |
| EP0070076B1 (en) | Foaming dishwashing liquid compositions | |
| EP0070075B1 (en) | Foaming dishwashing liquid compositions | |
| US4839098A (en) | Liquid detergent | |
| EP0341071B2 (en) | Detergent compositions | |
| CA1238545A (en) | Mild detergent compositions | |
| US5503779A (en) | High foaming light duty liquid detergent | |
| US5780417A (en) | Light duty liquid cleaning compositions | |
| US5972867A (en) | High foaming, grease cutting light duty liquid detergent | |
| CA1180974A (en) | Foaming surfactant compositions | |
| CA1209010A (en) | Foaming surfactant compositions | |
| JPH037718B2 (en) | ||
| CA1190450A (en) | Foaming surfactant compositions | |
| US6107263A (en) | High foaming, grease cutting light duty composition containing a C12 alkyl amido propyl dimethyl amine oxide | |
| CA2127656A1 (en) | High foaming nonionic surfactant based liquid detergent | |
| US6010992A (en) | Liquid detergent composition containing amine oxide and citric acid | |
| WO1997004057A1 (en) | Foaming composition | |
| US6127328A (en) | High foaming, grease cutting light duty composition containing a C12 alkyl amido propyl dimethyl amine oxide | |
| EA199901105A1 (en) | WASHING MEANS BASED ON PHOSPHATES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |